• 한국자기공명학회논문지
• /
• 제24권4호
• /
• pp.104-116
• /
• 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
• /
• 제23권6호
• /
• pp.82.1-82.6
• /
• 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.

• 농업과학연구
• /
• 제49권1호
• /
• pp.103-112
• /
• 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
• /
• 제48권6호
• /
• pp.459-465
• /
• 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.

• 대한화학회지
• /
• 제63권6호
• /
• pp.415-419
• /
• 2019

피프로닐은 N-페닐피라졸계의 살충제로 해충 방지제로 사용되고 있으며, WHO에서는 피프로닐을 발암물질 2급으로 분류 및 규제하고 있다. 피프로닐은 급성중독 시에 현기증, 근육약화, 호흡곤란, 피부자극, 심박수 증가 등의 다양한 증상이 나타나는 것으로 알려져 있고 피프로닐 설폰 또한 이와 비슷한 증상을 유발하는 것으로 알려져 있다. 최근 피프로닐이 함유된 계란이 유통되면서 전 세계적으로 독성 문제가 확산되고 있는 상황이다. 본 연구에서는 동물 혈청 시료 중 피프로닐 및 피프로닐 설폰의 노출량 분석법 개발을 시도하였다. 이동상에 따른 차이 및 액체-액체 추출과 고체상추출 전처리 방법에 따른 결과를 비교하였다. 이동상은 증류수(A)와 아세토니트릴(B)을 선정하였고, 전처리 방법은 고체상추출로 진행하였다. 분석법검증을 수행한 결과, 일내/일간 정확도는 82.2~114.1% 이었고, 정밀도는 20% 이하로 나타났다. 검출한계는 피프로닐 0.027 ng/ml, 피프로닐 설폰은 0.087 ng/mL 이었고, 검량선 회귀식의 결정계수(r²)는 0.99 이상으로 우수한 직선성을 보여주었다. 본 연구에서 개발된 동물 혈청 중 피프로닐 및 피프로닐 설폰 분석방법을 이용하여 일부 동물 혈청에서의 농도를 확인하였다. 본 연구에서 개발한 분석법을 이용하여 동물 혈청뿐만 아니라 피프로닐 및 피프로닐 설폰의 인체 모니터링을 위한 분석법으로도 사용 할 수 있을 것으로 판단된다.

• 한국환경농학회지
• /
• 제34권4호
• /
• pp.309-317
• /
• 2015

본 연구는 GC-ECD/MS법을 적용하여 농산물에 함유된 phenylpyrazole 살충제 fipronil의 잔류 분석법을 확립하였다. 대표 농산물은 사과, 고추, 배추, 현미 및 콩을 선정하였고, acetone에 의해 추출된 fipronil 성분을 n-hexane/dichloromethane 액-액 분배법과 florisil 흡착크로마토그래피법으로 정제하여 분석시료로 사용하였다. Fipronil의 정량적 분석을 위한 최적 GC-ECD 분석 조건을 확립하였으며 정량한계(LOQ)는 0.004 mg/kg이었다. 각 대표 농산물에 대해 정량한계, 정량한계의 10배 및 50배 수준에서 회수율을 검토한 결과, 모든 처리농도에서 86.6-106.0% 수준을 나타내었고, 반복 간 변이계수(CV)는 최대 5.7%를 나타내어 잔류분석 기준인 회수율 70-120% 및 분석오차 10% 이내를 충족시키는 결과를 도출하였으며, GC/MS/SIM을 이용하여 실제 농산물 시료에 적용하여 재확인하였다. 이상의 결과로 신규 fipronil의 GC-ECD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로 사용 가능할 것이다.

• 한국임상수의학회지
• /
• 제19권2호
• /
• pp.215-218
• /
• 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.

• 한국응용곤충학회지
• /
• 제43권3호
• /
• pp.241-247
• /
• 2004

시판되고 있는 61종 살충제에 대한 식이법으로 바퀴(Blattella germanica) 수컷성충의 우수 살충제를 탐색하고, 활성이 있는 약제를 이용하여 처리부위와 검정법에 따른 감수성 차이와 발현속도를 비교하였다. 식이법에서 $90\%$ 이상의 살충률을 나타낸 세 약제중에서 dichlorvos, fenitrothion, fipronil약제를 선발하여, 식이법과 여지접촉법으로 살충력을 비교한 결과, dichlorvos와 fenitrothion은 여지접촉법에서, fipronil은 식이법에서 더 높은 감수성을 나타내었다. 처리부위(머리, 가슴, 배, 다리)에 따라서는 dichlorvos와 fenitrothion은 머리처리에서, fipronil은 가슴처리에서 감수성이 가장 높았다. Fenitrothion과 fipronil의 $LT_{50}$(일)은 각각 1.05와 0.98로 속효성이었으며, boric acid와 hydramethylnon은 각각 3.92와 2.26으로 지효성이였다.

• 한국축산식품학회지
• /
• 제41권1호
• /
• pp.59-70
• /
• 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.

• 농약과학회지
• /
• 제13권1호
• /
• pp.39-44
• /
• 2009

벼농사용 살충제인 fipronil의 비의도적 노출에 의한 꿀벌(Apis mellifera L.)의 피해를 확인하기 위해 급성독성시험, 엽상잔류독성시험, cage를 이용한 소규모야외시험을 실시하였다. 급성접촉독성시험에서 24시간과 48시간의 $LD_{50}$은 각각 0.008, $0.005{\mu}g$ a.i./bee 로 꿀벌에 매우 강한 급성독성을 보였으며 급성위해지수(QHc)는 12,500으로 매우 높은 수준이었다. 엽상잔류독성시험에서는 피프로닐 액상수화제 살포 후 28일까지 90%이상 치사율을 보여 장기간 꿀벌에 독성이 있음을 알 수 있었다. 이때 fipronil의 표면부착잔류량(dislodgeable foliar residue)을 분석한 결과 $DT_{50}$은 9일, $DT_{90}$은 31일이었다. 야외시험의 결과에서도 28일의 치사율이 40%로 조사되어 실내 엽상잔류독성시험과 유사한 잔류독성을 보였다. 이상의 결과를 종합하면 fipronil은 꿀벌에 대한 급성독성이 매우 강하면서 장기간의 잔류독성이 있어 잎 표면의 매우 낮은 잔류량으로 꿀벌에 피해를 줄 가능성이 매우 높은 살충제이다. 따라서 재배작물뿐만 아니라 살포지역 인근의 밀원식물에 약제살포시 바람에 날려 오염될 경우 화분매개용 꿀벌과 자연생태계 유용곤충에 위해가능성이 매우 높기 때문에 꿀벌이 왕성한 활동을 하는 시기에는 야외살포를 금지하여야 하며, 궁극적으로 야외생태계 유용곤충을 보호하기 위해서는 실내사용 목적으로만 사용되도록 제한해야 할 것으로 판단된다.