Fipronil Research Articles

Phyto-toxicological effect of fipronil to plant seedlings: Assessing germination attributes, root-tip morphology, oxidative stress, and cellular respiration indices

Pesticides including insecticides are applied in agricultural practices to control insect pests. However, their excessive usage often poses a severe threat to the growth, physiology, and biochemistry of plants. Here, responses of chickpea and greengram seedlings exposed to three fipronil (FIP) concentrations i. e. 100 (1×), 200 (2×) and 300 (3×) μg mL−1 was evaluated under in vitro. Among doses, 3× had a greater negative impact on germination attributes, root-shoot elongation, vigor indices, length ratios, and survival of seedlings. Besides, the morphological distortion in root tips, oxidative stress generation, and cellular death in fipronil-supplemented root seedlings were observed under scanning electron (SEM) and confocal laser scanning (CLSM), respectively. A significant (p ≤ 0.05) and pronounced upsurge in plant stressor metabolites such as proline, malondialdehyde (MDA), electrolyte leakage (EL), hydrogen peroxide (H2O2) content, and antioxidants enzymes in plant seedlings further confirmed the fipronil toxicity. In addition, a concentration-dependent decrease in respiration efficiency (RE) and ATP content in FIP-treated seedlings was observed. Reduced mitotic index (MI) and numerous chromosomal anomalies (CAs) in root meristematic cells of seedlings are a clear indication of insecticide-induced cytotoxicity. Furthermore, a dose-dependent increase in DNA damage in root meristematic cells of greengram revealed the genotoxic potential of fipronil. Conclusively, fipronil suggested phyto and cyto-genotoxic effects that emphasize their careful monitoring in soils before application and their optimum addition in soil-plant systems. It is high time to prepare both target-specific and slow-released agrochemical formulations for crop protection with concurrent safeguarding of the soil.

Plasmonic Au-NPs photodecorated on NiCoLDH nanosheets as a flexible SERS sensor for the real-time detection of fipronil

Rapid extraction and detection of probe molecules from curved surfaces is critical for on-site and real-time detection. In this study, a flexible platform was developed using carbon cloth (CC) to create honeycomb-like nickel cobalt layered double hydroxides (NiCoLDH) nanosheets via a simple electrodeposition technique, which were then decorated with gold nanoparticles (Au-NPs) via photodeposition process. The Au-NPs/NiCoLDH/CC was designed as a surface-enhanced Raman scattering (SERS) substrate for detecting the broad-spectrum insecticide, Fipronil (FP). The fabricated sensor achieves a superior SERS activity due to the electrodeposited NiCoLDH, which provides the charge-transfer effect, and the photodeposited Au-NPs, which generate efficient SERS hotspots through the electromagnetic effect. The Density Functional Theory (DFT) calculation was used to estimate the optimal geometry and frontier molecular orbital diagrams of the FP molecules. The influence of electrodeposition time on NiCoLDH production and Au-NPs decorating quantity was investigated in detail. Furthermore, the flexible SERS sensor has excellent sensitivity, homogeneity, a low limit of detection (LOD), and high reproducibility for FP detection. Even after 40 cycles of bending and torsion, the SERS substrate maintained excellent mechanical endurance. Through a direct-sampling approach, FP molecules on the surfaces and mesocarp region of grapes and tomatoes were successfully detected with lower LOD. These findings highlight the outstanding potential of the produced flexible SERS sensor for real-time and on-site insecticide detection, making it valuable for food security analysis and monitoring.

Impact of environmental concentrations of fipronil on DNA integrity and brain structure of Bombus atratus bumblebees

Fipronil (FP) is an insecticide used in the treatment and control of pests, but it also adversely affects bees. Currently, there is no data on the genotoxic effects of FP in the brain of bumblebees. Thus, through the comet assay and routine morphological analysis, we analyzed the morphological effects and potential genotoxicity of environmentally relevant concentrations of FP on the brain of Bombus atratus. Bumblebees were exposed at concentrations of 2.5 μg/g and 3.5 μg/g for 96 hours. After the exposure, the brains were removed for morphological and morphometric analysis, and the comet assay procedure - used to detect DNA damage in individual cells using electrophoresis. Our data showed that both concentrations (2.5 μg/g and 3.5 μg/g) caused DNA damage in brain cells. These results corroborate the morphological data. We observed signs of synapse loss in the calyx structure, intercellular spaces between compact inner and non-compact inner cells, and cell swelling. This study provides unprecedented evidence of the effects of FP on DNA and cellular structures in the brain of B. atratus and reinforces the need to elucidate its toxic effects on other species to allow future risk assessments and conservation projects.

