Effects of Lipids on Analysis of Residue Pesticides in Herbal Medicines

김장억,이성은,김장억 한국응용생명화학회 2014 Applied Biological Chemistry (Appl Biol Chem) Vol.57 No.3

Serious problems in residue analysis of acetamipirid,chlorpyrifos, and bifenthrin caused by lipids present in herbalmedicines, platycodon root, safflower, and persicae semen havebeen found during the pesticide residue analysis using a currentlyused analytical method. Particularly, recovery tests for artificiallyspiked pesticides showed poor recoveries for bifenthrin in persicaesemen, which may be due to the low polarity of the pesticide andhigh lipid content in the matrix. An unclear layer separationbetween water and organic solvent, methylene chloride, has beenalso observed during the liquid-liquid partitioning process, whichfavors modification of the liquid-liquid partitioning by replacementwith acetonitrile and a macroporous diatomaceous earth column,respectively. The effectiveness of newly modified methods wasevaluated based on the recoveries of three pesticides in the herbalmedicines at two fortification levels (1.0 and 4.0 mg/kg). Themodified methods increased recoveries to 81.8–98.9%, suggestingthose methods could be effective and feasible alternatives todetermine acetamiprid, bifenthrin, and chlorpyrifos in lipidicsamples.

자연과학분야 / 통합연구 : 기독교와 환경오염 ( 초록 )

김장억 통합연구학회 1989 통합연구 Vol.2 No.4

제초제 Propanil 및 그 분해산물인 DCA(3,4-dichloroaniline) 와 Humic Monomer 들과의 산화적 짝지움반응

김장억,권태동 한국농화학회 1998 Applied Biological Chemistry (Appl Biol Chem) Vol.41 No.5

The herbicide propanil and its metabolite, DCA were incubated with oxidative catalysts in the presence or absence of humic monomers to evaluate the incorporation of them into humic substances. Propanil and DCA underwent little or no transformation by oxidatve catalysts in the absence of humic monomers. In the presence of humic monomers, the most effective co-substrate for transformation of propanil was syringic acid by laccase and HRP, that of DCA was catechol by laccase and HRP, and protocatechmic acid by birnessite. The transformation of DCA was the highest when it was incubated with catechol at pH 8.0 during 24 hrs by laccase, and with catechol at pH 3.0 during 2 hrs by HRP, and with protocatechuic acid at pH 5.0 during 2 hrs by birnessite. The DCA transformation increased with increasing concentration of humic monomers. The transformation of DCA was increased with about 5 times when it was incubated with lactase and birnessite together than lactase alone, but that of it was not effected when it was incubated with HRP and birnessite together. When DCA was incubated with dissolved organic carbon in the presence of oxidative catalysts, the transformation of it was not increased by lactase and birnessite but increased by HRP.

고감도 신속 다종농약다성분 검색/검사법 개발 연구 - LC-MS/MS법

김장억,이상협,곽세연,홍성현,조성찬,김효정 한국환경농학회 2018 한국환경농학회 학술대회집 Vol.2018 No.-

내년 1월 1일부터 시행될 농약허용물질 목록 관리 제도는 기준이 설정되지 않은 농약을 일률적으로 0.01 mg/kg으로 적용하는 것이다. 이 제도를 원활히 수행하기 위해서는 이 수준을 분석할 수 있는 국가 공정 분석법의 확립이 필요하다. 본 연구는 1차 및 2차연도에 수행한 LC-MS/MS 대상 340종중 다성분 분석에 적합하다고 판단되는264성분을 선별하여 Group 1로 지칭하였으며, 해당 성분을 다종농약다성분 분석법-제2법으로 검증하고자 한다. 시료는 오렌지를 사용하였으며, 유지 농산물 분석을 위한 탈지과정을 추가한 시험법은 대두 시료를 사용하였다. 다종농약다성분 분석법-제2법에 명시된 시료량 및 추출용매량을 조절하여 시료량 10 g 및 추출용매량 20 mL로 진행하였으며, 이에 따라 시험방법을 비율에 따라 조절하였다. 264종 농약에 대한 validation test를 실시한 결과, 분석대상농약의 정량한계는 모두 0.01 mg/kg 이하로 나타났으며, matrix-matched standard calibration의 상관계수가 오렌지의 경우 0.9901-1.000으로 나타났으며, 대두는 0.8923-0.9999로 나타났다. 다성분 분석법 기준인 70∼120%, 변이계수 22% 이하의 회수율 시험을 만족하는 농약의 수는 오렌지 250성분, 대두 245성분이었다. 표준혼합용액 조제물질 검증은 pH에 따른 저장안정성 및 저장온도에 따른 안정성을 확인하기 위하여 시험 중이다.

