Initial stability loss of insecticide solution mixed with fungicides and adjuvants

Initial stability loss of insecticide solution mixed with fungicides and adjuvants | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Initial stability loss of insecticide solution mixed with fungicides and adjuvants Ana Beatriz Dilena Spadoni, Marcelo C Ferreira This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1782058/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The practice of mixing different classes of crop protection products in tank is common for farmers, with efficience losses by compatibility problems, but a lack of research to better understand them. The aim of this study was to evaluate the initial stability loss of spray liquid mixtures obtained by association of fungicides and adjuvants with insecticides. Laboratory experiments were carried with nine treatments composed of the insecticide thiamethoxam + lambda-cyhalothrin (TL) mixed with the fungicides fluxapyroxad + pyraclostrobin (FP) and chlorothalonil (CL) and the adjuvants lecithin, propionic acid (LA), and mineral oil (MO). Assessment of initial loss solution stability was performed to verify when the product mixture in the sprayer tank starts. For this purpose, were carried rheological behavior and zeta potential analyses, and the determination of viscosity. The treatments containing insecticide TL with adjuvants LA and MO and the fungicide FP have shown the loss of physical-chemical stability, possibly due to changes in the layers around the particles of the components of the ingredients contained in the various combined solution formulations. dispersants solution instability tank mixture Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction The high demand for crop protection products and the farmers’ need to optimize financial and operational resources in the field makes the use of tank mixtures with different classes of products a commonly used technique 1 , 2 . This technique entails the use of more than one product formulation in a spray mixture for the simultaneous control of several pests and diseases, with a wider spectrum of action, lower level of spraying in an area, less soil compaction, greater work efficiency, decreased exposure time of workers to phytosanitary products, decreased number of machines to perform the same work, water-saving, phytosanitary control in less time, and decreased use of fuel 3 . There are, however, a few problems associated with the use of this technique and knowledge on tank mixtures with products of different classes and formulations is necessary to avoid possible crop damage, physical-chemical stability interference, and decreased efficiency of the plant protection products used 4 , 3 . In conventional laboratory tests, with standardized procedures, generally no incompatibilities between mixtures are observed, suggesting that the problem may result from the way of the preparation of the spray liquid. Using these mixtures can have advantages compared to the use of a single compound due to increased efficacy against target organisms and optimized use of the product and financial resources. The inordinate diversity of spraying-mixture preparation procedures leads some of them to present stability problems in the tank, which result in phase separation, precipitate formation, flakes, and incrustations in the tank, tubes, bars, filters, and sprayer tips, hindering equipment cleaning and operation, and interfering with the efficacy of the treatments. Physical interactions, in general, are associated with the inert ingredients contained in the pesticides (formulations, solvents), while chemical interactions are associated with the pesticide molecules. Even so, it should be noted that the interaction between pesticides is physical and is mostly controlled by the physical-chemical characteristics of the pesticides, leading to chemical interactions 4 . A mixture of phytosanitary products can change the chemical characteristics of the solution and affect its stability at different levels of compatibility influencing the efficacy of phytosanitary treatments and causing additive, antagonistic, or synergistic interactions that can interfere in target pest control and cause unknown toxic effects 4 . Given the above, more studies are necessary to understand the compatibility and physical-chemical properties of mixing different products in a phytosanitary solution. The objective of this study was to evaluate the initial stability loss of spray liquid mixtures obtained by mixing fungicides and adjuvants associated with an insecticide. Results Rheological determination. The rheological pattern of the solutions showed shear stress values as a function of the deformation rate. The samples were initially classified as Newtonian fluids, with the pattern of ideal liquids. Viscosity analyses were performed with linear adjustment of the data, with the curve generated from the origin showing Newtonian fluid characteristics, that the direct analysis shows a flow similar to water (Fig. 1 ). The R² values (Table 1 ) obtained by the linear adjustment starting at the origin show that the fluids exhibited Newtonian pattern due to the high coefficient of variation in all solutions, which was the ideal linear adjustment. The highest R² values (close to 1) were observed for TL; TL + FP, TL + CL; and TL + LA. Table 1 Angular coefficient and linear adjustment determination starting at the origin for Newtonian fluids. Treatments Linear equation R² TL 6 − 06 *-0,001 0,9863 TL + FP 6 − 06 *-0,001 0,9808 TL + CL 6 − 06 *-0,001 0,9802 TL + LA 6 − 06 *-0,001 0,9798 TL + MO 5 − 06 *-0,001 0,8894 TL + FP + LA 5 − 06 *-0,001 0,8817 TL + FP + MO 5 − 06 *-0,0011 0,9047 TL + CL + LA 5 − 06 *-0,0011 0,9047 TL + CL + MO 4 − 06 *-0,0011 0,9238 Viscosity determination. Complementary to the rheological behavior, the viscosity of the solutions was assessed, as it interferes with mixture balance and drop formation 5 . Compared with the other treatments, viscosity was higher in TL, TL + CL, TL + CL + LA, and TL + CL + MO (Fig. 2 ). Lower viscosity was observed in TL + FP, TL + LA, TL + MO, and TL + FP + MO. Viscosity was both lower and similar among treatments containing FP, LA, and MO (Fig. 2 ). Zeta potential. The zeta potential can be used as a solution stability indicator. High zeta potential indicates stable dispersion. In this method, the analyses should be performed in the shortest time possible and at standardized intervals for all treatments, since longer evaluation times may result in