Induction of Thymus Atrophy and Disruption of Thymocyte Development by Fipronil through Dysregulation of IL-7-Associated Genes.

The susceptibility of the immune system to immunotoxic chemicals is evident, particularly in the thymus, a vital primary immune organ prone to atrophy due to exposure to toxicants. Fipronil (FPN), a widely used insecticide, is of concern due to its potential neurotoxicity, hepatotoxicity, and immunotoxicity. Our previous study showed that FPN disturbed the antigen-specific T-cell functionality in vivo. As T-cell lineage commitment and thymopoiesis are closely interconnected with the normal function of the T-cell-mediated immune responses, this study aims to further examine the toxic effects of FPN on thymocyte development. In this study, 4-week-old BALB/c mice received seven doses of FPN (1, 5, 10 mg/kg) by gavage. Thymus size, medulla/cortex ratio, total thymocyte counts, double-positive thymocyte population, and IL-7-positive cells decreased dose-dependently. IL-7 aids the differentiation of early T-cell precursors into mature T cells, and several essential genes contribute to the maturation of T cells in the thymus. Foxn1 ensures that the thymic microenvironment is suitable for the maturation of T-cell precursors. Lyl1 is involved in specifying lymphoid cells and maintaining T-cell development in the thymus. The c-Kit/SCF collaboration fosters a supportive thymic milieu to promote the formation of functional T cells. The expression of IL-7, IL-7R, c-Kit, SCF, Foxn1, and Lyl1 genes in the thymus was significantly diminished in FPN-treated groups with the concordance with the reduction of IL-7 signaling proteins (IL-7, IL-7R, c-KIT, SCF, LYL1, FOXO3A, and GABPA), suggesting that the dysregulation of T-cell lineage-related genes may contribute to the thymic atrophy induced by FPN. In addition, FPN disturbed the functionality of thymocytes with an increase of IL-4 and IFN-γ production and a decrease of IL-2 secretion after T-cell mitogen stimulation ex vivo. Collectively, FPN significantly deregulated genes related to T-cell progenitor differentiation, survival, and expansion, potentially leading to impaired thymopoiesis.

Combined effects of TiO2 nanoparticle and fipronil co-exposure on microbiota in mouse intestine

Oral exposure to nanoparticles (NPs) may affect intestinal microbiota, and this effect may be further changed by co-contaminates. In the present study, we investigated the combined effects of TiO2 NPs and fipronil (FPN) on microbiota in mouse intestines. Mice were intragastric exposed to 5.74 mg/kg TiO2 NPs, 2.5 mg/kg FPN, or both of them, once a day, for 30 days. The results showed that individual exposure to TiO2 NPs or FPN decreased body weight and induced pathological changes in intestines. The exposure was also associated with increased cleaved caspase-3 protein, oxidative stress and decreased tight junction protein expression. Furthermore, the levels of diamine oxidase (DAO), lipopolysaccharide (LPS) and inflammatory cytokines in serum were also elevated, indicating increased intestinal barrier permeability. As expected, both TiO2 NPs and FPN decreased the diversity and altered the composition of microbiota. However, the observed effects were not further enhanced after the co-exposure to TiO2 NPs and FPN, except that Romboutsia was only significantly increased after the co-exposure to TiO2 NPs + FPN. We concluded that oral exposure to TiO2 NPs and FPN showed minimal synergistic effects on microbiota in mouse intestine.

Cellulase-responsive hydroxypropyl cellulose-anchored hollow mesoporous silica carriers for pesticide delivery

In this study, a cellulase-responsive controlled-release formulation (FPR-HMS-HPC) was developed by grafting hydroxypropyl cellulose (HPC) onto fipronil (FPR) loaded hollow mesoporous silica (HMS) nanoparticles via ester linkage. The FPR-HMS-HPC formulation was characterized using scanning and transmission electron microscopies, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The results indicated that FPR-HMS-HPC exhibited a high loading capacity of 10.0 % (w/w) and demonstrated favorable responsiveness to cellulase enzyme. Moreover, its insecticidal efficacy against Reticulitermes flaviceps surpassed that of an equivalent dose of FPR. Toxicology studies showed that the mortality and hatching rates of zebrafish exposed to FPR-HMS-HPC nanoparticles were reduced by >6.5 and 8.0 times, respectively. Thus, HPC-anchored HMS nanoparticles as insecticide delivery systems present a sustainable method for pest control significantly reducing harm to non-target organisms and the environment.

