들깻잎에서 Triazole계 살균제의 생물학적 반감기와 물리화학적 특성과의 상관관계

이상협,곽세연,황정인,김효정,김태화,김장억 한국응용생명화학회 2019 Journal of Applied Biological Chemistry (J. Appl. Vol.62 No.4

The biological half-life of pesticides applied on crops is the key indicator for ensuring the safety of agricultural products. The biological half-life is affected by the several factors like growing conditions of the crop, climate, application method, and physicochemical properties of pesticides. In this study, the biological half-life was calculated and the degradation rates of six triazole fungicides sprayed on perilla leaves were evaluated. Moreover, the statistical analysis confirmed the correlation between the biological half-life and physicochemical properties of six triazole pesticides. The recoveries of the six pesticides were between 84.8-104.9%, which satisfied the residual pesticide analysis criteria. The biological half-life of six pesticides sprayed on perilla leaves, calculated using the first-order kinetics model, ranged between 6.4-15.1 days. When the biological half-life and the physicochemical properties were correlated using the principal component analysis: pKa and Log P, the biological half-life was found to be affected by PC1. The correlation coefficient between biological half-life and physicochemical properties (pKa), calculated by Spearman rank-order correlation, was R2 = −0.928 (p <0.01). Biological half-life has been shown to correlate with pKa. In conclusion, it can be used as a database for the relationship between biological half-life and physicochemical properties and will contribute to ensure safe supply of agricultural products. 들깻잎에 살포된 triazole계 살균제 6종에 대하여 생물학적 반감기를 산출하고 분해 및 소실 속도를 확인하였으며, 통계분석으로 생물학적 반감기와 농약의 물리화학적 특성간의 상관관계를 확인하였다. 확립된 분석법으로 6종 농약의 회수율 시험 결과 84.8-104.9%로 잔류농약분석법 기준을 만족하였다. 들깻잎에살포한 농약 6종의 생물학적 반감기는 first-order kinetics model으로 산출하였으며, 그 결과 6.4-15.1일로 나타났다. 산출된 생물학적 반감기와 6종의 농약의 물리화학적 특성을 주성분분석으로 상관성을 확인하였을 때, pKa, Log P 및 생물학적 반감기가 PC1에 영향을 받아 상관성이 있는 것으로 나타났다. Spearman rank-order correlation으로 생물학적 반감기와 물리화학적 특성간의 상관계수를 산출하였을 때, 생물학적 반감기와pKa는 R2= −0.928, p <0.01로 나타나, 생물학적 반감기는 pKa와상관성이 있는 것으로 나타났다.

Triazole계 살균제의 사과 중 잔류양상의 Kinetic Model 적용

김지환 ( Ji Hwan Kim ),황정인 ( Jeong In Hwang ),전영환 ( Young Hwan Jeon ),김효영 ( Hyo Young Kim ),안지운 ( Ji Woon Ahn ),김장억 ( Jang Eok Kim ) 한국응용생명화학회 2012 Journal of Applied Biological Chemistry (J. Appl. Vol.55 No.4

While cultivating crops, it is important to predict the biological half-lives of applied pesticides to ensure the safety of agricultural products. Dissipation patterns of the triazole fungicides, such as diniconazole and metconazole, during the cultivation of apple were established by utilizing the dissipation curve. As well as, the biological half-lives of the pesticides in apples were calculated using the residue amounts of them. The apples were harvested from 0 to 14 days after spraying diniconazole (WP) and metconazole (SC) at a recommended and three times of the recommended dose. Initial concentrations of diniconazole in apple were 0.09 and 0.15 mg/kg at a recommended and three times of the recommended dose, respectively, which were below MRL 1.0 mg/kg established by KFDA. The equations of biological half-life were Ct=0.0811e-0.179x(half life: 3.9 days) and Ct=0.1451e-0.148x (half life: 4.7 days), respectively. In case of metconazole, initial concentrations in apple were 0.10 and 0.25 mg/kg, below MRL 1.0mg/kg, and biological half-life equations were Ct=0.0857e-0.055x (half life: 12.6 days) and Ct=0.2304e-0.052x (half life: 13.3 days), respectively. Therefore, when triazole fungicides were applied during the cultivation of apple, the biological half-life need to be calculated with the optimal equation model.

