Emulsifiable concentrates and oil suspensions are typical pesticide formulations. Many pesticides on the market use aromatic hydrocarbons as solvents. However, studies have revealed their potential risks to humans and the environment. Ethylene glycol diacetate (EGDA) is a low-toxicity and eco-friendly solvent with low utilization in pesticides. This study explores EGDA’s potential to replace xylene. Results indicate that EGDA formulations enhance droplet adhesion to leaves, boosting pesticide efficiency. They exhibit lower surface tension and contact angles, with a 24%–40% increase in leaf retention. Bioassays show that 15% cyhalofop-butyl EC and 10% nicosulfuron OF with EGDA offer weed control that is superior to xylene-based formulations by 9.1%–30.5% in greenhouses and 4.8%–6.7% in fields. Xylene preparations are 2–3 times more cytotoxic to human bronchial cells than EGDA-based ones. Thus, EGDA is a promising pesticide solvent, outperforming traditional aromatic solvents in environmental friendliness and reducing adverse effects.

As environmental and food safety requirements are increasingly emphasized, there is a trend to reduce pesticide use and explore green and efficient pesticide options. In order for this goal to be realized, the development of new pesticide solvents has been considered as one of the simplest, fastest and most effective methods.¹⁾ At present, various formulations such as soluble concentrates and microemulsions have emerged in pesticide formulation. However, traditional formulations such as emulsifiable concentrates (EC) and oil suspensions (OF) are still the main forms, especially EC, which occupies a large proportion of the pesticide market due to its many incomparable advantages.^2,3) The choice of solvent is extremely important for pesticides, but the safety of pesticides cannot be ignored.

Generally, formulation solvents are inert liquids and risk assessments for agrochemicals primarily consider the effects of formulation and spraying of pesticides on crops, as well as the residual toxicity of the prodrugs, but the toxicity of solvents is rarely considered.^4,5) However, research data suggest that the environment and organisms can be severely affected by certain solvents. For example, some aromatic compounds (such as toluene and xylene) are used as traditional solvents for the formulation of pesticides. These solvents have high toxicity and low biodegradability and can pollute the environment and affect human health.^6–8) Nowadays, green carrier solvents such as vegetable oils, animal fats or biodiesel are used in many studies to try to develop pesticide formulations.^9,10) However, some of these solvents have high viscosity or may be solid at low temperatures. Also, certain crops may be phytotoxicized by heavily used vegetable and mineral oils.¹¹⁾ Unintended species in the surrounding environment can be seriously harmed by drift, volatilization and residues that may occur during use.¹²⁾ The wettability and dispersibility of herbicides can be caused to deteriorate by some of the new solvents, and leaf transpiration and photosynthesis can be affected.¹³⁾ Solvents play an irreplaceable role in pesticides, so there is a need to explore some environmentally friendly alternatives.

Ethylene glycol diacetate (EGDA) is an environmentally friendly solvent with strong solubility, low odor, and low toxicity that is widely used in paints, coatings, adhesives, and other fields.^14–16) EGDA is relatively simple to be synthesized and does not require complicated equipment and technology, which ensures a reasonable cost and minimizes sourcing problems.¹⁷⁾ EGDA has a flash point of 88°C and can therefore be safely stored and transported.¹⁸⁾ Moreover, it can be mixed with alcohol, ether, and benzene while its solubility in water is as high as 12.5%, so it can be used as a solvent in pesticide systems. However, there are few reports on the use of EGDA as a solvent for pesticides¹⁸⁾; therefore, further study of ethylene glycol diacetate is essential for future reference. As an alternative solvent for pesticide formulations, EGDA can reduce the use of traditional aromatic solvents in agrochemical formulations.

Cyhalofop-butyl has been used as a major herbicide to combat weeds in annual rice fields in many parts of the world. Nicosulfuron is often considered to represent the sulfonylurea family and is one of the best-selling sulfonylurea herbicides.¹⁹⁾ In this study, 15% cyhalofop-butyl EC and 10% nicosulfuron OF formulations were prepared using EGDA as an alternative carrier. The physicochemical properties, phytotoxicity, herbicidal activity and cytotoxicity of the resulting formulations were systematically investigated to assess the advantages of using EGDA as solvents in pesticide systems.