Photodegradation of the phenylpyrazole insecticide ethiprole in aquatic environments and a comparison with fipronil

Ethiprole (ETH) is a phenylpyrazole insecticide that is used worldwide as an alternative to fipronil (FIP). Research on the photodegradation of ETH in aquatic environments has been limited compared with that on FIP. In this study, to clarify the photodegradation of ETH in aquatic systems, the photodegradation pathway and products were investigated using liquid chromatography and liquid chromatography-tandem mass spectrometry. We also determined the photochemical half-lives (t1/2) of ETH and its main degradation products. The primary photodegradation pathway was cyclization/dechlorination and hydroxylation/dechlorination of ETH to form the didechlorinated products (benzimidazole of des-chloro-hydroxy-ETH). Some newly identified photodegradation products and analogs of FIP photodegradation products were also detected as minor products. We compared the photodegradation of ETH with that of FIP under the same conditions. Didechlorinated products of ETH and FIP had the highest photostability. However, although the photochemical t1/2 of EHT was 2.7 times that of FIP, the photochemical t1/2 of the didechlorinated product of ETH was approximately one-third that of the didechlorinated product of FIP. This comparison of the photochemical processes of ETH and FIP provides new insight into the persistence and characteristics of both insecticides in the environment.

Enhancing spinach (Spinacia oleracea L.) resilience in pesticide-contaminated soil: Role of pesticide-tolerant Ciceribacter azotifigens and Serratia marcescens in root architecture, leaf gas exchange attributes and antioxidant response restoration

This study unveils the detoxification potential of insecticide-tolerant plant beneficial bacteria (PBB), i.e., Ciceribacter azotifigens SF1 and Serratia marcescens SRB1, in spinach treated with fipronil (FIP), profenofos (PF) and chlorantraniliprole (CLP) insecticides. Increasing insecticide doses (25–400 μg kg−1 soil) significantly curtailed germination attributes and growth of spinach cultivated at both bench-scale and in greenhouse experiments. Profenofos at 400 μg kg−1 exhibited maximum inhibitory effects and reduced germination by 55%; root and shoot length by 78% and 81%, respectively; dry matter accumulation in roots and shoots by 79% and 62%, respectively; leaf number by 87% and leaf area by 56%. Insecticide application caused morphological distortion in root tips/surfaces, increased levels of oxidative stress, and cell death in spinach. Application of insecticide-tolerant SF1 and SRB1 strains relieved insecticide pressure resulting in overall improvement in growth and physiology of spinach grown under insecticide stress. Ciceribacter azotifigens improved germination rate (10%); root biomass (53%); shoot biomass (25%); leaf area (10%); Chl-a (45%), Chl-b (36%) and carotenoid (48%) contents of spinach at 25 μg CLP kg−1 soil. PBB inoculation reinvigorated the stressed spinach and modulated the synthesis of phytochemicals, proline, malondialdehyde (MDA), superoxide anions (O2•–), and hydrogen peroxide (H2O2). Scanning electron microscopy (SEM) revealed recovery in root tip morphology and stomatal openings on abaxial leaf surfaces of PBB-inoculated spinach grown with insecticides. Ciceribacter azotifigens inoculation significantly increased intrinsic water use efficiency, transpiration rate, vapor pressure deficit, intracellular CO2 concentration, photosynthetic rate, and stomatal conductance in spinach exposed to 25 μg FIP kg−1. Also, C. azotifigens and S. marcescens modulated the antioxidant defense systems of insecticide-treated spinach. Bacterial strains were strongly colonized to root surfaces of insecticide-stressed spinach seedlings as revealed under SEM. The identification of insecticide-tolerant PBBs such as C. azotifigens and S. marcescens hold the potential for alleviating abiotic stress to spinach, thereby fostering enhanced and safe production within polluted agroecosystems.

Optical Control of Insect Behavior and Receptors with Azobenzene-Bridged Fipronil and Imidacloprid.

