Effects of Co-existence of Dichlorvos and Phosalone on the Bioconcentration in Zebrafish (Brachydanio rerio)

Min, Kyung Jin,Park, Jang Woo,Cha, Chun Geun 한국식품위생안전성학회 2003 한국식품위생안전성학회지 Vol.18 No.4

본 연구는 zebrafish를 실험어류로 하여 국내에서 혼합제로 사용되고 있는 dichlorvos와 phosalone을 선정하여 단독 및 혼합폭로시 생물농축계수와 배설속도상수를 측정함으로써, 두 농약의 공존이 개별농약의 생물농축성에 미치는 영향을 알아보고자 하였다. Dichlorvos의 phosalone의 혼합폭로시(dichlorvos : 0.55㎍/㎖, phosalone : 0.01㎍/㎖) zebrafish 체내에서 dichlorvos의 농축정도는 6시간에 정류상태에 도달하여 72시간까지 거의 일정하였으며 단독폭로시(12시간0보다 더 빠르게 정류상태에 도달하였다. 6시간에서 72시간 사이의 BCF평균값은 0.080(n=5)으로 단독폭로시의 12시간에서 72시간 사이의 BCF평균값 0.74(n=4)보다 더 높게 측정되었다. 배설속도상수는 0.12h^-1으로 단독폭로시와 차이가 거의 없었다. Dichlorvos와 phosalone의 혼합폭로시(dichlorvos : 0.55㎍/㎖, phosalone : 0.01㎍/㎖) zebrafish 체내에서 phosalone의 농축정도는 단독폭로시와 같이 12시간 정류상태에서 도달하여 72시간까지 거의 일정하였고, 12시간에서 72시간 사이의 BCF평균값은 53.89(n=4)로 단독폭로시의 BCF평균값 48.88(n=4)보다 더 높게 측정되었다. 배설속도상수는 단독폭로시와 같이 6시간 안에 어류체내에서 phosalone이 모두 배출되어 구하지 못했다. 두농약(dichlorvos, phosalone)의 혼합폭로시의 BCF평균값이 단독폭로시의 BCF평균값보다 더 높게 나왔으나 각 실험시간대(6, 12, 24, 48, 72시간)의 BCF실험값을 t-test로 분석한 결과 phosalone의 48시간을 제외하고는 두 농약의 단독폭로와 혼합폭로시의 BCF값에는 유의한 차이가 없었다(p<0.05). 이상의 결과를 종합해 볼 때, dichlorvos와 phosalone을 zebrafish에 혼합폭로시 개개 농약의 생물농축성과 배설속도상수에는 유의한 영향을 미치지 않는 것으로 나타났다. This study was performed to investigate the effect of co-existence of dichlorvos and phosalone on the bioconcentration in zebrafish (Brachydanio rerio). The bioconcentration of the pesticides was reached an equilibrium more rapidly in an exposure of the binary mixture than that in an individual exposure. The BCF values and depuration rate constants for dichlorvos and phosalone in the binary mixture in the zebrafish were not significantly different from that of single pesticide. The results suggest that the effect of co-existence of pesticides on bioconcentration and depuration in zebrafish can be evaluated with single pesticide datum.

