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The pyrethroid bifenthrin and the phenylpyrazole fipronil are widely employed insecticides, and their extensive use became an environmental issue. Therefore, this study evaluated their biodegradation employing bacterial strains of Bacillus species isolated from leaves of orange trees, aiming at new biocatalysts with high efficiency for use singly and in consortium. Experiments were performed in liquid culture medium at controlled temperature and stirring (32 °C, 130 rpm). After 5 days, residual quantification by HPLC-UV/Vis showed that Bacillus amyloliquefaciens RFD1C presented 93% biodegradation of fipronil (10.0 mg.L−1 initial concentration) and UPLC-HRMS analyses identified the metabolite fipronil sulfone. Moreover, Bacillus pseudomycoides 3RF2C showed a biodegradation of 88% bifenthrin (30.0 mg.L−1 initial concentration). A consortium composed of the 8 isolated strains biodegraded 81% fipronil and 51% bifenthrin, showing that this approach did not promote better results than the most efficient strains employed singly, although high rates of biodegradation were observed. In conclusion, bacteria of the Bacillus genus isolated from leaves of citrus biodegraded these pesticides widely applied to crops, showing the importance of the plant microbiome for degradation of toxic xenobiotics.

Fipronil, a widely used phenylpyrazole insecticide, is known to disrupt circulating thyroid hormone (TH) levels in rodents. Concentrations of fipronil and its metabolites (fipronil sulfone and fipronil sulfide) in serum samples collected in 2009–2011 were measured for 131 Japanese pregnant women by a sensitive and accurate liquid chromatography-tandem mass spectrometric method developed in our laboratory to relate TH levels. Fipronil sulfone was detected in all the subjects with the median being 21 ng/L (min–max: 6.8–89), but fipronil and fipronil sulfide were detected in none of the subjects (detection limit: 5.0 and 1.2 ng/L, respectively), indicating a rapid and exclusive oxidative conversion to fipronil sulfone upon exposure. The median concentration of fipronil sulfone was lower than those previously reported for general populations in other countries by one order of magnitude. There were no attributes or dietary habits of the subjects that significantly vary the serum fipronil sulfone concentrations. Multiple regression analyses found no significant association between serum concentrations of fipronil sulfone and free thyroxine- or thyroid-stimulating hormone levels, indicating the absence of adverse effects on circulating TH levels probably due to the lower exposure levels of the present subjects. The present result would be valuable for establishing a dose–effect relationship of fipronils in humans on population levels.

New information on the lethal and sublethal effects of neonicotinoids and fipronil on organisms is presented in this review, complementing the previous Worldwide Integrated Assessment (WIA) in 2015. The high toxicity of these systemic insecticides to invertebrates has been confirmed and expanded to include more species and compounds. Most of the recent research has focused on bees and the sublethal and ecological impacts these insecticides have on pollinators. Toxic effects on other invertebrate taxa also covered predatory and parasitoid natural enemies and aquatic arthropods. Little new information has been gathered on soil organisms. The impact on marine and coastal ecosystems is still largely uncharted. The chronic lethality of neonicotinoids to insects and crustaceans, and the strengthened evidence that these chemicals also impair the immune system and reproduction, highlights the dangers of this particular insecticidal class (neonicotinoids and fipronil), with the potential to greatly decrease populations of arthropods in both terrestrial and aquatic environments. Sublethal effects on fish, reptiles, frogs, birds, and mammals are also reported, showing a better understanding of the mechanisms of toxicity of these insecticides in vertebrates and their deleterious impacts on growth, reproduction, and neurobehaviour of most of the species tested. This review concludes with a summary of impacts on the ecosystem services and functioning, particularly on pollination, soil biota, and aquatic invertebrate communities, thus reinforcing the previous WIA conclusions (van der Sluijs et al. 2015 ).