Photopharmacology can be implemented in a way of regulating drug activities by light-controlling the molecular configuations. Three photochromic ligands (PCLs) that bind on one or two sites of GABARs and nAChRs were reported here. These multiphoton PCLs, including FIP-AB-FIP, IMI-AB-FIP, and IMI-AB-IMI, are constructed with an azobenzene (AB) bridge that covalently connects two fipronil (FIP) and imidacloprid (IMI) molecules. Interestingly, the three PCLs as well as FIP and IMI showed great insecticidal activities against Aedes albopictus larvae and Aphis craccivora. IMI-AB-FIP in both trans/cis isomers can be reversibly interconverted depending on light, accompanied by insecticidal activity decrease or increase by 1.5-2.3 folds. In addition, IMI-AB-FIP displayed synergistic effects against A. craccivora (LC50,IMI-AB-FIP = 14.84-22.10 μM, LC50,IMI-AB-IMI = 210.52-266.63 μM, LC50,andFIP-AB-FIP = 36.25-51.04 μM), mainly resulting from a conceivable reason for simultaneous targeting on both GABARs and nAChRs. Furthermore, modulations of wiggler-swimming behaviors and cockroach neuron function were conducted and the results indirectly demonstrated the ligand-receptor interactions. In other words, real-time regulations of receptors and insect behaviors can be spatiotemporally achieved by our two-photon PCLs using light.

Multiple barriers as an efficient treatment for removing pesticides aiming direct potable reuse: A pilot scale study

Water reuse for potable purposes can represent a realistic source supply of drinking water in areas with water scarcity. Therefore, combining conventional wastewater treatment technologies with advanced technologies is necessary to remove contaminants and obtain high-quality and safe water. In this study, the pesticides and degradation products, atrazine (ATZ), hydroxyatrazine (ATZOH), deethylatrazine (DEA), deisopropylatrazine (DIA), simazine (SMZ), ametryn (AMT), diuron (DIU), 2,4-D, fipronil (FIP), fipronil sulfide (FIP-SF) and fipronil sulfone (FIP-SN) were evaluated in effluent after membrane bioreactor (MBR), effluent after advanced treatment by multiple barriers (MBR, reverse osmosis, UV/H2O2 and activated carbon), in tap water collected in the urban region of Campinas and in the Atibaia River (water supply source from city of Campinas). The pesticide concentrations in the Atibaia River and the post-MBR effluent ranged between 1 and 434 ng L−1 and 1 and 470 ng L−1, respectively. Therefore, the Atibaia River and the post-MBR effluent had the same magnitude pesticide concentrations. In the production of potable water reuse, after the multiple barriers processes, only fipronil (1 ng L−1) and atrazine (3 ng L−1) were quantified in some of the samples. In tap water from Campinas, atrazine, ATZOH, DEA, diuron, and 2,4-D were quantified in concentrations ranging between 3 and 425 ng L−1. Therefore, when comparing drinking water obtained from conventional treatment with potable water reuse, according to the pesticides studied, it is possible to conclude that the advanced treatment used on a pilot scale is promising for use in a potable water reuse plant. However, studies involving more microbiological and chemical parameters should be conducted to classify potable water reuse as drinking water.

Protective effects of naringin on fipronil-induced cardiovascular and renal dysfunctions in rats

BackgroundNaringin as a bioflavanone glycoside is abundant in citrus fruits, which since ancient times have been utilized as natural herbal treatments in traditional medicine. Naringin has potent antioxidant effect that may mitigate oxidative stress mediated cardiovascular and renal dysfunctions in mammalian systems. ObjectiveTo explore probable modulatory actions of naringin on fipronil-induced cardio-renal dysfunctions. MethodsTwenty-four Wistar rats weighing 140 ± 3.0 g were divided into four groups including normal control (saline), 10 mg/kg Fipronil (FIP), FIP+100 mg/kg naringin, and 100 mg/kg naringin. Administration of naringin and fipronil was by oral gavage for 28 consecutive days. Urinalysis, blood pressure monitoring, biochemical assays, histology, and immunohistochemical evaluations were performed. ResultsNaringin significantly (P < 0.001) lessened blood pressure parameters, oxidative stress markers but significantly (P < 0.001) heightened the systemic antioxidants. Likewise, naringin prevented fipronil-induced histopathological lesions such as congestion and cellular infiltration in cardiac and renal tissues. Moreover, naringin attenuated the immunohistochemical expression of troponin 1 and matrix metalloperoxidase-2 in cardiac tissues, but heightened angiotensin converting enzyme 2 expression in contrast to that of fipronil group. ConclusionThe observation in this study shows potent attenuation of fipronil-induced toxicity by naringin, through inhibiting processes related to oxidation and inflammation.