Dichlorvos와 methidathion의 생분해율의 측정

민경진,차춘근,Min, Kyung-Jin,Cha, Chun-Geun 한국환경보건학회 1999 한국환경보건학회지 Vol.25 No.3

The present study was performed to investigate biodegradation rate of dichlorvos and methidathion. In the biodegradation test of two pesticides by the modified river die-away method from June 17 to August 22, 1998, the biodegradation rate constants and half-life were determined in Nakdong(A) and Kumho River(B). Biodegradation rate of dichlorvos was 4.51% in A sampling point, 6.88% in B sampling point after 7 days. Biodegradation rate constants and half-life of dichlorvos were 0.0066 and 105 days in A sampling point, 0.0102 and 67.9 days in B sampling point, respectively. Biodegradation rate of methidathion was 23% in A sampling point, 36% in B sampling point after 7 days. Biodegradation rate constants and half-life of methidathion were 0.0377 and 18.4 days in A sampling point, 0.0641 and 10.8 days in B sampling point, respectively. Biodegradation rate of methidathion was faster than that of dichlorvos. This suggested that the difference in biodegradation of pesticides was due to difference in the water quality and standard plate counts in the Nackdong and Kumho Rivers. The result of correlation analysis between biodegradation rate constants of the pesticides and water quality(DO, BOD, SS, ABS, NH$_3$-N, and NO$_3$-N) showed significant correlation with BOD, SS and NH$_3$-N at the 5% significant level. A significant linear equation was obtained from regression analysis at the 5% significant level, whereas, dependent variables were BOD, SS and NH$_3$-N, and the biodegradation rate constant was independent variable. It is suggested that dichlorvos will be mainly degraded by hydrolysis, and for methidathion was both hydrolysis and biodegradation. A significant QSAR equation was obtained from regression analysis at the 10% significant level, whereas, dependent variable is biodegradation rate constants of BPMC, chlorothalonil, dichlorvos and methidathion, vapor pressures, partition coefficients and water solubilities of the pesticides are independent variables. Also, a significant linear equation was obtained from regression analysis at the 1% significant level, whereas, dependent variable is biodegradation rate constants of BPMC, chlorothalonil, dichlorvos and methidathion, hydrolysis rate constants of the pesticides are independent variables. It is suggested that the pesticides will be degraded by main degradation factor when the pesticides was affected both hydrolysis and biodegradation.

시설재배 부추 중 Dichlorvos와 Valifenalate 사용에 따른 경시적 잔류량 변화와 잔류 안전성 평가

이득영,배지연,송영훈,오경열,김영진,이동열,김진효 한국농약과학회 2022 농약과학회지 Vol.26 No.1

부추 시설재배지에 20% dichlorvos 유제와 12% valifenalate 액상수화제를 살포하여 이들의 경시적 잔류변 화와 생물학적 반감기 및 잔류 안전성을 평가하였다 . 수확 당일 약액 살포 후 dichlorvos의 초기 잔류량은 1.709- 2.054 mg kg-1이었으나 , 이를 제외한 모든 시료에서 dichlorvos는 LOQ미만으로 불검출 되었으며 , 20% dichlorvos 유 제를 수확 7일 전까지 2회 처리하여도 잔류안전성에는 큰 영향이 없을 것으로 판단되었다 . Valifenalate의 총 환산잔 류량은 수확 당일 약액 살포 후 13.06-17.63 mg kg-1이었고 , 최종 약제 처리 21일 경과 후 잔류량은 0.891-0.955 mg kg-1으로 감소함을 확인하였고 , 이는 현재 부추에 설정되어 있는 최대 잔류 허용량인 0.05 mg kg-1을 초과하지 않았다 . Valifenalate에 대한 부추의 생물학적 반감기는 9.30일이었다 . 따라서 , 12% valifenalate 액상수화제를 수확 14일 전까 지 2회 처리하여도 잔류안전성에는 큰 영향이 없을 것으로 판단되었다 .

시설재배 애호박 중 Dichlorvos와 Etofenprox 사용에 따른 경시적 잔류량 변화

오경열(Kyeong-Yeol Oh),배지연(Ji-Yeon Bae),이득영(Deuk-Yeong Lee),김영진(Yeong-Jin Kim),이동열(Dong-Yeol Lee),김진효(Jin-Hyo Kim) 한국농약과학회 2021 농약과학회지 Vol.25 No.1

