140 contaminants belonging to various classes (organochlorine and organophosphorus pesticides, pyrethroid insecticides, carbamates, fungicides, acaricides, herbicides, synergists, insect growth regulators, polychlorobiphenyls, polycyclic aromatic hydrocarbons) were simultaneously analysed by GC-MS/MS in marine sediments, aquatic plant leaves and fish tissues samples. A total of 260 samples from five stations along the coast of Tunisia were evaluated. The results highlight that only 28 residues (12 polychlorobiphenyls, 8 organochlorine pesticides, 7 polycyclic aromatic hydrocarbons and triphenyl phosphate) were detected at levels higher than relative LOQ values. The amounts in sediment samples were compared with Sediment Quality Guidelines (SQGs) showing that the values are acceptable and no toxic effect is expected on aquatic organisms. A little variation of contaminant residues in sediment samples among coastal stations was recorded. Namely, with respect to almost all polychlorobiphenyls and organochlorine pesticides, higher values were recorder in summer. With respect to almost all polycyclic aromatic hydrocarbons, higher values were recorder in autumn. Aquatic plant leaves showed a residue accumulation higher than that of other compartments of marine system. The data about fish samples (Sparus aurata and Sarpa salpa, the two most frequently caught fish species at five sites on the central coast of Tunisia) do not pose direct hazard to human health because values were lower than protection limits.

As a widely used organotin acaricide nowadays, azocyclotin (ACT) could induce thyroidal endocrine disruption in fishes and amphibians, but its dominant disrupting mode remains unknown. In this study, zebrafish were firstly exposed to ACT (0.18–0.36 ng/mL) from 2 hpf (hours post fertilization) to 30 dpf (days post fertilization), and a series of developmental toxicological endpoints and thyroid hormones were measured. Result showed that no developmental toxicity to zebrafish was found in 0.18 and 0.24 ng/mL groups except decreased body weight (30 dpf, 0.24 ng/mL). However, exposed to 0.36 ng/mL ACT led to reductions in heartbeat (48 hpf), hatching rate (72 hpf) and bodyweight (30 dpf). General tendencies of decreases in free T3 but increases in free T4 and reductions in ratio of free T3/T4 were also found, inferring that type II deiodinase (Dio2) was repressed. This inference was confirmed by Western analysis that Dio2 expression reduced by 42.7% after 0.36 ng/mL ACT treatment. Moreover, RNA-Seq analysis implied that exposed to 0.36 ng/mL ACT altered the genome-wide gene expression profiles of zebrafish. Totally 5660 genes (involving 3154 down-regulated and 2596 up-regulated genes) were differentially expressed, and 13 deferentially expressed genes including down-regulated dio2 were significantly enriched in thyroid hormone signaling pathway. Subsequently, an in vitro thyroid receptor-reporter gene assay using GH3 cells was performed to further explore the potential disrupting mechanism. Result showed that luciferase activity slightly increased after exposure to ACT alone or ACT combined with low level T3, but was suppressed when combined with high level T3. It indicted there probably existed a competitive relationship in some extent between ACT and T3 in vivo. Overall, the present study provided preliminary evidences that long-term exposure to trace ACT repressed Dio2 expression, declined T3 and then activated thyroid receptor-mediated signaling, thereby leading to integrated thyroid endocrine disruption in zebrafish larvae.

Bifenazate is a novel acaricide for selective foliar spraying and is widely used to control mites in agricultural production. However, its toxicity to aquatic organisms is unknown. Here, a zebrafish model was used to study bifenazate toxicity to aquatic organisms. Exposure to bifenazate was found to cause severe cardiotoxicity in zebrafish embryos, along with disorders in the gene expression related to heart development. Bifenazate also caused oxidative stress. Cardiotoxicity caused by bifenazate was partially rescued by astaxanthin (an antioxidant), accompanied by cardiac genes and oxidative stress-related indicators becoming normalized. Our results showed that exposure to bifenazate can significantly change the ATPase activity and gene expression levels of the calcium signaling pathway. These led to heart failure, in which the blood accumulated outside the heart without entering it, eventually leading to death. The results indicated that bifenazate exposure caused cardiotoxicity in zebrafish embryos through the induction of oxidative stress and inhibition of the calcium signaling pathway.