The effect of fipronil exposure on the activity of biotransformation enzymes and histology in the liver of grass carp

Fipronil (FPN) is an insecticide used in agriculture. This study focused on the biotransformation process and the histopathological effects of FPN in the liver of grass carp. Fish were exposed to environmental concentrations of FPN (3, 6, and 10 ug l-1) for up to 14 d. The alterations in phase I and II biotransformation enzyme activity (ethoxyresorufin-O-deethylase [EROD] and glutathione-S-transferase [GST]), malondialdehyde (MDA) content, and histopathology in the liver were studied on the 1st, 3rd, 7th, and 14th days. Results showed that EROD (dose-dependent) and GST activity (time-dependent) increased. The MDA content increased in a time- and dose-dependent manner. The most common types of hepatological damage were steatosis, vein dilatation, pyknosis, and increased melanomacrophage centers, probably due to oxidative stress originating from biotransformation enzyme activity (R2 = 0.88 for GST and MDA). The degree of tissue change (DTC) at the highest dose indicated moderate damage to the liver (R2 = 0.82 for GST and DTC). Nevertheless, the level of EROD and GST activity and MDA content indicated complex interactions among various phase I and phase II biotransformation enzymes which should be investigated in future studies with more replications.

Microcontaminants degradation in tertiary effluent by modified solar photo-Fenton process at neutral pH using organic iron complexes: Influence of the peroxide source and matrix composition

Peroxymonosulfate (HSO5–) and persulfate (S2O82–), both sources of sulfate radicals (SO4*–), were evaluated for the first time in modified solar photo-Fenton using Fe-chelating agents (nitriloacetic acid (NTA), ethylene diaminetetraacetic acid (EDTA), ethylenediamine-N,N′-disuccinic acid (EDDS) and citrate (Cit)) in comparison with hydrogen peroxide (H2O2) to degrade benzophenone-3 (BP-3), fipronil (FIP) and propylparaben (PPB) (100 µg L–1 each) in municipal tertiary effluent. Increasing HSO5– concentrations from 1.5 to 5.9 mmol L–1 reached ≥ 96 % removal for all iron complexes, while treatment efficiencies for all tested S2O82– concentrations (1.5–5.9 mmol L–1) were limited to 20 % to 55 %. This difference can be attributed to a pH decrease in the HSO5– system. The influence of pH and matrix composition upon treatment performance were also assessed in the FeNTA/S2O82– system, which was more efficient at pH < 7.0 due to higher availability of soluble iron, and partial removal of bicarbonate and humic acids caused by acidification. Matrix composition significantly influenced the process as higher degradation rates were achieved after isolated or combined removals of chloride, bicarbonate and sulfate. The comparison between naproxen (a high electron density compound) degradation and that of BP-3, FIP, and PPB by SO4*– - based advanced oxidation processes (SR-AOPs) was used to evaluate the influence of target compound structures upon treatment performance. S2O82− and HSO5– were ineffective for treatment at pH 7.0. Thus, H2O2 was the best peroxide source for target compounds degradation at neutral pH as this is the natural pH of municipal tertiary effluent and results indicated that the assessment and choice for SR-AOPs should consider the chemical structure of target compounds.

Quantitative differentiation of toxicity contributions and predicted global risk of fipronil and its transformation products to aquatic invertebrates

Biotransformation often alters chemical toxicity, yet its impacts on risk assessment are hardly quantified due to the challenges in acquiring internal exposure-based thresholds for chemicals that are readily metabolizable. Here, we integrated toxic unit and toxicokinetics to quantitatively assess toxicity contributions and potential risk of both parent compound and transformation products (TPs) to aquatic organisms, using fipronil (FIP) as a representative toxicant. In aquatic invertebrates Chironomus dilutus and Hyalella azteca, approximately 90 % of FIP was transformed to fipronil sulfone (SUL). FIP and SUL exhibited similar intrinsic toxicity to these organisms, which was contrary to conventional perception that SUL was more toxic than FIP. However, biotransformation was still important in risk assessment because the TP had 10-fold slower depuration rate than FIP. The amphipod H. azteca was found to be as sensitive to FIPs as the insect C. dilutus, which was previously considered ten times more sensitive based on external thresholds. This discrepancy has led to overlooking the toxicity of FIP to H. azteca in regional risk assessments. Lastly, we predicted the lethal risk of FIPs in global surface water. When using external thresholds for prediction, FIPs in 3.4 % of the water samples were lethally toxic to H. azteca, and the percentage of water samples at risk increased to 14 % when internal thresholds were used and SUF dominated the risk. This study presents an improved method for quantifying aquatic risk of readily metabolized toxicants. Our findings underscore the urgency of considering TPs in water quality assessments, especially for sensitive species that are at risk in the environment.