Ticks are blood-feeding ecto-parasites that have a cosmopolitan distribution in tropical and subtropical regions of the world. Ticks cause economic losses in the form of reduced blood, meat and dairy products, as well as pathogen transmission. Different acaricides such as organochlorines, organophosphates, formamidines (e.g. amitraz), synthetic pyrethroids, macrocyclic lactones, fipronil, and fluazuron are currently used sequentially or simultaneously to control tick infestations. Most acaricide treatments now face increasingly high chances of failure, due to the resistance selection in different tick populations against these drugs. Acaricide resistance in ticks can be developed in different ways, including amino acid substitutions that result in morphological changes in the acaricide target, metabolic detoxification, and reduced acaricide entry through the outer layer of the tick body. The current literature brings a plethora of information regarding the use of different acaricides for tick control, resistance selection, analysis of mutations in target sites, and resistance mitigation. Alternatives such as synergistic use of different acaricides, plant-derived phytochemicals, fungi as biological control agents, and anti-tick vaccines have been recommended to avoid and mitigate acaricide resistance. The purpose of this review was to summarize and discuss different acaricides applied for tick control, their mechanisms of action and resistance selection, genetic polymorphisms in their target molecules, as well as the approaches used for diagnosis and mitigation of acaricide resistance, specifically in Rhipicephalus microplus ticks.

In this paper, a new synthetic route is introduced for the synthesis of high-luminescent greenish-yellow fluorescent copper nanoclusters (PVP@ A. senna -Cu NCs) using Avaram senna ( A. senna ) and polyvinylpyrrolidone (PVP) as templates. A. senna plant extract mainly contains variety of phytochemicals including glycosides, sugars, saponins, phenols, and terpenoids that show good pharmacological activities such as anti-inflammatory, antioxidant, and antidiabetic. PVP is a stable and biocompatible polymer that is used as a stabilizing agent for the synthesis of PVP@ A. senna -Cu NCs. The size, surface functionality, and element composition of the fabricated Cu NCs were confirmed by various analytical techniques. The as-prepared greenish-yellow fluorescent Cu NCs exhibit significant selectivity towards fipronil, thereby favoring to assay fipronil pesticide with good linearity in the range of 3.0–30 μM with a detection limit of 65.19 nM. More importantly, PVP@ A. senna -Cu NCs are successfully applied to assay fipronil in vegetable and grain samples.

We investigated insecticide resistance profiles of field populations of the German cockroach, Blattella germanica (L.), collected from central regions of Thailand. Seven strains (PW, RB, MTH, MTS, TL, AY, and SP) were evaluated with diagnostic doses (DD; 3 × LD95 generated from a susceptible strain) of deltamethrin, fipronil, and imidacloprid using topical assays and compared with a susceptible strain (DMSC). Results showed fipronil (2–27% mortality), deltamethrin (16–58% mortality), and imidacloprid (15–75% mortality) resistance in the field strains. Synergism studies with piperonyl butoxide (PBO) and S,S,S-tributyl phosphorotrithioate (DEF) in combination with the DD of insecticides significantly increased (P < 0.05) mortality of the test insects of the field strains suggesting the involvement of P450 monooxygenase and esterase pathways of detoxification. Gel bait evaluations demonstrated that all field-collected strains were resistant to Maxforce Forte (0.05% fipronil), Maxforce Fusion (2.15% imidacloprid), and Advion Cockroach Gel Bait (0.6% indoxacarb) with mean survival times ranging from 1.87–8.27, 1.77–11.72, and 1.19–3.56 days, respectively. Molecular detection revealed that the Rdl mutation was completely homozygous in all field-collected strains except in the PW strain. Field-collected strains were screened for 3 voltage-gated sodium channel (VGSC) mutations associated with pyrethroid resistance. The L993F mutation was present in 5 strains, but no C764R and E434K mutations were detected.

This work presents a surface-enhanced Raman scattering (SERS) and density functional theory (DFT) study of a fipronil adsorbed on colloidal silver nanoparticles (AgNPs). A standard curve was established to quantify fipronil within a range of 0.0001–0.1 ppm (r2 ≥ 0.985), relying on the unique fipronil Raman shift at ~2236 cm−1 adsorbed on AgNPs. DFT calculations suggest that the nitrile moiety (C≡N) binding should be slightly more favorable, by 1.92 kcal/mol, than those of the nitrogen atom of the pyrazole in fipronil and Ag6 atom clusters. The characteristic peaks of the SERS spectrum were identified, and both the calculated vibrational wavenumbers and the Raman intensity pattern were considered. The vibrational spectra of fipronil were obtained from the potential energy distribution (PED) analysis and selective Raman band enhancement.