Dichlorvos and etofenprox as insecticides were widely used for crop protection, but the residues of the pesticides in the fruit and the leaf of squash were not studied well. In here, the residues dissipation and the biological half-lives were investigated in the fruit and the leaf of squash. The residues of dichlorvos in the leaf and fruit of squash were detected 0.916-1.111 mg kg<SUP>-1</SUP> and 0.016-0.025mg kg<SUP>-1</SUP> on 0 day-after-treatment (DAT) respectively, but no detection showed after 3 DAT both in the fruit and in the leaf. The etofenprox residues were 0.075-0.098 mg kg<SUP>-1</SUP> and 6.378-7.443 mg kg<SUP>-1</SUP> on 0 DAT in the fruit and the leaf, but the residue concentration in the fruit was below the temporal maximum residue limit (0.2 mg kg<SUP>-1</SUP>) regardless of the harvest date. The half-lives of etofenprox in the fruit and the leaf were 3.5 and 7.1 day, respectively. In addition, the dietary exposure risks of etofenprox were estimated to 0.018% and 0.027% of acceptable daily intake (ADI) for all age group from the fruit and the leaf. Furthermore, the %ADI for the infant group (1-2-year-old, 0.044% ADI) and the elder age group (≥65-year-old, 0.031% ADI) were higher than all the age groups from the dietary of the fruit.

Dichlorvos가 흰쥐 심근의 미세구조에 미치는 영향

백태경,이화모,정호삼,Baik, Tai-Kyoung,Lee, Wha-Mo,Chung, Ho-Sam 한국현미경학회 1994 Applied microscopy Vol.24 No.3

It is well known that dichlorvos (DDVP), an organophosphate insecticide in common use, is so easily and rapidly hydrolyzed and excreted that it has usually little toxic effect on human body. In these days, however, it is widely used as an industrial and domestic insecticide and as an anthelmintic agent for animals, so that the accident of chemical poisoning occurs frequently. DDVP acts as a powerful inhibitor of carboxylic esterase, which can cause accumulation of acetylcholine at the synapses so paralysis of muscle and the transmission failure in cholinergic synapses dueing to desensitization of acetylcholin receptor may occure. Moreover accumulation of the acetylcholine brings about the elevation of the cyclic-AMP, which alters the cellular metabolisms of nucleic acid, carbohydrate, protein and lipid. Present study has undertaken to investigate the cardiotoxic effect of DDVP by electron microscopic study. A total of 30 Sprague-Dawley strain rats, weighing about 250gm were used as experimental animals. 2mg/kg/day of DDVP is intraperitonealy injected 3 times with intervals of every other day. On 1 day, 3 days, 5 days, 7 days and 14 days after drug administration, the animals were sacrified by cervical dislocation. Left ventricular cardiac muscles were resected and sliced into $1mm^3$. The specimens were embedded with Epon 812 and prepared by routine methods for electron microscopical observation. All preparations were stained with lead citrate and uranyl acetate and then observed with Hitachi-600 transmission electron microscope. The results were as follows: 1. In the cardiac muscle of DDVP treated rats, mitochondria with disorganized double membrane and mitochondrial crista, and vacuole formation in mitochondrial matrix were observed. But structures of mitochondria were recovered to normal in 14 days group. 2. In the cardiac muscle of DDVP treated rats, cisternae of sarcoplasmic reticulum were dilated and sacculated. But these changes were recovered to normal in 14 days group. 3. In the cardiac muscle of DDVP treated rats, glycogen particles around damaged myofibrils were decreased. But amount of glycogen particles were restored in 14 days group. 4. In the cardiac muscle of DDVP treated rats, disruption and discontinuation of myofilaments and disorganization of Z-disc were observed. But the structures of myofibrils were recovered to normal in 14 days group. It is consequently suggested that DDVP would induce the reversible degenerative changes on the ultrastructures in cardiac muscle of rat.