Rapid and Sensitive On-Site Detection of Fipronil in Foods Using Evanescent Wave Fluorescent Immunosensor

Fipronil (FIP), a broad-spectrum phenylpyrazole insecticide, is highly toxic and threatens human health and ecological balance. Developing convenient, rapid, portable analytical technology for on-site and high-frequency testing of FIP is essential to reduce its damage. Herein, a monoclonal antibody (Clone F-3F6) against FIP, with high affinity and specificity, was produced using a novel immunogen, FIP-BSA, which was simply and directly synthesized by conjugating FIP with bovine serum albumin (BSA). Among the previously reported antibodies, F-3F6 acts more specifically against FIP. The FIP metabolites fipronil desulfinyl, fipronil sulfide, and fipronil sulfone showed lower cross-reactivity, and other pesticides were not recognized. To achieve high-frequency and on-site measurements of FIP, an evanescent wave fluorescence biosensor was built by integrating evanescent wave fluorescence technology, a functionalized fiber bioprobe, and a fluorescence-labeled F-3F6 antibody. The detection limit of FIP was 0.032 μg/L. The detection results of real milk and water samples showed that all the coefficients of variation were less than 10%, and the recovery ranged from 90 to 120%. The high reusability and stability of functionalized fiber bioprobe enables the accurate, cost-effective, high-frequency, and facile quantitative detection of FIP. This highly specific and reliable evanescent wave fluorescence biosensor will be well suited to the sensitive and high-frequency on-site analysis of only FIP in food.

Effect of Fipronil Exposure on Hematological Aspects of Rhesus Monkeys (Macaca mulatta): Risk and Toxicity Assessment in Agro-Workers.

Fipronil (FPN) is a broad-spectrum phenylpyrazole insecticide, widely used in agriculture and veterinary medicine. Published research on FPN toxicity has established the fact that its inhalation or dermal exposure may lead to very serious clinical outcomes in non-target animals. In line to its exposure and toxicity related damage, FPN has been investigated in many invertebrates, however, its exposure-related noxiousness is less reported in higher animals. To assess the FPN-induced effects to agro-workers in the field, in the present study, we used physiological human surrogates, adult rhesus monkeys as models. We exposed well habituated, chair restraint adult rhesus monkeys with a field spray concentration of FPN (0.3 mg/1 mL distilled water) through an inhalation route in the closed system. Animals were divided into control and treatment groups, each containing three animals. Inflammatory and hematological effects were determined by evaluating the kidney and liver biomarker enzymes; serum creatinine and alanine transaminase (ALT), aspartate transaminase (AST) levels respectively. Our findings reveal that FPN treated monkeys show significantly increased levels of ALT (p = 0.000461), AST (p = 0.0681) and creatinine (p = 0.00656) as compared to the control group. Furthermore, significant differences of red blood cells (RBCs) (p = 0.0139) and white blood cells (WBCs) (p = 0.00642) were also observed in the treated and control group monkeys which reflect strong toxic effects on the blood cells. Our findings demonstrate that FPN exposure is very toxic to higher animals and causes severe damage to the liver and kidneys along with other clinical problems. The study highlights the effect and impact of passive inhalation of insecticides in intentionally carefree agro-workers and raises the concern of public awareness toward pesticides use.

A new N/Fe doped carbon dot nanosurface molecularly imprinted polymethacrylate nanoprobe for trace fipronil with SERS/RRS dimode technique

The N and Fe doped carbon dot (CDNFe) was prepared by microwave procedure. Using CDNFe as the nano-substrate, fipronil (FL) as the template molecule and α-methacrylic acid as the functional monomer, the molecular imprinted polymethacrylic acid nanoprobe (CDNFe@MIP) with difunction was synthesized by microwave procedure. The CDNFe@MIP was characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier infrared spectroscopy, and other techniques. The results show that the nanoprobe not only distinguish FL but also has a strong catalytic effect on the HAuCl4–Na2C2O4 nanogold indicator reaction. When the nanoprobes specifically recognize FL, their catalytic effect is significantly reduced. Since the AuNPs generated by HAuCl4 reduction have strong surface-enhanced Raman scattering (SERS) and resonance Rayleigh scattering (RRS) effects, a SERS/RRS dual-mode sensing platform for detecting 5–500 ng/L FL was constructed. The new analytical method was applied to detect FL in food samples with a relative standard deviation (RSD) of 3.3–8.1 % and a recovery rate of 94.6–104.5 %.

