송사리에서 제초제 Butachlor의 생물농축성

김용화,김균,Kim, Yong-Hwa,Kim, Kyun 한국응용생명화학회 2002 한국농화학회지 Vol.45 No.1

A bioconcentration experiment was performed for killifish using nonradioactive and radioactive butachlor. At 0.036 ppm concentration, the highest bioconcentration ratio $(C_f/C_w)$ and BCF at steady state recorded as 296 and 87 respectively. And at 0.0036 ppm concentration, the highest $C_f/C_w$ ratio was 169 and the BCF was 51 at steady state. Considering the experimental variation of the BCF's, the BCF of butachlor was tentatively determined to be $69{\pm}28$. And the $^{14}C-butachlor$ and its metabolites depurated about 50% within 12 hours and 90% within 30 hours after depuration experiment started. And in vivo metabolites, designated as M-I, M-II, and M-III, were found in killifish and the excretes as butachlor was metabolised. 제초제 butachlor의 어류농축 계수를 결정하기 위하여 동위원소 표지화합물과 비표지 화합물을 사용하여 송사리 체내에서의 농축시험을 수행하였다. 비표지 화합물을 사용하였을 때 송사리 체내에서의 butachlor농축은 0.036ppm농도에서 40시간 경과 후 가장 높은 어류생체 중 296의 생체 농도/수중 농도$(C_f/C_w)$ 비율을 보였고, 64시간 이후부터는 평형상태에 이르렀으며, 이 때의 bioconcentration factor(BCF)는 87이었다. 또한, 0.0036 ppm도에서는 18시간 경과 후 가장 높게 축적되어 $C_f/C_w$의 비율이 169였고, 60시간 이후에는 평형상태에 도달하여 BCF 값은 51이었으며, 이 두 농도로부터 결정된 BCF 값은 $69{\pm}28$이었다. $^{14}C-butachlor$의 송사리 체내에서의 농축 및 배설은 총 $^{14}C$를 기준으로 하였을 때 17시간 경과 후 가장 높은 539 $C_f/C_w$의 비율을 나타내었고, 74시간 이후부터는 평형상태에 이르러 BCF는 394로 계산되었다. 그러나 14C-butachlor의 양만을 고려했을 때 $C_f/C_w$의 비율은 총 흡수량의 1/3이었고, 2/3은 $^{14}C-butachlor$의 대사물 이었으며, 평형상태에서의 $^{14}C-butachlor$의 BCF는 334로 계산되었다. 또한, 송사리 체내로부터의 $^{14}C-butachlor$의 배설은 12시간 이내에 50% 이상이, 30시간이 되면서 90% 이상이 배설되었다. 생체 내에서의 대사물은 아주 극성이 강한 대사물들로서 TLC상에서 $R_f$이 0.43인 대사물 M-II와 $R_f$값이 0.7인 대사물 M-III로 확인되었고, 신선한 사육수로 어체내 대사산물을 배설시켰을 때 $R_f$ 값이 0.25인 대사물 M-I을 확인하였다. M-I은 어체내에서 배출되는 과정중의 주요한 중간 대사물 임을 예상할 수 있었다.

농약의 토양 표면유출에 관한 연구 - Ⅰ 포장에서 자연강우에 의한 Captafol 의 유출특성

김균(Kyun Kim),김용화(Yong Hwa Kim),김정한(Jeong Han Kim),박창규(Chang Kyu Park) 한국응용생명화학회 1996 Applied Biological Chemistry (Appl Biol Chem) Vol.39 No.6

As a first step of pesticide runoff studies, runoff losses of captafol were measured under natural rainfall conditions in apple orchard area. The maximum concentration of captafol was 180 ppb at 5 th sampling period when the rainfall occurred within 24 hours after captafol was applied, and the concentration of samples from other periods was below than 20 ppb. Total runoff loss of captafol was below 0.1%. About 10 fold of dilution factor was observed at the merging point with stream near outlet from orchard and about 50 fold was observed at the next merging point which is located further down. Therefore, captafol will not harm the aquatic organisms due to dilution factor(10∼50 fold) and rapid hydrolytic degradation rate even when it was run off into a stream nearby.