들깻잎 중 chlorantraniliprole과 tetraconazole 잔류양상의 kinetic model 적용

김효정(Hyo-Jeong Kim),이상협(Sang-Hyeob Lee),곽세연(Se-Yeon Kwak),김태화(Tae-Hwa Kim),김장억(Jang-Eok Kim) 한국농약과학회 2019 농약과학회지 Vol.23 No.4

Chlorantraniliprole and tebuconazole were different dissipation patterns in perilla leaves. As using kinetic model, it could be predicted dissipation patterns and half-lives of pesticides in perilla leaves. In this study, three kinetic models (zero order (ZO), first order (FO) and second order (SO)) were employed to compare and characterize the best-fit kinetic model describing the residual pattern of chlorantraniliprole and tetraconazole in perilla leaves as a minor crop. Chlorantraniloiprole (5%, WG) and tetraconazole (12.5%, EW) were diluted with water and sprayed 2 times and 3 times at interval of 7 days before harvesting. The residual amounts of chlorantraniliprole and tetraconazole were analyzed by HPLC-UVD and GC-ECD. Comparing the correlation coefficients (r2) of the kinetic models, chlorantraniliprole was 0.843, 0.847 and 0.851 for the ZO, FO, SO respectively and tetraconazole was 0.978, 0.980, 0.970 for the ZO, FO, SO respectively. Therefore SO was best fit to chlorantraniliprole but FO was best fit the dissipation patterns of tetraconazole. The equations of biological half-life of chlorantraniliprole were y = 0.0124x + 0.2926 (half-life: 23.7 days) by using SO and tetraconazole y = 10.9390e-0.043x (16.1 days) by using FO respectively. Therefore, the biological half-life needs to be calculated with the optimal equation to predict.

시설재배 참외 중 살균제의 생물학적 반감기

이주희 ( Ju Hee Lee ),전영환 ( Young Hwan Jeon ),신갑식 ( Kab Sik Shin ),김효영 ( Hyo Young Kim ),박은정 ( Eun Jeong Park ),김태화 ( Tae Hwa Kim ),김장억 ( Jang Eok Kim ) 한국환경농학회 2009 한국환경농학회지 Vol.28 No.4

This study was conducted to know the biological half-lives and dissipation patterns of fungicides, pyrimethanil, chlorothalonil and tetraconazole in Korean melon under green house condition. The instrument for analyzing pyrimethanil and chlorothalonil was HPLC equipped with UV detector. Initial residue amounts of pyrimethanil were 0.16 mg/kg at recommended rate and 0.28 mg/kg at double recommended rate in Korean melon. The biological half-lives of pyrimethanil were 11.2 days at recommended rate and 10.1 days at double recommended rate in Korean melon. In case of chlorothalonil, initial residue amounts of chlorothalonil were 0.06 mg/kg at recommended and 0.11 mg/kg at double recommended rate in Korean melon. The biological half-lives of chlorothalonil in Korean melon were 3.4 days at recommended rate and 6.6 days at double recommended rate. The instrument for analyzing tetraconazole was GLC equipped with electron capture detector. Initial residue amounts of tetraconazole were 0.14 mg/kg at recommended and 0.22 mg/kg at double recommended rate in Korean melon, respectively. The biological half-lives of tetraconazole were 9.6 days at recommended rate and 18.5 days at double recommended rate in Korean melon.