Determination of fipronil and its three degradates in water using stir bar sorptive extraction–thermal desorption–gas chromatography–tandem mass spectrometry

A method was developed for determination of fipronil (FIP) pesticide and its three major degradates (fipronil desulfinyl, fipronil sulfide, fipronil sulfone) in water at the levels required by the EU Commission in the Decision 2022/1307. The method combines solvent-free stir bar sorptive extraction (SBSE) with thermal desorption–gas chromatography–tandem mass spectrometry (TD–GC–MS/MS). Simple sample processing involves 16 h of stirring a 100 mL water sample with a polydimethylsiloxane-coated sorptive stir bar, followed by TD of the trapped analytes into the GC. The greenness assessment by analytical Eco-Scale approach resulted in classification of the entire analytical method as "an excellent green analysis". The obtained limits of quantification for all FIPs determined in tap, lake, MilliQ water and artificial seawater were in the range of 0.12–0.30 ng L–1. The recoveries ranged between 81.7 and 109% with relative standard deviations from 2.8 to 14%. The results show that the method is suitable for screening and monitoring the studied analytes in selected matrices.

Histopathological and Behavioral Impairments in Zebrafish (Danio rerio) Chronically Exposed to a Cocktail of Fipronil and Pyriproxyfen.

Lately, the high incidence of pesticide usage has attracted everyone's interest due to the serious effects produced. Fipronil (FIP) is a phenylpyrazole compound that acts on the insect's GABA neurotransmitter by inhibiting its activity. Moreover, the literature reports highlight its implication in neurodevelopmental abnormalities and oxidative stress production in different organisms. Similarly, pyriproxyfen (PYR) is known to affect insect activity by mimicking the natural hormones involved in the maturation of the young insects. The aim of the present study was to investigate the impact of the mixture of these pesticides on the tissues and behavior of zebrafish. To assess the influence of this cocktail on zebrafish, three groups of animals were randomly selected and exposed to 0, 0.05, and 0.1 mg L-1 FIP and PYR mixture for five days. The fish were evaluated daily by the T-maze tests for locomotor activity and the light-dark test and recordings lasted four min. The data were quantified using the EthoVision software. Our results indicated significant changes in locomotor activity parameters that showed increased levels following exposure to the mixture of FIP and PYR. On the other hand, the mixture also triggered anxiety in the zebrafish, which spent more time in the light area than in the dark area. In addition, mixture-induced histological changes were observed in the form of numerous hemosiderin deposits found in various zebrafish tissues. The current findings indicate that the mixture of FIP and PYR can have considerable consequences on adult zebrafish and may promote or cause functional neurological changes in addition to histological ones.

Removal of fipronil by advanced oxidative processes using sulfite activated by cobalt immobilized on silica

Sulfite auto-oxidation catalyzed by cobalt complexed with ammonia deposited on silica (CoNSi) was used to generate sulfate radicals. The material was characterized by ATR–FTIR, suggesting that the silica structure did not change, and SEM–EDS, indicating an uniform dispersion of cobalt across the material surface according with XRD results. BET analysis provided information on a mesoporous material (type IV isotherm) with regular morphology (H1 hysteresis). The DSC analysis showed that CoNSi is thermally stable under the studied conditions. Quantitative analysis of Fipronil (FIP) was performed by HPLC-DAD, where the applied method was selective and linear. The Box–Behnken experimental design (BBD) method was used to define the best condition for removing the analyte in water. It was found that in 60 min, 76% removal of 1.8 mg L−1 of FIP was reached by adding 0.30 g of the material and 0.30 g of the sulfite in a solution under stirring, aeration, pH 8.0, and room temperature and protected from radiation. However, analysis of cobalt leaching into the solution by FAAS showed a small amount of the metal (0.44 mg L−1) informing that the synthesis of the material must be improved.