Determination of Trichlorfon Pesticide Residues in Milk via Gas Chromatography with µ-Electron Capture Detection and GC-MS

Lina Hem,Sathya Khay,Jeong-Heui Choi,E.D. Morgan,A.M. Abd El-Aty,Jae-Han Shim 한국독성학회 2010 Toxicological Research Vol.26 No.2

The pesticide trichlorfon is readily degraded under experimental conditions to dichlorvos. A method has therefore been developed by which residues of trichlorfon in milk are determined as dichlorvos, using gas chromatography with μ-electron capture detection. The identification of dichlorvos was confirmed by mass spectrometry. Milk was extracted with acetonitrile followed by centrifugation, freezing lipid filtration, and partitioning into dichloromethane. The residue after partitioning of dichloromethane was dissolved in ethyl acetate for gas chromatography. Recovery concentration was determined at 0.5, 1.0, and 2.0 of times the maximum permitted residue limits (MRLs) for trichlorfon in milk. The average recoveries (n = 6) ranged from 92.4 to 103.6%. The repeatability of the measurements was expressed as relative standard deviations (RSDs) ranging from 3.6%, to 6.7%. Limit of detection (LOD) and limit of quantification (LOQ) were 3.7 and 11.1 ㎍/l, respectively. The accuracy and precision (expressed as RSD) were estimated at concentrations from 25 to 250 ㎍/l. The intra- and inter-day accuracy (n = 6) ranged from 89.2% to 91% and 91.3% to 96.3%, respectively. The intra- and inter-day precisions were lower than 8%. The developed method was applied to determine trichlorfon in real samples collected from the seven major cities in the Republic of Korea. No residual trichlorfon was detected in any samples.

Determination of Trichlorfon Pesticide Residues in Milk via Gas Chromatography with μ-Electron Capture Detection and GC-MS

Hem, Lina,Khay, Sathya,Choi, Jeong-Heui,Morgan, E.D.,El-Aty, A.M. Abd,Shim, Jae-Han Korean Society of ToxicologyKorea Environmental Mu 2010 Toxicological Research Vol.27 No.2

The pesticide trichlorfon is readily degraded under experimental conditions to dichlorvos. A method has therefore been developed by which residues of trichlorfon in milk are determined as dichlorvos, using gas chromatography with ${\mu}$-electron capture detection. The identification of dichlorvos was confirmed by mass spectrometry. Milk was extracted with acetonitrile followed by centrifugation, freezing lipid filtration, and partitioning into dichloromethane. The residue after partitioning of dichloromethane was dissolved in ethyl acetate for gas chromatography. Recovery concentration was determined at 0.5, 1.0, and 2.0 of times the maximum permitted residue limits (MRLs) for trichlorfon in milk. The average recoveries (n = 6) ranged from 92.4 to 103.6%. The repeatability of the measurements was expressed as relative standard deviations (RSDs) ranging from 3.6%, to 6.7%. Limit of detection (LOD) and limit of quantification (LOQ) were 3.7 and $11.1{\mu}g/l$, respectively. The accuracy and precision (expressed as RSD) were estimated at concentrations from 25 to $250{\mu}g/l$. The intra- and inter-day accuracy (n = 6) ranged from 89.2% to 91% and 91.3% to 96.3%, respectively. The intra- and inter-day precisions were lower than 8%. The developed method was applied to determine trichlorfon in real samples collected from the seven major cities in the Republic of Korea. No residual trichlorfon was detected in any samples.

