• Journal of the Korean Magnetic Resonance Society
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• v.24 no.4
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• pp.104-116
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• 2020

Fipronil, the phenylpyrazole insecticide, is effective and used in various fields. Especially, fipronil was reliable because it was known to be specific on invertebrate animals than vertebrate animals including mammals. However, fipronil had potential risks that affect vertebrate animals as it blocks the gamma-aminobutyric acid (GABA) receptors that also exists in vertebrates as well as invertebrates. Therefore, it was necessary that harmful effects of fipronil on vertebrates are clarified. For this purpose, the zebrafish (Danio rerio) were used on behalf of vertebrate animals in present study. The zebrafish were exposed to 5 ㎍/L, 25 ㎍/L, and 50 ㎍/L of fipronil during 12, 24 and 72 hours. To closely observe toxic process, 12 hours and 24 hours of additional time point were set in the exposure test. Nuclear magnetic resonance (NMR)-based metabolomics is an approach to detect metabolic changes in organism resulted from external stimuli. In this study, NMR-based metabolomics showed the metabolic changes in zebrafish caused by fipronil exposure. Metabolic analysis revealed that fipronil interfered with energy metabolism and decreased the antioxidant ability in zebrafish. Antioxidant ability decline was remarkable at high exposure concentration. In addition, metabolic analysis results over time suggested that reactions for alleviating the excessive nerve excitation occurred in zebrafish after fipronil exposure. Through this study, it was elucidated that the adverse effects of fipronil on vertebrate animals are evident. The risk of fipronil on vertebrates can be no longer ignored. Moreover, this study has a meaning of practically necessary research for organism by examining the effects of fipronil at low concentrations existed in real environment.

• Journal of Veterinary Science
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• v.23 no.6
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• pp.82.1-82.6
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• 2022

Domestic poultry are among the non-target species of exposure to fipronil, but limited information is available on the metabolic effects of fipronil exposure in avian. We investigated the comparative capacity of in vitro biotransformation of fipronil among chicken, duck, quail, goose, and rat. Interspecies differences in kinetic parameters were observed; the clearance rate calculations (Vmax/Km) indicated that chicken and duck are more efficient in the cytochrome P450-mediated metabolism of fipronil to sulfone than quail, goose and rat. The lower hepatic clearance of fipronil in quail, goose and rat, suggested that fipronil sulfone may serve as a biomarker to indicate fipronil exposure in these species.

• Korean Journal of Agricultural Science
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• v.49 no.1
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• pp.103-112
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• 2022

Fipronil is a popular insecticide used in both agricultural and domestic fields. Factors that affect sperm and eggs have a direct influence on reproductive outcomes. This study was undertaken to assess the effect of varying concentrations (10 - 200 μM) of fipronil and incubation times (30 min and 2 hrs) on boar spermatozoa. Spermatozoa were evaluated for motility, motion kinematics, viability, chromatin stability, and for the generation of intracellular reactive oxygen species (ROS) and the results were compared to those from corresponding controls. The findings revealed a significant, dose-dependent reduction in sperm motility in all fipronil treatment groups at 30 min of incubation (p < 0.05). A similar dose-dependent reduction in sperm motility was observed subsequent to fipronil exposure for 2 hrs of incubation (p < 0.05). Groups treated with fipronil showed a gradual reduction in motion kinematics (p < 0.05). Moreover, a significantly higher percentage of dead sperm was observed at 200 μM fipronil, as compared to the highest live percentage obtained in controls (p < 0.05). Evaluating the sperm chromatin integrity revealed a significantly higher percentage of damaged chromatin in spermatozoa incubated with 200 μM of fipronil. Moreover, ROS production was significantly higher in fipronil-exposed sperm (p < 0.05). In conclusion, boar spermatozoa incubated with fipronil showed decreased levels of sperm motility and viability, weaker chromatin integrity, and increased levels of intracellular ROS generation, all of which indicate that exposure to fipronil potentially impairs the fertilization competence of boar spermatozoa.