Ethylene glycol diacetate (EGDA CAS:111-55-7) by Shandong Rayon Chemical Co.. Dimethyl sulfoxide (DMSO) were purchased from Aladdin. 15% Cyhalofop butyl with EGDA as solvent is formulated as 30% EGDA +39% methyl oleate +16% emulsifier and with xylene as solvent is formulated as 30% xylene +39% methyl oleate +16% emulsifier. 10% Nicosulfuron with EGDA as solvent is formulated as 30% EGDA +44% methyl oleate +16% emulsifier and with xylene as solvent is formulated as 30% xylene +44% methyl oleate +16% emulsifier. Both formulations have been formulated by our laboratory.

Shortawn foxtail (Alopecurus aequalis Sobol.) were grown from seed in a controlled environment at 25±2°C and a 12 : 12 hr light/dark photoperiod. The experiment was carried out when weeds reached to 3–4 leaves (BBCH code: stage 13). The plant seeds used in the experiment were all from Shanghai Pesticide Research Institute. All seeds used were planted in prepared nutrient-balanced soil (Huai'an Huainong Agricultural Technology Development Co., Ltd. N, P, K total nutrients ≥2%, total organic matter ≥28%).

Rice (Oryza sativa L.) and cucumber (Cucumis sativus L.) were used as model plants for this experiment. Cucumber seedlings were grown in plastic pots (15 cm in diameter and 12 cm in height) and rice was planted in homemade planting boxes (L×W×H: 10×7×10 cm). Cyhalofop-butyl (EC) 15% and nicosulfuron (OF) 10% were applied in the formulations using EGDA and xylene as solvents in the combinations of EGDA-EC, EGDA-OF, xylene-EC, and xylene-OF. To improve the safety range, the samples were diluted to a maximum field concentration of 300 mg/L and two and four times the maximum recommended concentration (600 mg/L and 1200 mg/L, respectively). Rice and cucumber seedlings were sprayed with the above concentrations using a laboratory sprayer with a flat fan nozzle over an area of 0.1 m², with a dosage of 5 mL of liquid and an operating pressure of 0.2 MPa. Experimental plants were sprayed with these three concentrations, deionized water was sprayed as a blank control, with each treatment consisting of at least three biological replicates.

Potted shoots were spray-treated. The weeds at the 3–4 leaf stage were selected for observation. The concentrations of 15% cyhalofop-butyl (EGDA-EC and xylene-EC) were set at 0, 67, 96, 137, 196, 280, 400 g ha⁻¹. The concentrations of 10% Nicosulfuron (EGDA-OF and xylene-OF) were set at 0, 50, 72, 103, 147, 210 and 300 g ha⁻¹. Weeds were treated by spraying with a laboratory sprayer with a flat fan nozzle over an area of 0.1 m² with a dosage of 5 mL of liquid and an operating pressure of 0.2 MPa. Water was set up as a control and there were at least three pots of potted plants as biological replicates for each treatment. Then, samples were grown in a greenhouse, and the water was regularly replenished by bottom irrigation to maintain appropriate soil humidity. After 2 weeks of treatment, weeds what is collected for fresh weight. The control effect (%) was calculated by the Eq. 1. The relative toxicity index was calculated by the Eq. 2.

(1)

(2)

Short-awned foxtail was used as a field study in the Shixin Vegetable Zone in Shanghai (N31°4′27.207″, E121°2′1.568″), and each treatment consisted of a 5 m-long by 5 m-wide plot. A 2 m distance was established between each treatment group. The field concentration settings were 0, 137, 196, 280 and 400 g ha⁻¹ for the two different solvents of 15% cyhalofop butyl (EGDA-EC and xylene-EC) and 0, 103, 147, 210 and 300 g ha⁻¹ for the two different solvents of 10% Nicosulfuron (EGDA-OF and xylene-OF). Spraying was carried out with a sprayer at 450 L/ha. The average density was about 250 plants/m², accounting for more than 98% of the total weeds. Visual mortality data were recorded periodically and within 14 days after spraying with 0=no effect (healthy green leaves) and 100=total mortality (completely withered yellow leaves).^20,21) The fresh weight of aboveground parts was measured after 3 weeks, and the average fresh weight control rate was calculated using Eq. 1.