흰쥐에 정맥 주사한 수용성 크롬의 분포 및 배설

김용래,김치년,노재훈 한국산업위생학회 2001 한국산업보건학회지 Vol.11 No.1

Chromium exposure can be in the forms of environmental pollution and occupational exposure. The harmful effects of chromium on the body greatly differ depending on its valence or solubility. Accordingly, the recommended permissible exposure limit for each chromium compound is different. This study investigated the increase or decrease of distribution and excretion of total chromium exposed simultaneously the soluble Cr+6 and Cr+3 compounds. There were no difference of total chromium concentration in plasma, red bloods cells, urine, organs between simul-taneously injected and individually injected soluble Cr+6 and Cr+3 compounds. The chromium clearances in urine also showed that there were two phases in the two groups. In the first phase, biological half lives of the total chromium of the two groups have been similar within 24hr., but in the second phase, biological half life of the group injected simultane-ously was 62.7 hr. and was less than that of the other group's 188.3 hr. The average concentration of total chro- mium in plasma was same with the control, and that of RBCs was 0.218 n ㏖/㎖ and was slightly increased in comparison with 0.121 n ㏖/㎖ of the control, which was not statistically significant. As a result, there were no differences of distribution and excretion of chromium between the group exposed sim-ultaneously and the other group exposed separately the soluble Cr+6 and Cr+3 compounds. The biological half life of chromium of the former group in urine was less than that of the other group.

생산단계 잔류허용 기준 설정을 위한 시설 재배 오이 중 살균제 Amisulbrom의 잔류특성 연구

황규원(Kyu-Won Hwang),김태완(Tae Wan Kim),유재홍(Jae-Hong Yoo),박병수(Byeoung-Soo Park),문준관(Joon-Kwan Moon) 한국농약과학회 2012 농약과학회지 Vol.16 No.4

The dissipation patterns of amisulbrom in cucumber under a greenhouse condition was investigated to establish biological half-life and pre-harvest residue limit (PHRL). Amisulbrom residue in/on cucumber on the day of application under standard application condition was 0.15 mg kg^?1 and decreased to 0.06mg kg^?1 after 5 days after treatment, so that biological half-life calculated 3.6 day, while initial concentration of amisulbrom twice application 3 days interval under standard application condition was 0.35 mg kg^?1 and decreased to 0.09 mg kg^?1 after same period and the biological half-life calculated 2.4 day. PHRL was suggested by prediction curve calculated from the decay constant of amisulbrom at standard rate. For example, 1.83 mg kg^?1 at 5 days before harvest and 1.03 mg kg^?1 at 2 days before harvest were suggested.

인삼 중 Clothianidin 및 Thiacloprid의 생산단계 농약잔류허용기준 설정

나은식(Eun-Shik Na),이용재(Yong-Jae Lee),김경주(Kyoung-Ju Kim),김성수(Seong-Soo Kim),이규승(Kyu-Seung Lee) 한국농약과학회 2013 농약과학회지 Vol.17 No.3

The residue patterns of clothianidin and thiacloprid, insecticides registered in the ginseng, were investigated to predict pre-harvest residues limits (PHRL). Pesticides were treated under Korea GAP (Good Agricultural Practices) with the recommended dose (single dose) and twice of recommended dose (double dose). Samples were collected 11 times over 42 days (each 0, 2, 5, 8, 12, 16, 20, 24, 28, 33, 42 days after treatment). Residues of clothinidin and thiacloprid were analyzed by UPLC/TQD. Biological half-life of clothinidin in single dose and double dose were 14.6 days and 10.2 days and that of thiacloprid were also 9.7 days and 11.2 days, respectively. The PHRL of ginseng on 10 days before harvest was 0.3 mg/kg in clothianidin and 0.18 mg/kg in thiacloprid.

대추 중 살균제 boscalid와 pyraclostrobin의 잔류 소실 특성

조형욱(Hyeong-Wook Jo),손상현(Sang-Hyun Sohn),김경진(Kyoung-Jin Kim),황기준(Gi-Jun Hwang),조범행(Beom-Haeng Jo),길석주(Seok-Ju Gil),권찬혁(Chan-Hyeok Kwon),문준관(Joon-Kwan Moon) 한국농약과학회 2017 농약과학회지 Vol.21 No.1

Dissipation pattern and biological half-lives of fungicides boscalid and pyraclostrobin were calculated on jujube. The pesticides were sprayed on jujube in two different field at the standard rate, respectively. The raw agricultural commodities were harvested at 0 (2 hr), 1, 3, 5, 7, 10 and 14 days after treatment, and analyzed by HPLC/DAD. The method limit of quantification (MLOQ) was 0.02 mg kg<SUP>−1</SUP> for boscalid and pyraclostrobin. The recovery ranged 101.8~109.3% with below 5% of CV (Coefficient of variation) for boscalid and 104.2~115.4% with below 5% of CV for pyraclostrobin. An average initial deposit at field 1 and field 2 samples were observed 0.40 and 0.48 mg kg<SUP>−1</SUP> for boscalid and, 0.76 and 0.57 mg kg−1 for pyraclostrobin, respectively. The biological half-lives of field 1 and field 2 were 11.0 and 13.2 day for boscalid, and 6.1 and 12.7 days for pyraclostrobin.