• Entomological Research
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• v.48 no.6
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• pp.459-465
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• 2018

The present study evaluated the efficacy of Maxforce gel baits containing 0.01% fipronil (Maxforce), 0.05% fipronil (Maxforce Magnum), 1.0% clothianidin (Maxforce Impact), and 0.6% indoxacarb (Avion gel bait; all from Bayer Environmental Science, Clayton, CA, USA) against reference and wild strains (Mobasher, Andisheh, Tamin-e Ejtemaei, and Maskoni) of German cockroach collected in 2016. Test design and bait placement were according to World Health Organization (WHO) procedures for efficacy achieving a 95% mortality rate. Although cockroaches fed on all gel baits, gel baits containing clothianidin and indoxacarb were eaten at higher rates than gel baits containing 0.01% and 0.05% fipronil. The cumulative mortality rates reached 100% for all cockroach strains at 32, 28, 28 and 40 h after eating baits containing 0.01% fipronil, 0.05% fipronil, clothianidin, and indoxacarb, respectively. Efficacy (a 95% mortality rate) after exposure (consumption) of gel baits containing 0.05% fipronil and clothianidin was seen after 28 h, compared with 32 h for 0.01% fipronil and 40 h for indoxacarb. In conclusion, commercial gel baits have improved and may be more effective than spray formulations against German cockroaches.

• Journal of the Korean Chemical Society
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• v.63 no.6
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• pp.415-419
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• 2019

Fipronil is an insecticide that belongs to the N-phenylpytazole and has been used mainly for an insect pest control. However, it is known that acute poisoning of the human body causes various symptoms such as dizziness, muscle weakness, dyspnea, skin irritation, and increased heart rate. Lately, eggs containing fipronil have been distributed and toxic problems are spreading around the world. In this study, we tried to develop analytical methods to evaluate the exposure of fipronil and fipronil sulfone in animal serum samples. The differences according to mobile phase and the results of liquid - liquid extraction and solid phase extraction pretreatment method were compared. Distilled water (A) and acetonitrile (B) were selected for the mobile phase, and the pretreatment method was determined by solid phase extraction. As a result of the method validation, the intra-day / inter-day accuracies were 82.2~114.1% and the precisions were less than 20%. The detection limit was 0.027 ng/ml for fipronil and 0.087 ng/ml for fipronil sulfone. The linearity obtained was satisfying, with a coefficient of determination (r²) higher than 0.99. The concentrations in some animal sera were determined using the methods of analysis for fipronil and fipronil sulfone in animal sera developed in this study. Using the method developed in this study, it could be used as an analytical method for human bio-monitoring of fipronil and fipronil sulfone as well as animal serum.

• Korean Journal of Environmental Agriculture
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• v.34 no.4
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• pp.309-317
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• 2015

BACKGROUND: An analytical method was developed using GC-ECD/MS to precisely determine the residue of fipronil, a phenylpyrazole insecticide used to control a wide range of foliar and soil-borne pests.METHOD AND RESULTS: Fipronil residue was extracted with acetone from representative samples of five raw products which comprised hulled rice, soybean, Kimchi cabbage, green pepper, and apple. The extract was diluted with saline water, and fipronil was partitioned into n-hexane/dichloromethane (20/80, v/v) to remove polar co-extractives in the aqueous phase. Florisil column chromatography was additionally employed for final purification of the extract. Fipronil was separated and quantitated by GC-ECD using a DB-17 capillary column. Accuracy of the proposed method was validated by the recovery from crop samples fortified with fipronil at 3 levels per crop in each triplication.CONCLUSION: Mean recoveries ranged from 86.6% to 106.0% in five representative agricultural commodities. The coefficients of variation were less than 10%. Limit of quantitation of fipronil was 0.004 mg/kg as verified by the recovery experiment. A confirmatory technique using GC/MS with selected-ion monitoring was also provided to clearly identify the suspected residue. Therefore, this analytical method was reproducible and sensitive enough to determine the residue of fipronil in agricultural commodities.