increased particle aggregation in the analyzed solutions. The mean zeta potentials of the analyzed solutions are presented in Fig. 3 . In general, all treatments had high zeta potentials, except for TL + MO, TL + CL + LA, and TL + CL + MO, being, in module, which had zeta potentials significantly lower than the other treatments (p > 0.05). The TL, TL + FP, TL + CL, and TL + FP + MO treatments were similar, but the solution containing LA had the highest zeta potential. The results indicated that the most stable treatments were TL, TL + CL, and TL + LA, with zeta potentials from 38.3 to 40.33 mV, followed by TL + FP, TL + FP + LA, and TL + FP + MO, suggesting that adjuvant addition to the treatment containing FP did not significantly change solution stability. Adjuvant addition to the treatment containing CL decreased the zeta potential, giving a less stable solution that changed from 39.2 to 25.77 and then 26.87 mV, respectively. Discussion In Newtonian behavior, constant viscosity occurs due to macroscopic displacements, which is slow for low cutoff rates, with the possibility of microscopic rearrangements that establish new balance conditions in the solution and consequently, fluid stability 6 . These rearrangements provide a more stable solution after the combination of phytosanitary products, possibly resulting in greater preservation of the solution and the active ingredients; this may lead to the maintenance of efficacy of individual components in the solution to effectively control target organisms. Although the viscosity of the samples increased with an increase in the deformation rate (a characteristic of non-Newtonian fluids), in the analyzed mixtures, regardless of the products used, the solvents persisted with a rheological behavior consistent with that of water i.e. Newtonian behavior. The expectation is that these solutions will be more stable than others, with R 2 values closer to 0.9. Fluid behavior can also be characterized by the dependence of viscosity on time, and this effect is related to the various transformations present in the structure of the materials and their kinetics in the process of restoring this structure 7 . These solution-viscosity-related groupings are due to the composition and formulation of products that interact in the solution, which may affect physical-chemical characteristics and properties 8 . The mode of action of some chemicals in the interaction of more than one product and different concentrations is still unknown. It is understood that viscosity is directly related to stability and that the higher the viscosity, the lower the sedimentation caused by the interaction between the products used 9 . The chemical, physical, and biological interactions between products can modify their characteristics, making them different from expected. Therefore, the efficacy in controlling organisms in the field may be reduced 3 . Moreover, there may be agglomeration with the formation of particles and precipitates that will decrease solution flow in pipes, filters, and spray tips. This can result in difficulties in cleaning tanks and pipes, clogging filters and spray tips, reducing operational efficiency due to breaks taken to clean the equipment, in addition to changing the concentration of the products in the solution with consequent dosage errors. These changes in solution uniformity are expected to decrease target organism control. The higher absolute zeta potential for suspended particles indicates greater particle stability due to a greater tendency of charged particles to repel one another which helps overcome the natural tendency toward aggregation and flocculation. The threshold between stable and unstable suspensions is ± 30 mV, and suspensions are normally considered stable when they have an absolute value > 30 mV 10 . The adjuvants LA and MO possibly broke the dispersants present in the CL formulation, decanting these dispersants and consequently reducing their zeta potentials. The dispersants may be steric and/or electrostatic. Steric dispersants have a large molecular weight which stabilizes the system using molecule-liquid and molecule-particle affinities, in which the molecules bind to the particles through regions that highly resemble the surface, and the unbound regions of the molecules protect the solution, remaining totally dissolved in the liquid and imparting stability 11 . In electrostatic dispersants, the molecules adhere to the particles, increasing the electrical potential of the surface and its diffuse layer. As the attraction force is low, the diffusion force is greater, and the diffuse layer moves further away from the surface. The larger the layer, the greater the interaction resulting in greater repulsion 11 . The zeta potential is as dependent on the composition of the dispersed phase of the solutions as on the nature of the particle surface 12 . The mixtures assessed in the current study consisted of complex liquids, mostly with a water solvent and a mixture of different chemical substances, largely composed of inert ingredients. These compositions may result in precipitate formation during measurement, depending on the time interval of the analysis. The solutions with the highest zeta potential i.e., the most stable (TL, TL + CL, and TL + LA), have formulations chiefly comprising aggregates that do not interact with other system components. However, the solutions with less stability (TL + CL + LA and TL + CL + MO), undergo reactions between the products that are unknown, which may change surface loads modifying the diffuse layer and therefore its agglomeration. The existing surface state of the particles needs to be preserved during the dilution process to keep them scattered, which results in greater solution stability. The solutions in which there was an association of FP, LA, and MO showed an opposite phenomenon, with the stable, steric, or electrostatic system profile being maintained or increased. The aggregates of these products interact less with the medium, becoming more stable even in a mixture. There is little information available in the literature on zeta potential and its trends in phytosanitary solutions. A study on the development of poly-caprolactone nanocapsules containing the herbicide atrazine showed that the zeta potential of these nanocapsules depended mainly on the chemical nature of the polymer and stabilizer 13 . However, with complex liquid solutions, the reaction dynamism can change the nature of the particles, with an initial effect on solution stability and possible