Eighty 24-week-old laying hens were divided into eight groups, seven given a single oral dose per chicken with 7 dosing levels from 13.6 to 137 mg/kg body weight (bw) and one serving as sham control. The hens were observed for 28 days for clinical abnormalities, egg yield, and body weight. Egg samples from groups of low-to-medium doses were analyzed for residues of fipronil and its metabolites by LC–MS/MS. Blood and organ samples from hens of the group receiving 63.3 mg/kg bw were collected for hematochemical and histopathological analysis. We found that the median lethal dose (LD 50 ) of fipronil was 74 mg/kg bw for laying hens. No death occurred, and there were no obvious changes in body weight and egg production in the hens receiving doses at or below 20 mg/kg bw. In the hens that survived exposure to the dose at 63.3 mg/kg bw, there was significant reduction in body weight and egg yield; histopathological changes in the liver and kidney; and increased levels of creatine, urea, glutamate oxaloacetate transferase, and glutamate pyruvic transaminase. Fipronil-sulfone was the residual marker in eggs with significantly higher concentrations and longer withdrawal periods than its maternal compound. We conclude that fipronil is efficiently transformed into fipronil-sulfone in the body with subsequent excretion into eggs. More attention should be paid to the potential food safety risk of fipronil-sulfone because of its persistence in eggs.

Mass mortalities of honey bees occurred in France in the 1990s coincident with the introduction of two agricultural insecticides, imidacloprid and fipronil. Imidacloprid, a neonicotinoid, was widely blamed, but the differential potency of imidacloprid and fipronil has been unclear because of uncertainty over their capacity to bioaccumulate during sustained exposure to trace dietary residues and, thereby, cause time-reinforced toxicity (TRT). We experimentally quantified the toxicity of fipronil and imidacloprid to honey bees and incorporated the observed mortality rates into a demographic simulation of a honey bee colony in an environmentally realistic scenario. Additionally, we evaluated two bioassays from new international guidance for agrochemical regulation, which aim to detect TRT. Finally, we used analytical chemistry (GC-MS) to test for bioaccumulation of fipronil. We found in demographic simulations that only fipronil produced mass mortality in honey bees. In the bioassays, only fipronil caused TRT. GC-MS analysis revealed that virtually all of the fipronil ingested by a honey bee in a single meal was present 6 d later, which suggests that bioaccumulation is the basis of TRT in sustained dietary exposures. We therefore postulate that fipronil, not imidacloprid, caused the mass mortalities of honey bees in France during the 1990s because it is lethal to honey bees in even trace doses due to its capacity to bioaccumulate and generate TRT. Our results provide evidence that recently proposed laboratory bioassays can discriminate harmful bioaccumulative substances and, thereby, address evident shortcomings in a regulatory system that had formerly approved fipronil for agricultural use.

The sustainable control of many highly damaging insect crop pests and disease vectors is threatened by the evolution of insecticide resistance. As a consequence, strategies have been developed that aim to prevent or delay resistance development by rotating or mixing insecticides with different modes of action (MoA). However, these approaches can be compromised by the emergence of mechanisms that confer cross-resistance to insecticides with different MoA. Despite the applied importance of cross-resistance, its evolutionary underpinnings remain poorly understood. Here we reveal how a single gene evolved the capacity to detoxify two structurally unrelated insecticides with different MoA. Using transgenic approaches we demonstrate that a specific variant of the cytochrome P450 CYP6ER1, previously shown to confer resistance to the neonicotinoid imidacloprid in the brown planthopper, N . lugens , also confers cross-resistance to the phenylpyrazole ethiprole. CYP6ER1 is duplicated in resistant strains, and we show that while the acquisition of mutations in two encoded substrate recognition sites (SRS) of one of the parologs led to resistance to imidacloprid, a different set of mutations, outside of known SRS, are primarily responsible for resistance to ethiprole. Epistatic interactions between these mutations and their genetic background suggest that the evolution of dual resistance from the same gene copy involved functional trade-offs in respect to CYP6ER1 catalytic activity for ethiprole versus imidacloprid. Surprisingly, the mutations leading to ethiprole and imidacloprid resistance do not confer the ability to detoxify the insecticide fipronil, another phenylpyrazole with close structural similarity to ethiprole. Taken together, these findings reveal how gene duplication and divergence can lead to the evolution of multiple novel functions from a single gene. From an applied perspective they also demonstrate how cross-resistance to structurally unrelated insecticides can evolve, and illustrate the difficulty in predicting cross-resistance profiles mediated by metabolic mechanisms.