• Journal of Veterinary Clinics
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• v.19 no.2
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• pp.215-218
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• 2002

It is known that house dust mites which settle on sofa, carpet, and dust in the house ignite asthma and allergic rhinitis. Dermatophagoides farinae and Dermatophagoides pteronyssinus distribute widely and densely in Korea. In this study we carried out to identify that shed hair of dogs which was applied topically with fipronil ($\Frontline^{circledR}$) kill house dust mites. We co-cultured house dust mites with fipronil-applied hair of dog during 12 hours, and then compared the death rate of mites here with that cultured without hair. The larger amount of hair, the more mites were killed. The death rate of mites was higher than control significantly until 2 weeks after $\Frontline^{circledR}$ application. Hair which had been shed at 3 days after $\Frontline^{circledR}$ application always killed the smaller number of mites than not shed. The present study suggested that the use of $\Frontline^{circledR}$ to our pets control house dust mites effectively.

• Korean journal of applied entomology
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• v.43 no.3 s.136
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• pp.241-247
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• 2004

Susceptibility of Blattella germanica male adults to 61 commercial insecticides was evaluated by diet dipping method. Among them three insecticides of dichlorvos, fenitrothion, and fipronil showed over $90\%$ mortality. The insect was more susceptible to dichlorvos and fenitrothion in filter paper contact method than in diet dipping one, but fipronil was vice versa. Toxicities of the three chemicals were evaluated by application parts of the such as head, thorax, abdomen, and legs. Dichlorvos and fenitrothion were more toxic when applied to head, and flpronil was thorax. $LT_{50}$ values by diet dipping method showed that fenitrothion and fipronil acted more rapidly than boric acid and hydramethylnon. The values of the former two were 1.05 and 0.98 days, and those of the latter two were 3.92 and 2.26 days, respectively.

• Food Science of Animal Resources
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• v.41 no.1
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• pp.59-70
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• 2021

A method for simultaneous detection of fipronil (F) and its metabolites fipronil desulfinyl (FD), fipronil sulfide (FS), fipronil sulfone (FSO) in chicken eggs was applied and validated. It includes single-step, cheap, effective, rugged, safe-based method (SinChERS) for sample preparation and ultra high performance liquid chromatography coupled with mass spectrometry (UHPLC-MS/MS) for chemical analysis. Results suggested that formic acid enhanced the recovery of 4 target residues and 1% supplementation to acetonitrile gained higher recoveries than that of 5%. SinChERS integrated extraction and clean-up steps into one, with shorter time (1.5 h) to operate and higher recoveries (97%-100%) than HLB, Envi-Carb-NH2 and quik-easy-cheap-effective-rugged-safe method (QuEChERS), and it consumed the smallest volume of extracting solvent (10 mL) as QuEChERS. Quantitative analyses using external standard method suggested the linear ranges of 4 target compounds were 1-20 ㎍/L with R2 >0.9947. The limit of detection (S/N>3) and quantification (S/N>10) were 0.3 ㎍/kg and 1 ㎍/kg. Recoveries ranged from 89.0% to 104.4%, and the relative standard deviations (n=6) at 1, 10, and 20 ㎍/kg were lower than 6.03%. Thirty batches of domestic eggs (500 g each) were detected by the established SinChERS-based UHPLC-MS/MS and no target residues were detected in all samples. The method developed in this study is a rapid, sensitive, accurate and economic way for multi-residue analysis of fipronil and its metabolites in eggs.

• The Korean Journal of Pesticide Science
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• v.13 no.1
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• pp.39-44
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• 2009

This study was conducted to evaluate the actual risk of fipronil on worker honey bees (Apis mellifera L.) through acute contact toxicity test, acute oral toxicity test, toxicity of residues on foliage test, and small scale field test. The $48h-LD_{50s}$ of fipronil SC on honeybee were $0.005{\mu}g$ a.i./bee in acute contact toxicity test and $0.004{\mu}g$ a.i./bee in acute oral toxicity test, respectively. In toxicity of residues on foliage test, fipronil showed over 90% of mortality during 28days after treatment at recommended application rate. The $DT_{50}$ of dislodgeable foliar residue was 9 days. Finally, In small scale field test, fipronil showed similar toxicity in the residues on foliage test. It was concluded that fipronil has very high acute toxicity and long residual toxicity to honeybee. Therefore, fipronil is highly toxic to bees exposed to direct treatment or residues on blooming crops or weeds. Do not apply this product or allow it to drift to blooming crops or weeds if bees are visiting the treatment area. To protect honeybee and wild pollinators from outdoor use of fipronil, ultimately it should need to limit for only indoor use to prevent pollinators from unintentionally exposure of fipronil.