To investigate whether EGDA as a herbicide solvent improves the physicochemical properties of herbicides, the indicated tensions at different concentrations (0, 100, 200, 300 and 400 g ha⁻¹) and the contact angle at a constant concentration (400 g ha⁻¹) were determined. Measurements were repeated at least three times for each concentration with platinum-iridium plates. The mixture’s surface tension was measured using a TX500C spinning droplet interface tensiometer (Kino Industries, Boston, MA, USA) at room temperature. After measuring the samples, the platinum-iridium plate was successively washed three times with deionized water and ethanol and dried with a flame. Make sure the platinum-iridium plate is clean.

Shortawn foxtail leaf was cut into 1 cm×2 cm rectangles and fixed on an Angle Goniometer (Powereach, JC2000D3, Shanghai, China) with double-sided adhesive tape. Droplets were generated by the microinjector and deposited on the surface of the fixed leaves. The volume of each droplet was controlled at 5 µL. Droplet images are obtained by using the instrument’s imaging system (Powereach, JC2000D3, Shanghai, China) and the contact angle of the liquid on the blade is calculated. The contact angle change can be observed throughout the retention time and recorded by taking pictures at 0.5-sec intervals. Each group of samples was processed three times.

Droplet spreading performance was set at 200 g ha⁻¹, and leaf retention capacity was measured at 100, 200 and 300 g ha⁻¹.

5 µL of 15% Cyhalofop-butyl (EGDA-EC and xylene-EC) was dropped onto the surface of Shortawn foxtail leaves using a microsyringe. After five minutes, droplets were observed under a microscope, and the diameter of the diffused area was determined under a microscope.²²⁾ The experiment was repeated three times.

The leaves of weeds were cut into evenly spaced strips of 1×2 cm. Then, blades were weighed before and after being immersed in a sample solution, and each experiment was repeated three times. Then, the following equation was used to calculate retention:

(3)

W₁ is the weight before immersion, W₂ is the weight after immersion, S is the leaves area.¹⁸⁾

Cell viability can be detected using a methyl thiazole tetrazolium (MTT) assay.²³⁾ To determine the cytotoxicity of the prepared samples, 16-HBE cells (Cells were purchased from the American Model Culture Collection) was selected as in vitro cell models. Cells were all cultured in DMEM high sugar medium containing 10% heat-inactivated fetal bovine serum and 1% antibiotics (penicillin penicillin 100 U/mL, streptomycin streotomycin 100 µg/mL). A cell counting apparatus adjusted the cell density to 1×10⁵ cells mL⁻¹. Then, 100 µL of the cell suspension was poured onto a 96-well plate and incubated at 37°C in a 5% CO₂ incubator (SPX-280 Intelligent Biochemical Incubator, Thermo Fisher Scientific Inc.) for 24 hr. 15% Cyhalofop-butyl (EGDA-EC and xylene-EC) was diluted to 0 mg/L, 5 mg/L, 10 mg/L, 20 mg/L, 40 mg/L and 80 mg/L with fresh medium, and 10% Nicosulfuron (EGDA-OF and xylene-OF) was diluted to 0 mg/L, 1 mg/L, 4 mg/L, 8 mg/L, 12 mg/L and 16 mg/L with fresh medium.Then the medium in each well of the 96-well plate was discarded, and 200 µL of the test solution was added to each well, and then the 96-well plate was placed into the incubator (5% CO₂ and 37°C) for 24 hr. Replicate experiments were set up with three wells in the culture plate for each concentration, and each set of experiments was independently repeated three times. After 24 hr of treatment, 20 µL of MTT reagent (5 mg mL⁻¹) was added to each well and placed in the incubator for 4 hr while the MTT and culture solution were absorbed and 150 µL of DMSO was added to dissolve the thyroxine. Finally, the absorbance of each well was measured at 572 nm using a Synergy H1 microplate reader (Bio-Teck, Winooski, VT, America).

Data are expressed as an average with standard deviation, and variance analysis was conducted using SPSS 22.0. The least significant difference (LSD) test compared the mean separation between treatments. The level of significant difference was 0.05.