compositional changes in the ingredients. Thus, the evaluation of the variables that make it possible to assess either the molecular state of the solutions or their physical, chemical, and biological aspects will make it possible to infer treatment results in the field. Conclusion The combination of the insecticide thiamethoxam + lambda-cyhalothrin (TL) with the adjuvants lecithin, propionic acid (LA) and mineral oil (MO) and the fungicide fluxapyroxad + pyraclostrobin (FP) resulted in loss of physicochemical stability during spraying, possibly due to changes in the layers around the particles resulting from the interaction between the ingredients contained in the various combined solution formulations. The other treatments showed less interaction between the formulation components and therefore less loss of stability. Methods The initial solution instability was assessed to verify when solution instability due to mixing products in the sprayer tank starts. For this purpose, rheological behavior and zeta potential analyses were performed in the Malvern Panalytical Scientific Instrumentation laboratory, and viscosity was determined in the ecotoxicology laboratory of the FCAV/UNESP department of plant health. Treatments. The treatments included products based on actual tank mixes commonly used by farmers in peanut crop management, a widely cultivated crop in several countries 14 . In peanut cultivation, phytosanitary products are used at different stages of the production cycle, with it being a common practice to mix products in the sprayer to target several pests and diseases simultaneously and rationalize equipment use. The study analyzed fungicides and adjuvants associated with an insecticide normally used for the peanut crop [insecticide: thiamethoxam + lambda-cyhalothrin (TL); fungicides: fluxapyroxad + pyraclostrobin (FP) and chlorothalonil (CL); adjuvants: lecithin and propionic acid (LA) and mineral oil (MO)] 15 . The solutions were prepared at a volume of 150 L ha − 1 . The experiments were conducted using nine treatment mixtures (Table 2 ). Table 2 Treatments, phytosanitary product mixtures, and doses used. Treatments Mixtures Dose (mL/ha or mL/100 L) 1 TL 1 150 2 TL + FP 2 150 + 250 3 TL + CL 3 150 + 2500 4 TL + LA 4 150 + 500 5 TL + MO 5 150 + 500 6 TL + FP + LA 150 + 250 + 500 7 TL + FP + MO 150 + 250 + 500 8 TL + CL + LA 150 + 2500 + 500 9 TL + CL + MO 150 + 2500 + 500 1 Engeo Pleno (Syngenta Proteção de Cultivos Ltda.) - insecticide of the neonicotinoid and pyrethroid groups; 2 Orkestra® SC (Basf SA) - fungicide of the strobilurin and carboxamide chemical groups; 3 Bravonil® 500 (Syngenta Proteção de Cultivos Ltda.) - fungicide of the isophthalonitrile chemical group; 4 Li 700 (De Sangosse Agroquímica Ltda.) - agricultural adjuvant; and 5 NIMBUS (Syngenta Proteção de Cultivos Ltda.) - adjuvant of the aliphatic hydrocarbon chemical group. Rheological determination. A Malvern Kinexus lab + concentric cylinder rheometer (Malvern Panalytical, Malvern, United Kingdom) was used to determine the rheological behavior of the solutions. The rheometer was programmed to apply continuous shear stress of 0.01 to 1000 Pa on the solutions at a temperature of 25°C. The system balance time was five minutes before the tests started. Measurements were conducted immediately after solution preparation. After obtaining the viscosity data as a function of the shear rate, Newton’s law of viscosity was used to evaluate the very low shear rate interval according to 8 . Newton’s law of viscosity can be described using the following equation: \(\sigma =\eta .\gamma\) , where σ is the shear stress required to produce the movement, γ is the shear rate (or speed gradient) and η is the proportionality constant between the stress and the strain rate, which is called the coefficient of viscosity 8 .Rheology is the study of the deformation, flow, or flow behavior of a material subjected to stress under certain thermodynamic conditions over a period. This stress can be presented in several ways, one of which is shear 16 . As for emulsions, rheology provides information on physical stability 17 . Fluids are usually classified by the shear stress curve profile by the rate of deformation (flow curves). These profiles are divided into two groups: Newtonian and non-Newtonian fluids (Fig. 4 ). There is a correlation between the stress and the rate at which the shear of the sample occurs, this relationship defines the flow behavior according to the flow curves 16 . Newtonian fluids exhibit proportionality between shear stress and shear rate, while non-Newtonian fluids have a nonlinear relationship with the same 18 . Viscosity determination. A Brookfield DV-I Prime viscometer (Brookfield Engineering, Middleboro, MA, USA) was used to determine the viscosity [in millipascal seconds (mPa s)] of the solutions at a temperature of 25°C and agitation speed of 100 rpm. The readings were taken immediately after solution preparation. The procedure was replicated four times for each solution. Zeta potential. A Zetasizer NANO ZS90 analyzer (Malvern Panalytical) was used to determine the zeta potential of the mixtures using the laser Doppler microelectrophoresis technique with three replications per solution. The zeta potential was determined from the evaluation during a 3-min distribution curve assessment of each solution. The data were analyzed using Zetasizer software. Data analysis. The data obtained for viscosity and zeta potential were subjected to one-way ANOVA and the treatment means were compared using Tukey’s test (α = 0.05). Linear regression was used to assess rheological behavior and physical stability data with a trend line for data adjustment. Declarations Data availability. The datasets generated and/or analyzed during the current study are available in the files listed in the paper submission, available by the corresponding author upon request. Acknowledgements To the laboratory Malvern Panalytical Scientific Instrumentation for making available the Malvern Kinexus lab+ concentric cylinder rheometer. Author contributions A.B.D.S. participated in the data collection, tabulation, and formatting of the final manuscript. A.B.D.S., and M.C.F. participated in the writing and revision of the manuscript. Funding Tis study was fnanced in part by the Conselho Nacional de Desenvolvimento Científico e Tecnológico—Brasil (CNPq)—Finance Code 001 Competing interests Te authors declare no competing interests. Additional information Correspondence and requests for materials should be addressed to A.B.D.S. or M.F.C. References Gazziero, D.L.P. Misturas de agrotóxicos em tanque nas propriedades agrícolas do Brasil. Planta Daninha.v. 33, n. 1, p. 83–92. https://doi.org/10.1590/S0100-83582015000100010 . (2015) Regupathy A, Ramasubramanian T, Ayyasamy R. Rationale behind the use of insecticide mixtures for the management of insecticide resistance in India. Food Agric Environ.v.2:278–284. (2004) Della Vechia, J.F.; Ferreira, M.C.; Andrade, D.J. (2018). Interaction of spirodiclofen with insecticides for the control of in citrus. PEST MANAGEMENT SCIENCE. v. 74, p. 1–6. https://doi.org/10.1002/ps.4918 . (2018) Petter, F. A.; Segate, D.; Almeida, F. A.; Alcântara Neto, F.; Pacheco, L. P. 