Benzoylphenylurea 계 살충제 Bistrfluron의 물리화학적 특성

김균 ( Kyun Kim ),장희라 ( Hee Ra Chang ),양규완 ( Kyu Wan Yang ),정봉진 ( Bong Jin Jeong ),김용화 ( Yong Hwa Kim ) 韓國環境農學會 2007 한국환경농학회지 Vol.26 No.3

화학물질의 생분해성 측정을 위한 OECD 시험법의 평가

김하강(Ha Kang Kim),김균(Kyun Kim),김용화(Yong Hwa Kim),이영하(Young Ha Rhee) 한국환경생물학회 1999 환경생물 : 환경생물학회지 Vol.17 No.2

The efficiency of the OECD MITI(Ⅰ) test which is designated as a standard method for measuring the biodegradability of chemicals by the Korean Ministry of Environment was evaluated and compared with those of two other OECD ready biodegradability test : the manometric respirometry test and the closed bottle test. All the tests were applicable to a wide variety of organic chemicals and there were no significant differences in biodegradation rates of eight test chemicals and a reference chemical with three methods. However, the MITI(Ⅰ) test had unnecessary expense and complexity in preparation of a mixed inoculum. Decrease in bacterial diversity during pre-conditioning of the inoculum for 1 month was observed and therefore the mixed inoculum did not ensure the presence of a variety of species in the test. Based on the simplicity, cost-effectiveness and reproducibility of the test procedure, it is considered that the manometric respirometry test is the most adequate method which can replace the MITI(Ⅰ) test method.

농약의 물리화학적 특성 연구 (II) Flupyrazofos의 수용성, 가수분해, 증기압, 옥탄올/물 분배계수

김정한,김용화,김균,Kim, Jeong-Han,Kim, Yong-Hwa,Kim, Kyun 한국응용생명화학회 1997 Applied Biological Chemistry (Appl Biol Chem) Vol.43 No.1

국내에서 최초로 합성, 개발된 유기인계 살충제인 flupyrazofos(KH-502)의 물리화학적 특성으로 수용성, 가수분해, 증기압, 분배계수를 EPA와 OECD 방법에 준하여 측정하였다. 수용성은 $25^{\circ}C$에서 0.80 ppm으로 낮았고 가수분해 반감기는 $25^{\circ}C$에서 266.5시간(pH 4.0), 180.0시간(pH 7.0), 120.9시간(pH 9.0)으로 알칼리 조건에서 불안정하였으며 $40^{\circ}C$에서는 $25^{\circ}C$보다 $2{\sim}4$배 정도 가수분해가 빠르게 진행되었다. 상은($25^{\circ}C$)에서의 증기압은 $2.81{\times}10^{-5}$ torr로 측정되었고, 다른 두 온도(35, $45^{\circ}C$)에서 증기압을 측정하여 log P=0.673-(1565.4/T)라는 관계식을 구하였다. Flupyrazofos의 상온($25^{\circ}C$)에서의 증기압은 diazinon과 유사한 수준이었고, DDVP보다는 약 1,000배 정도 낮은 수치로 휘발에 의하여 환경에 영향을 미칠 가능성은 낮을 것으로 판단되었다. Flupyrazofos의 옥탄올/물 분배계수치를 보면(log Kow=5.24) 먹이연쇄를 통한 생물농축이 예상되나 비교적 가수분해가 빠르기 때문에 비록 수계에 노출된다고 하여도 그 가능성은 매우 낮을 것으로 사료된다. Several physicochemical properties such as water solubility, vapor pressure, hydrolysis and octanol/water partition coefficient(Kow) of flupyrazofos, the first organophosphorus insecticide developed in Korea, were measured based on EPA and OECD methods. Water solubility was low showing 0.80 ppm at $25^{\circ}C$ and in hydrolysis study, half-life at $25^{\circ}C$ was 266.5 hr(pH 4.0), 180.0 hr(pH 7.0) and 120.9 hr(pH 9.0) demonstrating instability in alkaline solution. At $40^{\circ}C$ hydrolysis rate was $2{\sim}4$ times higher than that at $25^{\circ}C$. The equation log P=0.673-(1565.4/T) was obtained from vapor pressure experiments at three different temperatures (25, 35, $45^{\circ}C$) and $2.81{\times}10^{-5}$ torr was obtained at $25^{\circ}C$. This value is similar to that of diazinon and 1,000 times lower than that of DDVP suggesting it would not give environmental contamination by volatilization. High log Kow(5.24) was observed and this might result in bioconcentration through food chain. However, its possibility is not likely to be high due to its relatively rapid hydrolysis.