According to the visual evaluation criteria in Table 1. At the maximum recommended concentration, there was no significant difference in plant height and leaf growth of rice in the four treatment groups of EGDA-EC, EGDA-OF, xylene-EC and xylene-OF compared with the control group of clear water. During the growth of cucumber, there were no significant differences in the number of leaves, stem thickness and plant height compared with the control group, indicating that none of them caused damage to the crop.

Our results show that EGDA-EC and EGDA have no harmful plant effects and are safe for crops after spraying.

When EGDA was used as a solvent to 15% Cyhalofop-butyl and 10% Nicosulfuron, suppression of Shortawn foxtail was greater than 90% at concentrations above 280 g ha⁻¹ and 210 g ha⁻¹, respectively, 14 days after spraying (Fig. 1A and B).

Fig. 1. Nicosulfuron (EGDA-OF and Xylene-OF) (A). Cyhalofop-butyl (EGDA-EC and Xylene-EC) (B). Experiment on inhibition rate of fresh weight of Chinese sprangletop in greenhouse (C and D).

In contrast, xylene as a solvent resulted in over 90% control of Shortawn foxtail at concentrations above 400 g ha⁻¹ and 300 g ha⁻¹, respectively (Fig. 1A and C).

For cyhalofop butyl, the LC₅₀ was 63.5 g ha⁻¹ for EGDA-EC and 72.72 g ha⁻¹ for xylene-EC. EGDA-EC was 1.145 times more toxic than xylene-EC to Short-horned Foxtail. For 10% Nicosulfuron the LC₅₀ was 38.36 g ha⁻¹ for EGDA-OF and 41.85 g ha⁻¹ for xylene-OF (Table 2). EGDA-OF was 1.091 times more toxic than xylene-OF to Shortawn Foxtail. This shows that herbicidal control effect with EGDA is better than with xylene.

The results showed that the control efficacy of different concentrations of EGDA-EC was 52.31%, 66.58%, 75.67% and 78.87% against Shortawn foxtail, while that of Xylene-EC was 45.16%, 71.37%, 76.00% and 77.48% against Shortawn foxtail (Table 3). The LC₅₀ value of the EGDA-EC treatment group was 49.9 g ha⁻¹, while the LC₅₀ value of Xylene-EC was 52.3 g ha⁻¹. The results showed that the relative toxicity index of the EGDA-EC treatment group was 1.04 times higher than that of the Xylene-EC treatment group, and the field results showed that the inhibitory effects of EGDA-EC and Xylene-EC treatments were comparable to each other, with no significant difference.

The same method was applied after 15 days of 10% Nicosulfuron treatment. The results showed that the efficacy of different concentrations of EGDA-OF was 55.61%, 68.97%, 71.48% and 77.02% against Shortawn foxtail, while that of Xylene-OF was 51.19%, 66.50%, 76.49% and 79.95% (Table 4). The LC₅₀ value of EGDA-OF treated group was 50.63 mg/L, whereas the LC₅₀ value of Xylene-OF treated group was 54 mg/L (Table 5). The results showed that the relative toxicity index of EGDA-OF was 1.07 times higher than that of Xylene-OF, and the field results showed that the inhibitory effects of EGDA-OF and Xylene-OF were comparable to those of Shortawn foxtail, with no significant difference.

Results showed an LSD value of 5% with no significant difference compared to the negative control. It indicates that the herbicidal activity of the two samples was equal in the field experiment.

The results show that the surface tension of 15% Cyhalofop-butyl and 10% Nicosulfuron decreases with increasing concentration, regardless of the solvent. However, at the same concentration, the surface tension of cyhalofop butyl and 10% Nicosulfuron with EGDA as solvent was always lower than that with xylene as solvent (Fig. 2A and B).

Fig. 2. The surface tension of ECGA-EC is less than Xylene-EC (A and B). The blade holding capacity of the formulations containing EGDA is greater than formulations containing Xylene (C). The contact angle of the formulations containing EGDA is less than formulations containing Xylene (D).