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Caracterização e estabilidade físico-química de sistemas poliméricos nanoparticulados para administração de fármacos. Quím. Nova . v.269, n.5, pp.726–737. ISSN 1678–7064. https://doi.org/10.1590/S0100-40422003000500017 . (2003) Souza, P.M.S.; Lobo F.A.; Rosa A.H.R.; Fraceto, L.F. Desenvolvimento de Nanocápsulas de Poli-ε-Caprolactona Contendo o Herbicida Atrazina. Quimica Nova. v . 35 (1): 132–37. https://doi.org/10.1590/ S0100-40422012000100024. ( 2012 ) Castro RHR, Gouvêa D. Estudo da estabilidade de dispersões de SnO2 utilizando L-Arginina ou quitosana como dispersantes. Cerâmica. 46 214–219. https://doi.org/10.1590/S0366-69132000000400008 . (2000) Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-1782058","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":120756396,"identity":"e8d627ad-c9f3-40aa-a548-101807fefc02","order_by":0,"name":"Ana Beatriz Dilena Spadoni","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA70lEQVRIie2QsQrCMBCGEw7aJers5CtEHKSg+CqKq4KPUCjUpTrbQXwFXTo3ZOhSnIU4ODk5xE2kg2kGcTHVTTAfx+WG++D+IGSx/CAUVCPllKqS6nXcbxS2KhWoUtCLAnqoUrounNClOLbq2YLx3j1p1QFheZ28V7zAoXgdnttxvh/y6VK0Q0DQjBPDYVzFqfkcbw8TyqeRwEpxoGZUXAmk4AOteJEYfKAQCsThI62gmxhVKl5AZkxlGcd5TtnCF+MQcGDM0m1ku5P6sf4yizryVoj+Zh4weTUoJamuEhzq7pv3n5am+GTZYrFY/o0HubFYq7s2pJEAAAAASUVORK5CYII=","orcid":"","institution":"São Paulo State University (UNESP)","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Ana","middleName":"Beatriz Dilena","lastName":"Spadoni","suffix":""},{"id":120756398,"identity":"6ce022cf-8b36-4443-9aad-aec2c0012ee1","order_by":1,"name":"Marcelo C Ferreira","email":"","orcid":"","institution":"São Paulo State University (UNESP)","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Marcelo","middleName":"C","lastName":"Ferreira","suffix":""}],"badges":[],"createdAt":"2022-06-21 20:29:08","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1782058/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1782058/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":24151032,"identity":"50deda39-da0e-4583-85c3-662538eaf241","added_by":"auto","created_at":"2022-07-21 16:31:45","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":86677,"visible":true,"origin":"","legend":"\u003cp\u003e(2A) Rheological behavior of the analyzed solutions with continuous shear stress and (2B) adjustment for linear behavior.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Fig1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-1782058/v1/858f1c6ab425e71c6b4ea344.jpg"},{"id":24151436,"identity":"844dac45-b638-4355-825c-5487bb616aaa","added_by":"auto","created_at":"2022-07-21 16:36:45","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":66978,"visible":true,"origin":"","legend":"\u003cp\u003eMean viscosity of the solutions in tank mixtures.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Fig2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-1782058/v1/60214ef6150fdf78b4bfd05c.jpg"},{"id":24151031,"identity":"8a2ac353-0d7e-4a98-979f-235500a4cd71","added_by":"auto","created_at":"2022-07-21 16:31:45","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":49493,"visible":true,"origin":"","legend":"\u003cp\u003eZeta potential of the analyzed solutions measured in mV.\u003c/p\u003e","description":"","filename":"Fig3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-1782058/v1/7fd107f4901f0adfd1737ddf.jpg"},{"id":24151034,"identity":"cb1fa8c4-1a01-4e50-907a-718bc468a70e","added_by":"auto","created_at":"2022-07-21 16:31:46","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":49305,"visible":true,"origin":"","legend":"\u003cp\u003eFlow curve representation for rheological behavior.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Fig4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-1782058/v1/2a8d68d1f48b70d715dbfce6.jpg"},{"id":44172527,"identity":"5bf245a4-45b3-45d8-b461-8dc48ebc5f1b","added_by":"auto","created_at":"2023-10-06 05:52:31","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":471574,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1782058/v1/775513c1-2258-4d7c-8c4f-90dc398da1cb.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Initial stability loss of insecticide solution mixed with fungicides and adjuvants","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe high demand for crop protection products and the farmers\u0026rsquo; need to optimize financial and operational resources in the field makes the use of tank mixtures with different classes of products a commonly used technique\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. This technique entails the use of more than one product formulation in a spray mixture for the simultaneous control of several pests and diseases, with a wider spectrum of action, lower level of spraying in an area, less soil compaction, greater work efficiency, decreased exposure time of workers to phytosanitary products, decreased number of machines to perform the same work, water-saving, phytosanitary control in less time, and decreased use of fuel\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThere are, however, a few problems associated with the use of this technique and knowledge on tank mixtures with products of different classes and formulations is necessary to avoid possible crop damage, physical-chemical stability interference, and decreased efficiency of the plant protection products used\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e,\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. In conventional laboratory tests, with standardized procedures, generally no incompatibilities between mixtures are observed, suggesting that the problem may result from the way of the preparation of the spray liquid.