Spirotetramat, a member of tetronic and tetramic acid derivatives, is a unique insecticide and acaricide. Although the effect on zebrafish embryos lipid biosynthesis of spirotetramat has been characterized, the energy metabolism and toxic effect mechanism warrant further investigation. To investigate the toxic mechanism of spirotetramat on energy metabolism, zebrafish embryos were exposed to 100, 500 and 1000 µg/L of spirotetramat for 4 days. Untargeted metabolomics showed the synthesis and degradation of ketone pathway metabolites (R)-3-Hydroxybutyric acid and Acetoacetate significantly decreased, as well as increasing the abundance of Anti-Acetyl Coenzyme A Carboxylase protein (ACC1). Down-regulation of the genes related to ß-oxidation and the tricarboxylic acid cycle in the embryos show decreased energy metabolism. Carnitine palmitoyltransferase 1 (CPT- I) significantly decreased while citrate synthase (CS) significantly increased. Additionally, mitochondrial lesions in embryos were found using electron microscopy. Our study provides novel and robust perspectives, which show that spirotetramat treatment in embryos leads to metabolic disturbances that adversely affect cellular energy homeostasis.

Chlorpyrifos (O, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate) is a broad-spectrum organophosphate insecticide and acaricide, widely used in our country. Nowadays, it is the principal insecticide in the market employed for agricultural purposes. A number of studies tending to study the affinity of different pesticides with soil have been performed, but only a few refer to chlorpyrifos. Because of its intensive use, a wide range of terrestrial ecosystems may be contaminated with chlorpyrifos, and there is a need to evaluate its environmental behavior and effects. The aim of our work is to study the interaction and persistence of a commercial formulation of chlorpyrifos on an agricultural soil from Provincia de Buenos Aires, Argentina. In this case, recovery percentages increased with the increase of initial concentration of the pesticide until a concentration of about 25 ppm is reached, and then a decrease was observed. The half-time life was not affected by an increase in chlorpyrifos concentration.

Dimethoate ([O,O-dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate]) is an organophosphate insecticide and acaricide widely used for agricultural purposes. Genotoxicity refers to the ability of a chemical agent interact directly to DNA or act indirectly leading to DNA damage by affecting spindle apparatus or enzymes involved in DNA replication, thereby causing mutations. Taking into consideration the importance of genotoxicity induced by dimethoate, the purpose of this manuscript was to provide a mini review regarding genotoxicity induced by dimethoate as a result of oxidative stress. The present study was conducted on studies available in MEDLINE, PUBMED, EMBASE, and Google scholar for all kind of articles (all publications published until May, 2020) using the following key words: dimethoate, omethoate, DNA damage, genetic damage, oxidative stress, genotoxicity, mutation, and mutagenicity. The results showed that many studies were published in the scientific literature; the approach was clearly demonstrated in multiple tissues and organs, but few papers were designed in humans. In summary, new studies within the field are important for better understanding the pathobiological events of genotoxicity on human cells, particularly to explain what cells and/or tissues are more sensitive to genotoxic insult induced by dimethoate.

The use of pesticides is considered one of the most important threats to pollinators, especially since they are widely used in agriculture for pest control. In the last years, several studies have reported severe secondary effects on various bee species, including exotic and native bees. In this study, lethal (mortality) and sublethal (locomotor activity) effects of insecticides and acaricides used in strawberries in Brazil (abamectin, novaluron, spinetoram, and thiamethoxam) were evaluated on the native stingless bees Melipona quadrifasciata and Tetragonisca fiebrigi. The results showed that the effects varied significantly according to the pesticide, type of exposure (oral or topical), and bee species. Through oral exposure, M. quadrifasciata was more susceptible to all insecticides except for abamectin, while in topical exposure, T. fiebrigi was more sensitive. Thiamethoxam followed by spinetoram and abamectin were the most lethal, regardless of species or exposure route; novaluron was not harmful at the highest tested dose. The locomotor activity of bees was altered in the presence of sublethal doses (LC₁₀ and LC₅₀) of all insecticides. Spinetoram and abamectin can be as much as toxic as thiamethoxam against M. quadrifasciata and T. fiebrigi in laboratory experiments. These findings should be confirmed in field experiments to define possibilities to combine pest control and pollinator management. In crops like strawberries, the selectivity of native pollinators should be considered.