The contact angle magnitudes of 15% Cyhalofop-butyl and 10% Nicosulfuron with EGDA as solvent were 48.6° and 59.4°, respectively, while those of 15% Cyhalofop-butyl and 10% Nicosulfuron with xylene as solvent were 64.5° and 75.3°, respectively (Fig. 2D).

The spreading properties and the ability of the droplets to adhere to the leaves were also determined. For the spreading properties, 15% Cyhalofop-butyl droplet diameters were 5.06 mm and 3.97 mm with EGDA and xylene as solvent, respectively, and 1.27 times greater for EGDA-EC than for xylene-EGDA. 10% Nicosulfuron droplets with EGDA and xylene as solvent were 5.19 mm and 4.15 mm in diameter, respectively, and EGDA-EC was 1.25 times larger than xylene-EGDA (Table 6).

The retention capacity of the leaves showed that the amount of droplets attached to the leaves increased with increasing concentration. For example, at 200 g ha⁻¹, cyhalofop butyl and 10% Nicosulfuron were 1.4 and 1.24 times greater than xylene as solvent, respectively (Fig. 2C).

When cells were treated with two different models with various concentrations for 24 hr, the cell survival rate was negatively correlated with the sample concentration. Generally, the higher the attention, the more pronounced the control rate (Fig. 3). Results also showed that for 16-HBE cells, the IC₅₀ of 15% Cyhalofop-butyl EGDA-EC was 27.78 µM mL⁻¹, while xylene-EC was 13.82 µM mL⁻¹. The IC₅₀ of 10% Nicosulfuron EGDA-OF was 8.28 µM mL⁻¹, while xylene-OF was 1.77 µM mL⁻¹ (Table 7). Lower cytotoxicity was observed in formulations containing EGDA than in xylene, indicating that EGDA can reduce cytotoxicity.

Fig. 3. Effect on the activity of 16-HBE cells. Formulations containing EGDA have less influence on the activity of 16-HBE cells than formulations containing Xylene. Cyhalofop-butyl (EGDA-EC and Xylene-EC) (A). Nicosulfuron (EGDA-OF and Xylene-OF) (B). Different lowercase letters in the figure indicate significant differences between any two groups (p≤0.05).

The application of chemical herbicides plays a vital role in agricultural production. As herbicides are used phytotoxicity, weed resistance, residues and other problems arise, with the emergence of phytotoxicity, weed resistance, residue and other problems during the use of herbicides, improving the efficacy of herbicides and the processing quality of preparations, reducing the dosage of herbicides have become urgent problems in agricultural production. The development of new varieties of herbicides and the analysis and use of new solvents have been cited as major solutions to the above problems. It is expected that the development and use of new solvents will require minimal research and development cycle, will have a noticeable effect and will result in a low cost. This focus will become an effective measure to improve the efficacy of herbicides and reduce the amount required. For example, the commonly used solvent mineral oil is a non-renewable resource with limited sources, serious environmental hazards, and strict environmental requirements for pesticide application.²⁴⁾ Therefore, the exploration of new, green, efficient, and environment-friendly pesticide solvents is needed. In this study, EGDA, which is a new low-toxic organic solvent, was selected to replace the aromatic hydrocarbon solvent of traditional pesticides, and its application as a herbicide solvent was examined.

First, we assessed the effectiveness of the control. The results show that after aromatic solvents were replaced with EGDA, these two sample types had different synergistic effects on the new weight control of weeds in the greenhouse and field. Moreover, in the greenhouse test, the addition of EGDA improved the herbicide control. The control in the greenhouse was statistically significant. In the field, although herbicide control with EGDA as solvent was better than that with xylene as solvent, it was not statistically significant, probably due to the complex environmental factors in the field which led to non-significant differences between the two. To further investigate the reasons for the improved control, the physicochemical properties of the herbicides with EGDA and xylene as solvents were determined separately.