감광제/광촉매에 의한 공기오염물질 제거

이재구,안기창,박주형,권정욱 충북대학교 첨단원예기술개발연구센터 1999 연구보고서 Vol.4 No.-

일반 주거환경 또는 재배시설 내의 공기오염물질인 농약 및 병원성 미생물을 인위적으로 제거하기 위해서 자연광 또는 인공광 조건하에서 몇몇 감광제/광촉매에 의한 광분해 촉진효과와 미생물의 살균효과 시험을 수행하였다. 광촉매로는 반도체 물질인 PC-1과 PC-2, 그리고 산화제로 사용되는 PC-3, PC-4, PC-5 및 PC-6과 감광제로 PS-7과 PS-8을 선발하였다. 그리고 시험화합물로는 유기인계 살충제인 dichlorvos와 dicarboximide계 살균제인 procymidone, 환경오염물질인 methyl tert-butyl ether (MTBE)를 선정하였고, 유해 미생물로는 Pseudomonas putida, Phytophthora capsici, Salmonella typhimurium, 및 Escherichia coli를 선정하였다. Dichlorvos의 경우에는 자연광과 인공광 조건하에서, 광촉매 무처리구에 비해 각각의 광촉매가 처리된 모든 처리구에서 4배 이상의 광분해 촉진효과를 보였으나, MTBE의 경우에는 단지 광촉매 PC-1 처리구만 이 광촉매 무처리구에 비해 약 17배 이상의 분해 촉진효과를 보였다. 또한 procymidone의 경우에도 PC-1, PC-6 및 PS-8에 의한 광분해가 약 3배 이상 촉진되었다. 공기 중의 미생물을 제거하기 위한 예비시험에서는 미생물 현탁액에 PC-1을 첨가하고 인공광을 조사함으로서 미생물의 생육이 저해됨을 확인할 수 있었다. 또한 평판배지에 도말된 Salmonella typhimurium은 광촉매 PC-1의 주변에서 미생물 생육이 저해됨을 보였다. 이상의 결과에서 볼 때, 광조건 하에서 이러한 감광제/광촉매를 이용한 기술은 농약을 비롯한 여러 환경 오염물질을 제거하여 재배시설 내의 작업자와 일반 대중의 환경오염원에 대한 노출을 예방할 수 있을 것으로 기대된다. For the artificial removal of the air pollutants such as pesticides, environmental toxicants, and pathogenic microorganisms in the greenhouse or the living environment, the accelerated photodegradation and the biocidal effects by some photosensitizers (PS)/photocatalysts (PC) were tested under the sunlight and/or artificial light. The selected photosensitizers/photocatalysts were the semiconductors (PC-1 and PC-2), the oxidizers (PC-3, PC-4, PC-5 and PC-6), the aromatic ketone (PS-7) and the aromatic amine(PS-8). The test toxic pollutants included the organophosphorus insecticide dichlorvos (DDVP), the dicarboximide fungicide procymidone, and the gasoline additive, methyl tert-butyl ether(MTBE) as the organic pollutants, and Pseudomonas putida, Phytophthora capsici, Escherichia coli and Salmonella typhimuriums as the pathogenic organisms. In the case of dichlorvos, all the photocatalysts selected showed more accelerated photodegradation than the control without photocatalyst under both the sunlight and artificial light. Whereas, only the photocatalyst PC-1 accelerated the degradation of MTBE about 17 times more than the control under both the sunlight and artificial light. Procymidone was much more degraded by the photosensitizer PS-8 and the two photocatalysts (PC-1, PC-6) than by PS-7. In the preliminary experiments to diminish the population of the microorganisms in the air, the photocatalyst-1 added to the microbial suspensions obviously inhibited the microbial growth under the artificial light. The photocatalyst-1 showed the bactericidal activity against Salmonella typhimurium spread on the nutrient broth agar medium. These results suggest that the photosensitizers/ photocatalysts under the light can remove some air pollutants and hence they can be used to reduce the exposure of the workers in the horticultural facilities and/or the public in the environment to the harmful pollutants.

국내 급성 dichlorvos 중독 현황과 임상상 분석

이미진,박준석,권운용,어은경,오범진,이성우,서주현,노형근,Lee, Mi-Jin,Park, Joon-Seok,Kwon, Woon-Yong,Eo, Eun-Kyung,Oh, Bum-Jin,Lee, Sung-Woo,Suh, Joo-Hyun,Roh, Hyung-Keun 대한임상독성학회 2008 대한임상독성학회지 Vol.6 No.1