\u003c/p\u003e \u003cp\u003eUsing these mixtures can have advantages compared to the use of a single compound due to increased efficacy against target organisms and optimized use of the product and financial resources. The inordinate diversity of spraying-mixture preparation procedures leads some of them to present stability problems in the tank, which result in phase separation, precipitate formation, flakes, and incrustations in the tank, tubes, bars, filters, and sprayer tips, hindering equipment cleaning and operation, and interfering with the efficacy of the treatments.\u003c/p\u003e \u003cp\u003ePhysical interactions, in general, are associated with the inert ingredients contained in the pesticides (formulations, solvents), while chemical interactions are associated with the pesticide molecules. Even so, it should be noted that the interaction between pesticides is physical and is mostly controlled by the physical-chemical characteristics of the pesticides, leading to chemical interactions\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eA mixture of phytosanitary products can change the chemical characteristics of the solution and affect its stability at different levels of compatibility influencing the efficacy of phytosanitary treatments and causing additive, antagonistic, or synergistic interactions that can interfere in target pest control and cause unknown toxic effects\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e. Given the above, more studies are necessary to understand the compatibility and physical-chemical properties of mixing different products in a phytosanitary solution. The objective of this study was to evaluate the initial stability loss of spray liquid mixtures obtained by mixing fungicides and adjuvants associated with an insecticide.\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e \u003cb\u003eRheological determination.\u003c/b\u003e The rheological pattern of the solutions showed shear stress values as a function of the deformation rate. The samples were initially classified as Newtonian fluids, with the pattern of ideal liquids. Viscosity analyses were performed with linear adjustment of the data, with the curve generated from the origin showing Newtonian fluid characteristics, that the direct analysis shows a flow similar to water (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The R\u0026sup2; values (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) obtained by the linear adjustment starting at the origin show that the fluids exhibited Newtonian pattern due to the high coefficient of variation in all solutions, which was the ideal linear adjustment. The highest R\u0026sup2; values (close to 1) were observed for TL; TL\u0026thinsp;+\u0026thinsp;FP, TL\u0026thinsp;+\u0026thinsp;CL; and TL\u0026thinsp;+\u0026thinsp;LA.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eAngular coefficient and linear adjustment determination starting at the origin for Newtonian fluids.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026minus;\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTreatments\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLinear equation\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eR\u0026sup2;\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e6\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9863\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;FP\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e6\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9808\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;CL\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e6\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9802\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;LA\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e6\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9798\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;MO\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e5\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,8894\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;LA\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e5\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,8817\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;MO\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e5\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,0011\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9047\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;LA\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e5\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,0011\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9047\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;MO\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e \u003cp\u003e4\u003csup\u003e\u0026minus;\u0026thinsp;06\u003c/sup\u003e*-0,0011\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0,9238\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eViscosity determination.\u003c/b\u003e Complementary to the rheological behavior, the viscosity of the solutions was assessed, as it interferes with mixture balance and drop formation\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. Compared with the other treatments, viscosity was higher in TL, TL\u0026thinsp;+\u0026thinsp;CL, TL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;LA, and TL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;MO (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). Lower viscosity was observed in TL\u0026thinsp;+\u0026thinsp;FP, TL\u0026thinsp;+\u0026thinsp;LA, TL\u0026thinsp;+\u0026thinsp;MO, and TL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;MO. Viscosity was both lower and similar among treatments containing FP, LA, and MO (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e\u003cp\u003e \u003cb\u003eZeta potential.