Previous studies have shown that the active ingredient in pesticide formulations has a very low rate of bio-absorption (<0.1%).^25,26) The addition of spray adjuvants to pesticides can facilitate the uptake of the active ingredient into plant leaves, thereby improving efficacy, particularly on plant species that are difficult to wet, such as Goosegrass (Eleusine indica (L.)Gaertn) and Crab grass (Digitaria sanguinalis).^27–29) The effect of pesticides on crop diseases and insect pests is affected by the toxicity of insecticides themselves and depends on the characteristics of active ingredients on the surface of plant leaves and the ability of leaves to retain the active ingredients.^30–32) Solvents are often thought to reduce the surface tension of pesticide and increase the spreading of the pesticide on plant leaves. We therefore investigated the effect of EGDA as an solvent on pesticide droplets. The results showed that 15% Cyhalofop-butyl and 10% Nicosulfuron with EGDA as a solvent improved the surface tension and contact angle of pesticide droplets significantly better than with xylene as a solvent. EGDA also performed better than xylene as a solvent in terms of the spreading and holding capacity of droplets on plant leaves. As a solvent, EGDA can reduce the surface tension, increase the diffusion area, reduce the contact angle, and increase the retention of leaves. It suggests that EGDA can make pesticide droplets adhere better to the leaves and promote the uptake of pesticides by the leaves. In summary, EGDA increased the efficacy of both herbicides and improved herbicide availability, probably due to its use as a solvent to improve the physicochemical properties of the herbicides. This facilitates the reduction of herbicide doses and has good application prospects.

Cell viability assays are often used to assess the toxicity of contaminants.³³⁾ HepG2 has been shown to be a good cellular model for assessing health risks.³⁴⁾ Traditional aromatic solvents, such as xylene, result in high cytotoxicity. Therefore, we determined the toxicity of Cyhalofop-butyl and 10% Nicosulfuron with EGDA and xylene as solvents, respectively, on HepG2 cells. MTT results showed that the cytotoxicity of the formulations containing EGDA was less than that of the formulations containing xylene (whether it was 15% Cyhalofop-butyl or 10% Nicosulfuron). Furthermore, the cytotoxicity of 15% Cyhalofop-butyl xylen-EC was 2.08 times greater than that of EGDA-EC, and 10% Nicosulfuron xylene-OF was 2.98 times greater than that of EGDA-OF. Compared with traditional formulations containing xylene, formulations containing EGDA showed lower cytotoxicity, which reduces the risk to human health.

In this study, environmentally friendly cyhalofop-butyl emulsifiable concentrate formulations and nicosulfuron oil suspension formulations were prepared using ethylene glycol diacetate (EGDA) as solvent. The formulations with EGDA as solvent had excellent wettability, spreadability and adhesion compared with the traditional xylene formulations, which ensured higher pesticide utilization, improved pesticide control and further reduced the amount of agrochemicals and the number of applications. Meanwhile, compared with traditional xylene formulations, EGDA formulations are less toxic to cells, which reduces the risk to the environment as well as the hazard to human health. In conclusion, EGDA is a safe and environmentally friendly solvent and can be a promising alternative to solvents in agrochemical formulations.

The research received funding from the National Key Research and Development Plan under Grant Agreement 2022YFD1700502.

The authors declare no conflict of interest.