Purpose: Dichlorvos has been in widespread use as an organophosphate (OP) insecticide compound. The purpose of this study was to access the epidemiology and clinical features of dichlorvos in Korea. Methods: This was a 38 multi-center prospective study of dichlorvos poisoning using surveys, a structural reporting system and review of hospital records from August 2005 to July 2006. A total of 54 patients with acute dichlorvos poisoning on a national basis were enrolled. We analyzed the epidemiologic characteristics and clinical manifestations of dichlorvos poisoning. In addition, the clinical features of dichlorvos poisoning were compared with others OP compounds. Results: During the study period, compounds involving pure OP poisoning were dichlorvos (22.7%), methidathion (8.4%), and phosphamidon (6.7%). In acute dichlorvos poisoning, all ingestion routes were oral. Intentional poisoning involved 74.1% of cases. The common initial complaints involved gastrointestinal (64.8%), systemic (61.1%), central or peripheral nervous system (53.7%), and respiratory symptoms (50.0%). The median arrival time to hospital after dichlorvos poisoning was 2.6 hours and mean hospitalization duration was 7.1 days. 2-PAM was administered in 35 patients in mean doses of 6.3 g/day intravenously. Atropine was administered in 30 patients with a mean dose of 62.8 mg/day (maximal 240 mg/day). Overall mortality rate for dichlorvos poisonings were 14.8% (8/54). Immediate causes for death included sudden cardiac arrest or ventricular dysrhythmias (50%), multi-organ failure (25%), acute renal failure (12.5%), and unknown causes (12.5%). Conclusion: When compared to previous reports, dichlorvos poisoning displayed relatively moderate severity. The presence of a lower GCS score, altered mental status, serious dysrhythmias, systemic shock, acute renal failure, and respiratory complications upon presentation were associated with a more serious and fatal poisoning.

Brachydanio rerio와 Xiphophorus hellieri를 이용한 Dichlorvos, Methidathion 및 Phosalone의 단기간 생물농축계수의 측정

민경진,전봉식,차춘근,김근배,조영주 한국환경보건학회 1998 한국환경보건학회지 Vol.24 No.3

This study was performed to investigate the bioconcentration of dichlorvos, methidathion and phosalone in zebrafish (brachydanio rerio), red sword tail(Xiphophorus hellieri). The fishes were exposed to 0.05 ppm, 0.01 ppm, 0.50 ppm, one-hundredth concentration of 96-hrs LC$_{50}$ and one-thousandth concentration of 96-hrs LC$_{50}$ and test periods were 3, 5 and 8 days. The deputation rate of each pesticide from the whole body of fish was determined over the 24-hr period after treatment. Obtained results are summerized as follows: In the case of dichlorvos, dichlorvos concentration in zebrafish extract and BCF$_{s}$ of dichlorvos were increased as increasing test concentration. In the case of same experimental concentrations, dichlorvos concentration in zebrafish extract and BCF$_{s}$ of dichlorvos were decreased as proloning test periods, especially dropped after 5days. Dichlorvos concentration in red sword tail extract were increased as increasing test concentration, lyat BCF$_{s}$ in concentration of 0.05 ppm, 0.01 ppm and one-hundredth of 96-hrs LC$_{50}$ were decreased. Methidathion and phosalone concentration in zebrafish extract in zebrafish extract were increased as increasing test concentration, but there was little difference in BCF$_{s}$. In the case of same experimental concentrations, there were little differences in BCF$_{s}$ and concentration in zebrafish extract. In the case of red sword tail, it was impossible to calculate on BCF$_{s}$ data because test concentration was under the detecting limit on GC or test fish were die. Determined deputation rate conatant were highest on dichlorvos, and followed by methidathion, and phosalone. The results of determining depuration rate of these pesticides showed that the high BCF in fish might be due to the slow depuration rate in fish, it is thought to be responsible for vapor pressure, water solubility and partition coefficient. It is suggested that one-hundredth concentration of 96-hrs LC$_{50}$ will be proper test concentration because one-thousundth of LC$_{50}$ was under the detecting limit on GC. Dichlorvos, methidathion and phosalone, organophosphorous pesticides, were examined to their BCF$_{s}$ and depuration rates by means of fish test.