\u003c/b\u003e The zeta potential can be used as a solution stability indicator. High zeta potential indicates stable dispersion. In this method, the analyses should be performed in the shortest time possible and at standardized intervals for all treatments, since longer evaluation times may result in increased particle aggregation in the analyzed solutions. The mean zeta potentials of the analyzed solutions are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. In general, all treatments had high zeta potentials, except for TL\u0026thinsp;+\u0026thinsp;MO, TL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;LA, and TL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;MO, being, in module, which had zeta potentials significantly lower than the other treatments (p\u0026thinsp;\u0026gt;\u0026thinsp;0.05). The TL, TL\u0026thinsp;+\u0026thinsp;FP, TL\u0026thinsp;+\u0026thinsp;CL, and TL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;MO treatments were similar, but the solution containing LA had the highest zeta potential. The results indicated that the most stable treatments were TL, TL\u0026thinsp;+\u0026thinsp;CL, and TL\u0026thinsp;+\u0026thinsp;LA, with zeta potentials from 38.3 to 40.33 mV, followed by TL\u0026thinsp;+\u0026thinsp;FP, TL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;LA, and TL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;MO, suggesting that adjuvant addition to the treatment containing FP did not significantly change solution stability. Adjuvant addition to the treatment containing CL decreased the zeta potential, giving a less stable solution that changed from 39.2 to 25.77 and then 26.87 mV, respectively.\u003c/p\u003e "},{"header":"Discussion","content":"\u003cp\u003eIn Newtonian behavior, constant viscosity occurs due to macroscopic displacements, which is slow for low cutoff rates, with the possibility of microscopic rearrangements that establish new balance conditions in the solution and consequently, fluid stability\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. These rearrangements provide a more stable solution after the combination of phytosanitary products, possibly resulting in greater preservation of the solution and the active ingredients; this may lead to the maintenance of efficacy of individual components in the solution to effectively control target organisms.\u003c/p\u003e \u003cp\u003eAlthough the viscosity of the samples increased with an increase in the deformation rate (a characteristic of non-Newtonian fluids), in the analyzed mixtures, regardless of the products used, the solvents persisted with a rheological behavior consistent with that of water i.e. Newtonian behavior. The expectation is that these solutions will be more stable than others, with R\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e values closer to 0.9. Fluid behavior can also be characterized by the dependence of viscosity on time, and this effect is related to the various transformations present in the structure of the materials and their kinetics in the process of restoring this structure\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThese solution-viscosity-related groupings are due to the composition and formulation of products that interact in the solution, which may affect physical-chemical characteristics and properties\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe mode of action of some chemicals in the interaction of more than one product and different concentrations is still unknown.\u003c/p\u003e \u003cp\u003eIt is understood that viscosity is directly related to stability and that the higher the viscosity, the lower the sedimentation caused by the interaction between the products used\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e. The chemical, physical, and biological interactions between products can modify their characteristics, making them different from expected. Therefore, the efficacy in controlling organisms in the field may be reduced\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. Moreover, there may be agglomeration with the formation of particles and precipitates that will decrease solution flow in pipes, filters, and spray tips. This can result in difficulties in cleaning tanks and pipes, clogging filters and spray tips, reducing operational efficiency due to breaks taken to clean the equipment, in addition to changing the concentration of the products in the solution with consequent dosage errors. These changes in solution uniformity are expected to decrease target organism control.\u003c/p\u003e \u003cp\u003eThe higher absolute zeta potential for suspended particles indicates greater particle stability due to a greater tendency of charged particles to repel one another which helps overcome the natural tendency toward aggregation and flocculation. The threshold between stable and unstable suspensions is \u0026plusmn;\u0026thinsp;30 mV, and suspensions are normally considered stable when they have an absolute value\u0026thinsp;\u0026gt;\u0026thinsp;30 mV\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe adjuvants LA and MO possibly broke the dispersants present in the CL formulation, decanting these dispersants and consequently reducing their zeta potentials. The dispersants may be steric and/or electrostatic. Steric dispersants have a large molecular weight which stabilizes the system using molecule-liquid and molecule-particle affinities, in which the molecules bind to the particles through regions that highly resemble the surface, and the unbound regions of the molecules protect the solution, remaining totally dissolved in the liquid and imparting stability\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e. In electrostatic dispersants, the molecules adhere to the particles, increasing the electrical potential of the surface and its diffuse layer. As the attraction force is low, the diffusion force is greater, and the diffuse layer moves further away from the surface. The larger the layer, the greater the interaction resulting in greater repulsion\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe zeta potential is as dependent on the composition of the dispersed phase of the solutions as on the nature of the particle surface\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. The mixtures assessed in the current study consisted of complex liquids, mostly with a water solvent and a mixture of different chemical substances, largely composed of inert ingredients. These compositions may result in precipitate formation during measurement, depending on the time interval of the analysis.\u003c/p\u003e \u003cp\u003eThe solutions with the highest zeta potential i.e., the most stable (TL, TL\u0026thinsp;+\u0026thinsp;CL, and TL\u0026thinsp;+\u0026thinsp;LA), have formulations chiefly comprising aggregates that do not interact with other system components. However, the solutions with less stability (TL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;LA and TL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;MO), undergo reactions between the products that are unknown, which may change surface loads modifying the diffuse layer and therefore its agglomeration. The existing surface state of the particles needs to be preserved during the dilution process to keep them scattered, which results in greater solution stability. The solutions in which there was an association of FP, LA, and MO showed an opposite phenomenon, with the stable, steric, or electrostatic system profile being maintained or increased. The aggregates of these products interact less with the medium, becoming more stable even in a mixture.