• 1) M. R. Uddin, S. U. Park, F. E. Dayan and J. Y. Pyon: Herbicidal activity of formulated sorgoleone, a natural product of sorghum root exudate. Pest Manag. Sci. 70, 252–257 (2014).
• 2) E. N. Yunira, A. Suryani, Dadang and S. Tursiloadi: Dadang and S. Tursiloadi: Synthesis and aplication CTAC surfactant from palmityl alcohol in insecticide emulsifiable concentrate formulation. IOP Conf. Ser. Earth Environ. Sci. 209, 012039 (2018).
• 3) N. H. Tran, T. V. T. Hieu, T. Dang-Bao and T. T. K. Anh: Assessment of methyl ester as a green carrier solvent in pesticide emulsifiable concentrate formulation. IOP Conf. Ser. Earth Environ. Sci. 947, 012031 (2021).
• 4) A. Edlinger, G. Garland, K. Hartman, S. Banerjee, F. Degrune, P. García-Palacios, S. Hallin, A. Valzano-Held, C. Herzog, J. Jansa, E. Kost, F. T. Maestre, D. S. Pescador, L. Philippot, M. C. Rillig, S. Romdhane, A. Saghaï, A. Spor, E. Frossard and M. G. A. van der Heijden: Agricultural management and pesticide use reduce the functioning of beneficial plant symbionts. Nat. Ecol. Evol. 6, 1145–1154 (2022).
• 5) G. Hu, H. Wang, Y. Wan, L. Zhou, Q. Wang and M. Wang: Combined toxicities of cadmium and five agrochemicals to the larval zebrafish (Danio rerio). Sci. Rep. 12, 16045 (2022).
• 6) R. Kandyala, S. P. C. Raghavendra and S. T. Rajasekharan: Xylene: An overview of its health hazards and preventive measures. J. Oral Maxillofac. Pathol. 14, 1–5 (2010).
• 7) J. Maliszewska and E. Tęgowska: Toxicity of insecticide carrier solvent: Effect of Xylene on hemolymph biochemical parameters in Blaberus giganteus L. Pol. J. Environ. Stud. 27, 2385–2390 (2018).
• 8) M. Tobiszewski and J. Namieśnik: Scoring of solvents used in analytical laboratories by their toxicological and exposure hazards. Ecotoxicol. Environ. Saf. 120, 169–173 (2015).
• 9) A. Purkait and D. K. Hazra: Biodiesel as a carrier for pesticide formulations: A green chemistry approach. Int. J. Pest Manag. 66, 341–350 (2020).
• 10) C.-P. Chin, C.-W. Lan and H.-S. Wu: Study on the performance of lambda cyhalothrin microemulsion with biodiesel as an alternative solvent. Ind. Eng. Chem. Res. 51, 4710–4718 (2012).
• 11) L. D. Bainard, M. B. Isman and M. K. Upadhyaya: Phytotoxicity of clove oil and its primary constituent eugenol and the role of leaf epicuticular wax in the susceptibility to these essential oils. Weed Sci. 54, 833–837 (2006).
• 12) H. Qionghui, L. Yong, Z. Huajiao, L. Jianyu, F. Jianwei and Y. Xikai: Effect on residue of methylamino abamectin benzoate mixed with plant oil substitute for xylene solvent in Brassica campestris. Zhongguo Nongxue Tongbao 2011, 356–361 (2011).
• 13) A. Räsch, M. Hunsche, M. Mail, J. Burkhardt, G. Noga and S. Pariyar: Agricultural adjuvants may impair leaf transpiration and photosynthetic activity. Plant Physiol. Biochem. 132, 229–237 (2018).
• 14) R. Min, K. Li, D. Wang, W. Xiao, C. Liu, Z. Wang and S. Bian: A novel method for layer separation of photovoltaic modules by using green reagent EGDA. Sol. Energy 253, 117–126 (2023).
• 15) Y. Xiao, W. Cai, H. Sun, F. Shi and G. Li: Kinetics study and process simulation of transesterification of ethylene glycol with methyl acetate for ethylene glycol diacetate. Can. J. Chem. Eng. 96, 722–730 (2018).
• 16) J. Yang, L. Zhou, X. Guo, L. Li, P. Zhang, R. Hong and T. Qiu: Study on the esterification for ethylene glycol diacetate using supported ionic liquids as catalyst: Catalysts preparation, characterization, and reaction kinetics, process. Chem. Eng. J. 280, 147–157 (2015).
• 17) F. Huang, S. Xu, T. Li and D. Zhu: Innovative Ethylene Glycol Diacetate synthesis process in a single reactive distillation column. Chem. Eng. Process. 109, 80–89 (2016).
