Studies have shown that the mixture toxicity of compounds with similar modes of action (MOAs) is usually predicted by the concentration addition (CA) model. However, due to the lack of toxicological information on compounds, more evidence is needed to determine whether the above conclusion is generally applicable. In general, the same type of compounds with similar chemical structures have similar MOAs, so whether the toxicities of the mixture of these compounds are additive needs to be further studied. In this paper, three types of pesticides with similar chemical structures (three organophosphoruses, two carbamates and two neonicotinoids) that may have similar MOAs were selected and five binary mixture systems were constructed. For each system, five mixture rays with different concentration ratios were designed by the direct equipartition ray design (EquRay) method. The mortality of Caenorhabditis elegans was regarded as the endpoint for the toxicity exposure to single pesticides and binary mixtures. The combined toxicities were evaluated simultaneously using the CA model, isobologram and combination index. The structural similarity of the same type of pesticides was quantitatively analyzed according to the MACCS molecular fingerprint and the slope of dose-response curve at pEC₅₀. The results show that the toxicities of neonicotinoid mixtures and carbamate mixtures are almost antagonistic. The entire mixture system of dichlorvos and dimethoate produced synergism, and four of the five mixture rays of dimethoate and methamidophos induced antagonism, while among the mixture rays of dichlorvos and methamidophos, different concentrations showed different interaction types. The results of structural similarity analysis show that the size of structural similarity showed a certain quantitative relationship with the toxicity interaction of mixtures, that is, the structural similarity of the same type of pesticides may show an additive action in a certain range.

Pesticides are used for controlling the development of various pests in agricultural crops worldwide. Despite their agricultural benefits, pesticides are often considered a serious threat to the environment because of their persistent nature and the anomalies they create. Hence removal of such pesticides from the environment is a topic of interest for the researchers nowadays. During the recent years, use of biological resources to degrade or remove pesticides has emerged as a powerful tool for their in situ degradation and remediation. Fungi are among such bioresources that have been widely characterized and applied for biodegradation and bioremediation of pesticides. This review article presents the perspectives of using fungi for biodegradation and bioremediation of pesticides in liquid and soil media. This review clearly indicates that fungal isolates are an effective bioresource to degrade different pesticides including lindane, methamidophos, endosulfan, chlorpyrifos, atrazine, cypermethrin, dieldrin, methyl parathion, heptachlor, etc. However, rate of fungal degradation of pesticides depends on soil moisture content, nutrient availability, pH, temperature, oxygen level, etc. Fungal strains were found to harbor different processes including hydroxylation, demethylation, dechlorination, dioxygenation, esterification, dehydrochlorination, oxidation, etc during the biodegradation of different pesticides having varying functional groups. Moreover, the biodegradation of different pesticides was found to be mediated by involvement of different enzymes including laccase, hydrolase, peroxidase, esterase, dehydrogenase, manganese peroxidase, lignin peroxidase, etc. The recent advances in understanding the fungal biodegradation of pesticides focusing on the processes, pathways, genes/enzymes and factors affecting the biodegradation have also been presented in this review article.

Since the invasion of the fall armyworm moth (Spodoptera frugiperda) in China in January 2019, damage to maize crops has gradually intensified, and chemical control has become the main control measure. This study aimed to examine methods of effective pest control while monitoring the environmental impact of pesticide use. The effectiveness of S. frugiperda pest control by foliar spraying and root irrigation of maize plants with acephate was determined, and the absorption, distribution, and dissipation of acephate and methamidophos by maize were studied. Field trials showed that acephate treatment at 6000 g a.i. ha⁻¹ was the most effective for controlling S. frugiperda. Acephate and methamidophos were absorbed from the roots, transported upward, and concentrated in the leaves, particularly new leaves. The terminal residues of acephate and methamidophos in maize grains were below detectable levels at 60 days after treatment. The results demonstrate that acephate treatment via root irrigation can more effectively control the infestation of S. frugiperda in maize than acephate treatment via foliar spraying. The translocation and distribution of acephate and methamidophos by root irrigation were more uniform, and the holding efficiency was higher than those in foliar spraying, suggesting an extended period of control efficacy. This pest control method could be utilized to reduce pesticide residues while safely and efficiently controlling S. frugiperda infestation.