\u003c/p\u003e \u003cp\u003eThere is little information available in the literature on zeta potential and its trends in phytosanitary solutions. A study on the development of poly-caprolactone nanocapsules containing the herbicide atrazine showed that the zeta potential of these nanocapsules depended mainly on the chemical nature of the polymer and stabilizer\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. However, with complex liquid solutions, the reaction dynamism can change the nature of the particles, with an initial effect on solution stability and possible compositional changes in the ingredients.\u003c/p\u003e \u003cp\u003eThus, the evaluation of the variables that make it possible to assess either the molecular state of the solutions or their physical, chemical, and biological aspects will make it possible to infer treatment results in the field.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe combination of the insecticide thiamethoxam\u0026thinsp;+\u0026thinsp;lambda-cyhalothrin (TL) with the adjuvants lecithin, propionic acid (LA) and mineral oil (MO) and the fungicide fluxapyroxad\u0026thinsp;+\u0026thinsp;pyraclostrobin (FP) resulted in loss of physicochemical stability during spraying, possibly due to changes in the layers around the particles resulting from the interaction between the ingredients contained in the various combined solution formulations. The other treatments showed less interaction between the formulation components and therefore less loss of stability.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003eThe initial solution instability was assessed to verify when solution instability due to mixing products in the sprayer tank starts. For this purpose, rheological behavior and zeta potential analyses were performed in the Malvern Panalytical Scientific Instrumentation laboratory, and viscosity was determined in the ecotoxicology laboratory of the FCAV/UNESP department of plant health.\u003c/p\u003e \u003cp\u003e \u003cb\u003eTreatments.\u003c/b\u003e The treatments included products based on actual tank mixes commonly used by farmers in peanut crop management, a widely cultivated crop in several countries\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. In peanut cultivation, phytosanitary products are used at different stages of the production cycle, with it being a common practice to mix products in the sprayer to target several pests and diseases simultaneously and rationalize equipment use. The study analyzed fungicides and adjuvants associated with an insecticide normally used for the peanut crop [insecticide: thiamethoxam\u0026thinsp;+\u0026thinsp;lambda-cyhalothrin (TL); fungicides: fluxapyroxad\u0026thinsp;+\u0026thinsp;pyraclostrobin (FP) and chlorothalonil (CL); adjuvants: lecithin and propionic acid (LA) and mineral oil (MO)]\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e. The solutions were prepared at a volume of 150 L ha\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The experiments were conducted using nine treatment mixtures (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTreatments, phytosanitary product mixtures, and doses used.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTreatments\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMixtures\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDose (mL/ha or mL/100 L)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e1\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;FP\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;250\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;CL\u003csup\u003e3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;2500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;LA\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;MO\u003csup\u003e5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e6\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;LA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;250\u0026thinsp;+\u0026thinsp;500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e7\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;FP\u0026thinsp;+\u0026thinsp;MO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;250\u0026thinsp;+\u0026thinsp;500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e8\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;LA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;2500\u0026thinsp;+\u0026thinsp;500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e9\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTL\u0026thinsp;+\u0026thinsp;CL\u0026thinsp;+\u0026thinsp;MO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e150\u0026thinsp;+\u0026thinsp;2500\u0026thinsp;+\u0026thinsp;500\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003ctfoot\u003e \u003ctr\u003e\u003ctd colspan=\"3\"\u003e\u003csup\u003e1\u003c/sup\u003eEngeo Pleno (Syngenta Prote\u0026ccedil;\u0026atilde;o de Cultivos Ltda.) - insecticide of the neonicotinoid and pyrethroid groups; \u003csup\u003e2\u003c/sup\u003eOrkestra\u0026reg; SC (Basf SA) - fungicide of the strobilurin and carboxamide chemical groups; \u003csup\u003e3\u003c/sup\u003eBravonil\u0026reg; 500 (Syngenta Prote\u0026ccedil;\u0026atilde;o de Cultivos Ltda.) - fungicide of the isophthalonitrile chemical group; \u003csup\u003e4\u003c/sup\u003eLi 700 (De Sangosse Agroqu\u0026iacute;mica Ltda.) - agricultural adjuvant; and \u003csup\u003e5\u003c/sup\u003eNIMBUS (Syngenta Prote\u0026ccedil;\u0026atilde;o de Cultivos Ltda.) - adjuvant of the aliphatic hydrocarbon chemical group.\u003c/td\u003e\u003c/tr\u003e \u003c/tfoot\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eRheological determination.\u003c/b\u003e A Malvern Kinexus lab\u0026thinsp;+\u0026thinsp;concentric cylinder rheometer (Malvern Panalytical, Malvern, United Kingdom) was used to determine the rheological behavior of the solutions. The rheometer was programmed to apply continuous shear stress of 0.01 to 1000 Pa on the solutions at a temperature of 25\u0026deg;C. The system balance time was five minutes before the tests started. Measurements were conducted immediately after solution preparation. After obtaining the viscosity data as a function of the shear rate, Newton\u0026rsquo;s law of viscosity was used to evaluate the very low shear rate interval according to\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. Newton\u0026rsquo;s law of viscosity can be described using the following equation: \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\sigma =\\eta .