Nowadays, Varroa destructor is considered as a serious pest of honeybees (Apis mellifera) and its resistance to acaricides has been reported in Europe since the early 1990s. That is why new methods of treatment for Varroa mites are still in focus of many scientists. In our study, we determined the lethal concentration LC₅₀ (72 h) of 2.425% oxalic acid solution following single spray exposure of honeybee larvae under laboratory conditions (Guideline OECD 237 2013). Potential sublethal effects of oxalic acid were monitored through the determination of the activity of antioxidant enzymes. Activation of primary antioxidant enzymes was observed at 1.75% of oxalic acid; 3.5% of oxalic acid brought on a statistically significant increase of glutathione S-transferase activity. This change was accompanied by an increase in thiobarbituric acid reactive substances, products of lipid peroxidation. Our results indicate that oxalic acid may be harmful to bee brood when present during application.

Cyflumetofen is a novel benzoyl acetonitrile acaricide without cross-resistance to existing acaricides. In the present study, for the first time, the environmental behaviors of cyflumetofen and the formation of its main metabolites, 2-(trifluoromethyl) benzoic acid (B-1) and 2-(trifluoromethyl) benzamide (B-3), in the four types of soil (black soil, sierozem, krasnozem, and fluvo-aquic soil) and three types of water/sediment systems (Northeast Lake, Hunan paddy field, and Beijng Shangzhuang reservoir) under aerobic and anaerobic conditions were investigated. The degradation dynamics of cyflumetofen followed first-order kinetics. Under aerobic environment, the half-lives of cyflumetofen in black soil, sierozem, krasnozem and fluvo-aquic soil were 11.2, 10.3, 12.4, and 11.4 days. Under water anaerobic conditions, the half-lives were 13.1, 10.8, 13.9, and 12.8 days. The effects of different conditions and soil types on the half-lives of cyflumetofen were studied using a one-way ANOVA test with post hoc comparison (Tukey’s test). It was shown that the differences in black soil, krasnozem, and fluvo-aquic soil were extremely significant difference (p < 0.05) under aerobic and water anaerobic conditions. And there is a strong correlation between half-life and pH. Under aerobic environment, the half-lives of cyflumetofen in Northeast Lake, Hunan paddy field, and Beijng Shangzhuang reservoir were 15.4, 16.9, and 15.1 days. Under anaerobic conditions, they were 16.5, 17.3, and 16.1 days. Analyzing the differences of the half-lives under aerobic and anaerobic conditions, the difference only in Shangzhuang reservoir was extremely significant difference (p < 0.05). In soils, cyflumetofen degraded metabolites B-1 and B-3, from the first day 0.24 % B-1 was generated, while, only very low levels of B-3 generated at the same time. As time increased, B-3 gradually increased, cyflumetofen reduced gradually. Until 100 days, there were about 3.5 % B-1 and B-3 in the soils. In the water/sediment systems, from the first day, it degraded into B-1 in the sediment, and in the water mainly degraded into B-3.

The stereoselective cytotoxicity of new chiral acaricide etoxazole and its dissipation in citrus and soil were investigated for the first time. Enantioselective toxicity and oxidative stress of etoxazole toward MCF-7 cells was conducted. The phenomenon of dose- and form-dependent cytotoxicity was demonstrated by MTT and LDH assays, ROS generation, and SOD and CAT activity alternation. Cytotoxicity ranks were found to be consistent with oxidative damage as (R)- > Rac- > (S)-etoxazole. Moreover, the results of enantioselective degradation showed that (S)-etoxazole degraded faster than its antipode (R)-etoxazole. The gradual raise of EF values indicated the achievement of enantioselective degradation in citrus and soil, leaving the enrichment of (R)-etoxazole isomer. Significant differences of environmental behavior and cytotoxicity of etoxazole enantiomers were found in this study which provided valuable insight into the mechanism of potential toxicity and warranted more careful assessment of this pesticide before its agricultural application.