농약의 물리화학적 특성 연구 (2) Flupyrazofos의 수용성 , 가수분해 , 증기압 , 옥탄올 / 물 분배계수

김균,김정한,김용화 ( Kyun Kim,Jeong Han Kim,Yong Hwa Kim ) 한국응용생명화학회 1997 Applied Biological Chemistry (Appl Biol Chem) Vol.40 No.1

Several physicochemical properties such as water solubility, vapor pressure, hydrolysis and octanol/ water partition coefficient(Kow) of flupyrazofos, the first organophosphorus insecticide developed in Korea, were measured based on EPA and OECD methods. Water solubility was low showing 0.80 ppm at 25℃ and in hydrolysis study, half-life at 25℃ was 266.5 hr(pH 4.0), 180.0 hr(pH 7.0) and 120.9 hr(pH 9.0) demonstrating instability in alkaline solution. At 40℃ hydrolysis rate was 2∼4 times higher than that at 25℃. The equation log P=0.673-(1565.4/T) was obtained from vapor pressure experiments at three different temperatures (25, 35, 45℃) and 2.81×10^(-5) torr was obtained at 25℃. This value is similar to that of diazinon and 1,000 times lower than that of DDVP suggesting it would not give environmental contamination by volatilization. High log Kow(5.24) was observed and this might result in bioconcentration through food chain. However, its possibility is not likely to be high due to its relatively rapid hydrolysis.

농약 Chlorothalonil 과 Command 의 수용성 및 증기압

김균,김영배,김용화,노정구,Kim, Kyun,Kim, Yong-Bae,Kim, Yong-Hwa,Roh, Jung-Koo 한국환경농학회 1987 한국환경농학회지 Vol.6 No.2

Chlorothalonil 과 Command 의 수용성과 증기압을 미국 EPA 와 OECD의 방법에 준하여 측정하였다. 두 화합물의 수용성은 문헌치와 잘 일치하였다. 그러나 chlorothalonil의 증기압은 handbook 에 나타난 수치보다 5,000배 낮았고($25^{\circ}C$에서 $2{\times}10torr$)의 Command 증기압은 100배 이상 낮음($45^{\circ}C$에서 $1{\times}10\;torr$ 이하)을 발견하였다. 따라서 handbook 류의 문헌의 물리화학적 특성치를 이용하여 환경동태를 예측하는 데는 주의를 요한다. 이상의 실험을 통하여 실험상의 난점들을 파악할 수 있었고 미국내에서 Command 가 주위작물에 준 표백현상은 증기확산에 의한 것이라기 보다는 살포시 유실에 의한 현상일 가능성이 높을 것으로 추론하였다. 이러한 접근방법은 새로운 화학물질의 개발단계에서 환경동태의 예측, 기존 화학물질의 오염가능성 예측, 오염저감 대책의 제시에 기초가 될 것으로 사료된다. The water solubilities and vapor pressures of chlorothalonil and Command were measured following the guidelines of the U.S. EPA and OECD. Water solubility of the two compounds is consistent with respective values in the literature. However, the vapor pressures of Chlorothalonil and Command were 5,000 times$(2{\times}10^{-7}\;torr\;at\;25^{\circ}C)$ and 100 times$(<1{\times}10^{-6}\;torr\;at\;45^{\circ}C)$ lower than the literature values, respectively. Courteous use of the vapor pressure values in the handbooks is suggested. With this study, experimental difficulties involved were recognized. Based on the low vapor pressure of Command, the cause of the accidental bleach of non-target plants in the United States might not be attributed to the volatilization of Command, but to the drift during the application of the herbicide. These approaches will be utilized to predict the environmental fate of new chemicals under development, to screen the potential environmental pollutants among chemicals already in use, and to assess measures to minimize the hazards.