During this research, chemometric approaches were applied for optimization of the low-temperature partitioning extraction (LTPE) for the simultaneous analysis of the pesticides: acephate, difenoconazole, fenamidone, fluazifop, fluazinam, methamidophos, and thiamethoxam from surface water samples and determination by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry. It was used the 2³ full factorial and the Doehlert experimental designs. The extraction technique was optimized by evaluating the effects of the three variables: sample pH, ionic strength (addition of Na₂HPO₄), and organic solvent volume. Considering the interest to find an optimal condition for all analytes simultaneously, the best extraction parameters found were as follows: pH = 5.33, concentration of Na₂HPO₄ = 0.0088 mol L⁻¹ and organic phase volume = 4.5 mL. The optimized methodology showed LOD and LOQ levels from 0.33 to 8.13 ng L⁻¹ and from 1.09 to 26.84 ng L⁻¹, respectively. The recovery values ranged from 38.37 and 99.83% and the RSD values varied from 2.33 to 18.92%. The method was applied to surface water analysis sampled in areas with intensive agricultural practices in Ouro Branco City, Minas Gerais, Brazil. The difenoconazole was detected in concentrations between 12.53 and 94.76 ng L⁻¹.

Farmland soil sprayed with organophosphorus pesticides (OPs) annually was investigated for the identification and characterization of OP-degrading microorganisms. Six bacterial strains were identified, including Brevundimonas faecalis MA-B12 and Alcaligenes faecalis subsp. parafaecalis MA-B13 for methamidophos degradation, Citrobacter freundii TF-B21 and Ochrobactrum intermedium TF-B23 for trichlorfon degradation, Ochrobactrum intermedium DV-B31 for dichlorvos degradation, and Bacillus cereus for dimethoate degradation. The optimal biodegradation conditions for OPs were obtained at pH 7.0 and incubation temperature ranging from 28 to 37 °C. In an 8-day batch test, biodegradation of the four OPs all followed first-order kinetics, with biodegradation rates ranging from 58.08 to 96.42%. Functional genes responsible for OPs degradation were obtained, including ophB, ampA, opdE, opd, opdA, and mpd. As these strains were indigenous strains isolated from farmland soils, they can be potentially used as bacterial consortium for the bioremediation of mixed OP-contaminated soils. A time-course genotoxicity assessment of the degradation products was done by a bacterial whole-cell bioreporter, revealing that biodegradation of trichlorfon, dichlorvos, and dimethoate resulted a decreased genotoxicity within 5 days, which, however, significantly increased on day 8. The result demonstrated that more toxic products may be produced during the biodegradation processes of OPs, and more attention should be put not only on the pesticides themselves, but also on the toxic effects of their degradation products. To the best of our knowledge, this is for the first time that the genotoxicity of OP degradation products was evaluated by the bioreporter assay, broadening our understanding on the genotoxic risks of OPs during biodegradation process. Graphical Abstract

The main objective of the review is to document, assess and analyze the results of the previously reported data on levels of different pesticides in selected fruits and vegetables from Pakistan. The findings of the previous studies clearly indicated that more than 50 % of the samples were contaminated with organophosphate, pyrethroids and organochlorine pesticides. Many studies reported that among fresh fruits and vegetables tomato, apple, melon, mango, grapes, and plum crossed the FAO/WHO permissible limits for these contaminants residual levels. The comparison of other regions showed that observed levels were found above maximum residue limits (MRLs) in 50 % of the samples but were in agreement with the studies from neighboring countries like China and Bangladesh. Higher hazard risk index (HRI) values were calculated for dieldrin, methamidophos, o,p′-DDT, diazinon and p,p′-DDT in apple, mango, banana, melon, potato and onion. The review also highlights that data on pesticide residues in foodstuff is scarce which should be overcome by further extending studies from different areas of Pakistan. In order to ascertain the provision of food suitable for human consumption, it is imperative to monitor pesticides in food commodities by the country’s authorities and enforce guidelines based on permissible limits.