\\gamma\\)\u003c/span\u003e\u003c/span\u003e, where \u003cem\u003eσ\u003c/em\u003e is the shear stress required to produce the movement, \u003cem\u003eγ\u003c/em\u003e is the shear rate (or speed gradient) and \u003cem\u003eη\u003c/em\u003e is the proportionality constant between the stress and the strain rate, which is called the coefficient of viscosity \u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e.Rheology is the study of the deformation, flow, or flow behavior of a material subjected to stress under certain thermodynamic conditions over a period. This stress can be presented in several ways, one of which is shear\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. As for emulsions, rheology provides information on physical stability\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. Fluids are usually classified by the shear stress curve profile by the rate of deformation (flow curves). These profiles are divided into two groups: Newtonian and non-Newtonian fluids (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). There is a correlation between the stress and the rate at which the shear of the sample occurs, this relationship defines the flow behavior according to the flow curves\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. Newtonian fluids exhibit proportionality between shear stress and shear rate, while non-Newtonian fluids have a nonlinear relationship with the same\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003e \u003cb\u003eViscosity determination.\u003c/b\u003e A Brookfield DV-I Prime viscometer (Brookfield Engineering, Middleboro, MA, USA) was used to determine the viscosity [in millipascal seconds (mPa s)] of the solutions at a temperature of 25\u0026deg;C and agitation speed of 100 rpm. The readings were taken immediately after solution preparation. The procedure was replicated four times for each solution.\u003c/p\u003e \u003cp\u003e \u003cb\u003eZeta potential.\u003c/b\u003e A Zetasizer NANO ZS90 analyzer (Malvern Panalytical) was used to determine the zeta potential of the mixtures using the laser Doppler microelectrophoresis technique with three replications per solution. The zeta potential was determined from the evaluation during a 3-min distribution curve assessment of each solution. The data were analyzed using Zetasizer software.\u003c/p\u003e \u003cp\u003e \u003cb\u003eData analysis.\u003c/b\u003e The data obtained for viscosity and zeta potential were subjected to one-way ANOVA and the treatment means were compared using Tukey\u0026rsquo;s test (α\u0026thinsp;=\u0026thinsp;0.05). Linear regression was used to assess rheological behavior and physical stability data with a trend line for data adjustment.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability.\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe datasets generated and/or analyzed during the current study are available in the files listed in the paper submission, available by the corresponding author upon request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo the laboratory Malvern Panalytical Scientific Instrumentation for making available the Malvern Kinexus lab+ concentric cylinder rheometer.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA.B.D.S. participated in the data collection, tabulation, and formatting of\u0026nbsp;the final manuscript. A.B.D.S., and M.C.F. participated in the writing and revision of the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTis study was fnanced in part by the Conselho Nacional de Desenvolvimento Cient\u0026iacute;fico e Tecnol\u0026oacute;gico\u0026mdash;Brasil (CNPq)\u0026mdash;Finance Code 001\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTe authors declare no competing interests.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCorrespondence and requests for materials should be addressed to A.B.D.S. or M.F.C.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eGazziero, D.L.P. Misturas de agrot\u0026oacute;xicos em tanque nas propriedades agr\u0026iacute;colas do Brasil. 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(2000)\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"dispersants, solution instability, tank mixture","lastPublishedDoi":"10.21203/rs.3.rs-1782058/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-1782058/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe practice of mixing different classes of crop protection products in tank is common for farmers, with efficience losses by compatibility problems, but a lack of research to better understand them. The aim of this study was to evaluate the initial stability loss of spray liquid mixtures obtained by association of fungicides and adjuvants with insecticides. Laboratory experiments were carried with nine treatments composed of the insecticide thiamethoxam\u0026thinsp;+\u0026thinsp;lambda-cyhalothrin (TL) mixed with the fungicides fluxapyroxad\u0026thinsp;+\u0026thinsp;pyraclostrobin (FP) and chlorothalonil (CL) and the adjuvants lecithin, propionic acid (LA), and mineral oil (MO). Assessment of initial loss solution stability was performed to verify when the product mixture in the sprayer tank starts. For this purpose, were carried rheological behavior and zeta potential analyses, and the determination of viscosity. The treatments containing insecticide TL with adjuvants LA and MO and the fungicide FP have shown the loss of physical-chemical stability, possibly due to changes in the layers around the particles of the components of the ingredients contained in the various combined solution formulations.\u003c/p\u003e","manuscriptTitle":"Initial stability loss of insecticide solution mixed with fungicides and adjuvants","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2022-07-21 16:31:44","doi":"10.21203/rs.3.rs-1782058/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"408f83d3-0e13-4ce0-8710-2acf4d9128ac","owner":[],"postedDate":"July 21st, 2022","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2023-10-06T05:44:23+00:00","versionOfRecord":[],"versionCreatedAt":"2022-07-21 16:31:44","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-1782058","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1782058","identity":"rs-1782058","version":["v1"]},"buildId":"7rjqhiLT3MXkJMwkYKINL","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}