Formaldehyde 가스 흡입에 의한 마우스의 급성독성 및 소핵 유발성에 관한 연구

김충용,김균,심점순,김용화,노정구,Kim, Choong-Yong,Kim, Kyun,Shim, Jeom-Soon,Kim, Yong-Hwa,Roh, Jung-Koo 한국독성학회 1991 Toxicological Research Vol.7 No.1

The acute and genetic effect of formaldehyde on mice through inhalation route was studied. The Riley's chamber with one stack of cage was used for the exposure and the micronucleus test was performed under unprecedently maximum exposure concentration. LC50's of formaldehyde in mice by whole body exposure for 4 hours were 105.5 ppm with 95% confidence interval of 72.6 ppm and 143.2 ppm for male, and 159.2 ppm with 95% confidence interval of 116.5 ppm and 272.7 ppm for female. Cinicial symptoms by acute exposure were salivation, lacrimation, and abnormal respiration.

농약의 물리화학적 특성연구 (1) Captafol의 수용성 , 가수분해 , 증기압 , 옥탄올 / 물 분배계수

김균,김정한,이성규,김용화 ( Kyun Kim,Jeong Han Kim,Sung Kyu Lee,Yong Hwa Kim ) 한국응용생명화학회 1997 Applied Biological Chemistry (Appl Biol Chem) Vol.40 No.1

Important physicochemical properties of captafol[N-(1,1,2,2-tetrachloro- ethylthio)cyclohex-4-ene-1,2-dicarboximide], water solubility, vapor pressure, hydrolysis and octanol/water partition coefficient(Kow) were measured based on the standard EPA and OECD methods. Water solubility of the chemical was 2.24 ppm at 25℃. Half-life by hydrolysis at 25℃ in the buffer solution of pH 3.0, pH 7.0, and pH 8.0 was 77.8 hr, 6.54 hr and 0.72 hr, respectively, demonstrating instability in alkaline solution. The half-life in acid condition was not significantly different by temperature change, however, that in neutral or alkaline solution became shorter at 40℃. Hydrolysis study with a reference compound, diazinon, proved that the experimental method of the present study is reliable. Vapor pressure of captafol, 8.27×10^(-9) torr at 20℃, was calculated from the equation, log P=6.94-(4401.6/T) plotted on the experiment results under different temperature conditions, 40, 50, and 60℃. Judging from this vapor pressure of captafol, the contamination of captafol would not happen easily in environment by vaporization. High Kow value of 1,523 was observed and this might result in bioconcentration through food chain when captafol was exposed. However, affecting human health through aquatic bioaccumulation is not likely to occur due to its rapid hydrolysis in the environment.

농약의 토양 표면 유출에 관한 연구-II 포장에서 인공강우에 의한 phorate의 유출특성

김균,염동혁,김정한,이성규,김용화,박창규 ( Kyun Kim,Dong Hyuk Yeom,Jeong Han Kim,Sung Kyu Lee,Yong Hwa Kim,Chang Kyu Park ) 한국응용생명화학회 1997 Applied Biological Chemistry (Appl Biol Chem) Vol.40 No.4

Runoff of phorate, soil insecticide, were measured under simulated rainfall conditions in field using small test plot(120×120 ㎝) at the loam area and loamy sand area. Fish acute toxicity tests were performed with runoff water to elucidate its toxicological effect on organisms in ecosystem. The average concentrations of phorate in runoff water from loam and loamy sand soil were 11.3 ppb and 4.8 ppb, respectively. However, there was no significant concentration difference between the heavy and the light rain. With loam soil, average runoff rates were 1.31 and 0.18%, while with loamy sand soil those were 0.48 and 0.012% under the heavy and the light rain conditions, respectively. Total average runoff rate was 0.50%. With killifish, no mortality was observed in runoff water from loamy sand soil, whereas half of the population was dead in runoff water from loam soil when it was diluted to 54.4% content.