• 18) X.-P. Zhang, T.-F. Jing, D.-X. Zhang, J. Luo, B.-X. Li and F. Liu: Assessment of ethylene glycol diacetate as an alternative carrier for use in agrochemical emulsifiable concentrate formulation. Ecotoxicol. Environ. Saf. 163, 349–355 (2018).
• 19) L. Carles, M. Joly, F. Bonnemoy, M. Leremboure, I. Batisson and P. Besse-Hoggan: Identification of sulfonylurea biodegradation pathways enabled by a novel nicosulfuron-transforming strain Pseudomonas fluorescens SG-1: Toxicity assessment and effect of formulation. J. Hazard. Mater. 324(Pt B), 184–193 (2017).
• 20) D. Chikoye, A. F. Lum and U. E. Udensi: Efficacy of a new glyphosate formulation for weed control in maize in southwest Nigeria. Crop Prot. 29, 947–952 (2010).
• 21) Q. Peng, F. Liu and C. Zhang: Efficacy of difenoconazole emulsifiable concentrate with ionic liquids against cucumbers powdery mildew. Int. J. Chem. Eng. 2017, 8286358 (2017).
• 22) C. Palma-Bautista, J. G. Vazquez-Garcia, I. Travlos, A. Tataridas, P. Kanatas, J. A. Dominguez-Valenzuela and R. De Prado: Effect of adjuvant on glyphosate effectiveness, retention, absorption and translocation in Lolium rigidum and Conyza canadensis. Plants 9, 297 (2020).
• 23) C. K. Constante, J. Rodriguez, S. Sonnenholzner and C. Domínguez-Borbor: Adaptation of the methyl thiazole tetrazolium (MTT) reduction assay to measure cell viability in Vibrio spp. Aquaculture 560, 738568 (2022).
• 24) G. MacKinnon and H. J. Duncan: Phytotoxicity of branched cyclohexanes found in the volatile fraction of diesel fuel on germination of selected grass species. Chemosphere 90, 952–957 (2013).
• 25) T. Liu, J. Luo, S. Liu, T. Li, H. Li, L. Zhang, W. Mu and N. Zou: Clothianidin loaded TA/Fe (III) controlled-release granules: Improve pesticide bioavailability and alleviate oxidative stress. J. Hazard. Mater. 416, 125861 (2021).
• 26) D. Pimentel: Amounts of pesticides reaching target pests: Environmental impacts and ethics. J. Agric. Environ. Ethics 8, 17–29 (1995).
• 27) W. A. Forster and M. O. Kimberley: The contribution of spray formulation component variables to foliar uptake of agrichemicals. Pest Manag. Sci. 71, 1324–1334 (2015).
• 28) P. Spanoghe, M. De Schampheleire, P. Van der Meeren and W. Steurbaut: Influence of agricultural adjuvants on droplet spectra. Pest Manag. Sci. 63, 4–16 (2007).
• 29) R. Zhao, Z. Sun, N. Bird, Y.-C. Gu, Y. Xu, Z.-H. Zhang and X.-M. Wu: Effects of tank-mix adjuvants on physicochemical properties and dosage delivery at low dilution ratios for unmanned aerial vehicle application in paddy fields. Pest Manag. Sci. 78, 1582–1593 (2022).
• 30) G. Ji, H. Chen, Y. Zhang, J. Xiang, Y. Wang, Z. Wang, D. Zhu and Y. Zhang: Leaf surface characteristics affect the deposition and distribution of droplets in rice (Oryza sativa L.). Sci. Rep. 11, 17846 (2021).
• 31) H. Li, I. Travlos, L. Qi, P. Kanatas and P. Wang: Optimization of herbicide use: Study on spreading and evaporation characteristics of glyphosate-organic silicone mixture droplets on weed leaves. Agronomy (Basel) 9, 547 (2019).
• 32) Q. Liu, Y. Liu, F. Dong, J. B. Sallach, X. Wu, X. Liu, J. Xu, Y. Zheng and Y. Li: Uptake kinetics and accumulation of pesticides in wheat (Triticum aestivum L.): Impact of chemical and plant properties. Environ. Pollut. 275, 116637 (2021).
• 33) X. Wang, H. Ni, W. Xu, B. Wu, T. Xie, C. Zhang, J. Cheng, Z. Li, L. Tao and Y. Zhang: Difenoconazole induces oxidative DNA damage and mitochondria mediated apoptosis in SH-SY5Y cells. Chemosphere 283, 131160 (2021).
• 34) T. Ramirez, A. Strigun, A. Verlohner, H.-A. Huener, E. Peter, M. Herold, N. Bordag, W. Mellert, T. Walk, M. Spitzer, X. Jiang, S. Sperber, T. Hofmann, T. Hartung, H. Kamp and B. van Ravenzwaay: Prediction of liver toxicity and mode of action using metabolomics in vitro in HepG2 cells. Arch. Toxicol. 92, 893–906 (2018).