복숭아 중 Methoxyfenozide와 Novaluron의 생산단계 농약잔류허용기준 설정

조경원(Kyung-Won Cho),박재훈(Jae-Hun Park),김지원(Ji-Won Kim),윤지영(Ji-Yeong Yoon),문혜리(Hye-Ree Moon),이규승(Kyu-Seung Lee) 한국농약과학회 2013 농약과학회지 Vol.17 No.1

Methoxyfenozide and novaluron were sprayed with single and triple treatments separately on peach during cultivation period. Samples were collected over 14 days, 8 times in total (0, 2, 4, 6, 8, 10, 12, 14 days). Methoxyfenozide and novaluron were extracted with acetone and partitioned with dichloromethane, and analyzed by HPLC/DAD. Method Quantitation Limit (MQL) were both 0.005 mg/kg, average recoveries of methoxyfenozide at two fortification levels of 0.05 and 0.25 mg/kg were determined 92.7±2.9% and 102.8±3.1%, and novaluron were 98.2±4.8% and 96.7±9.0%, respectively. The biological half-life of methoxyfenozide was about 4.41 days at single treatment, and 4.24 days at triple treatments. The biological half-life of novaluron was about 14.81 days at single treatment, and 14.50 days at triple treatments. Dissipation of pesticides on peach was influenced by growth dilution effect. In case of application of methoxyfenozide and novaluron following guidelines on safe use of pesticides, the final residue level was predicted to be lower than Maximum Residue Limit (MRL).

매실 중 살균제 azoxystrobin과 difenoconazole의 생산단계 잔류허용기준 설정

이동열(Dong Yeol Lee),김영진(Yeong Jin Kim),박민호(Min Ho Park),이승화(Seung Hwa Lee),김상곤(Sang Gon Kim),강남준(Nam Jun Kang),강규영(Kyu Young Kang) 한국농약과학회 2013 농약과학회지 Vol.17 No.4

This study was carried out to investigate the residual characteristics of fungicide azoxystrobin and difenoconazole in Prunus mume fruits, and establish pre-harvest residue limits (PHRL) based on dissipation and biological half-lives of fungicide residues. The fungicides were sprayed onto the crop at recommended dosage once and 3 times in 7 days interval, respectively. The samples were harvested at 0, 1, 2, 4, 6, 8, 10, 12 and 14 days after treatment. These residual pesticides were extracted with QuEChERS method, clean-up with NH<SUB>2</SUB> SPE cartridge, and residues were analyzed by HPLC/DAD and GLC/ECD, respectively. Method quantitative limits (MQL) of azoxystrobin were 0.03 mg kg<SUP>?1</SUP> and of difenoconazole were 0.006 mg kg<SUP>?1</SUP>. Average recovery were 93.2 ± 2.49%, 85.5 ± 1.97% for azoxystrobin at fortification levels at 0.3 and 1.5 mg kg<SUP>?1</SUP>, and 100.8 ± 6.74%, 87.6 ± 9.92% for difenoconazole at fortification levels at 0.06 and 0.3 mg kg<SUP>?1</SUP>, respectively. The biological half-lives of azoxystrobin were 5.9 and 5.2 days at recommended dosage once and 3 times in 7 days interval, respectively. The biological half-lives of difenoconazole were 9.3 and 8.0 days at recommended dosage once and 3 times in 7 days interval, respectively. The PHRL of azoxystrobin and difenoconazole were recommended as 5.32 and 1.64 mg kg<SUP>?1</SUP> for 10 days before harvest, respectively.