애그플레이션 시대 작물보호제의 위상과 역할

김장억 한국농약과학회 2008 한국농약과학회 학술발표대회 논문집 Vol.- No.-

토양의 자기방어 능력과 농약의 결합잔류물 - 토양이 농약을 분해한다

김장억 한국작물보호협회 1998 자연과 농업 Vol.19 No.2

살충제가 토양중 효소활성에 미치는 영향

김장억,홍종욱 한국토양비료학회 1986 한국토양비료학회 학술발표회 Vol.1986 No.36

제초제(除草劑) Propanil의 용액중(溶液中) 분해산물(分解産物)의 분리(分離) 및 동정(同定)

김장억,신윤교,홍종욱,Kim, Jang Eok,Shin, Yun Gyo,Hong, Jong Uck 경북대학교 농업과학기술연구소 1987 慶北大農學誌 Vol.5 No.-

용액중(溶液中) propanil 분해산물(分解産物)의 분리(分離) 및 동정(同定)을 위해서 2000ppm으로 처리(處理)한 후 2주(週) 간격(間隔)으로 12주(週)까지 일정(一定)한 온도(溫度)로 유지(維持)시키면서 주분해산물(主分解産物)을 조사(調査)한 결과(結果)는 다음과 같다. 추출(抽出)한 혼합물(混合物)로부터 benzene을 전개용매(展開溶媒)로 한 TLC에서 분해산물(分解産物)인 DCA와 TCAB를 Rf치(値) 0.65와 0.94에서 분리(分離)할 수 있었다. GC분석(分析)은 column 온도(溫度) $200^{\circ}C$에서 분리(分離)가 가능(可能)하지만 정량적(定量的) 분석(分析)에서 DCA는 $140^{\circ}C$, TCAB는 $250^{\circ}C$로 달리하여 분해경로(分解經路)를 조사(調査)하였다. IR spectrum에서 $3400cm^{-1}$와 $800cm^{-1}$의 흡수(吸收) band에 의(依)해 DCA의 작용기(作用基)가 결정(決定)되었다. NMR spectrum에서 $6.7{\delta}$와 $3.7{\delta}$의 peak는 DCA의proton과 일치(一致)하였다. 이와 같이 용액중(溶液中) 혼합추출물(混合抽出物)로부터propanil의 주분해산물(主分解産物)을 TLC로 분리(分離)하여 GC, IR, NMR로 동정(同定)한결과 propanil은 용액(溶液) 내(內)에서 DCA를 거쳐서 TCAB로 분해(分解)되는 것으로 나타났다. To isolate and identify degradation products of propanil in solution which propanil concentration was 2000ppm with a certain temperature, degradation products and pathway were investigated every 2 weeks for 12 weeks. Extracted mixture was developed with benzene on TLC plate, and Rf values of isolated DCA and TCAB were 0.65 and 0.94 respectively. At the GC analysis, propanil and its degradation products could seperate at the column temperature $200^{\circ}C$, but in order to more good resolution, the column temperature of DCA and TCAB was $140^{\circ}C$ and $250^{\circ}C$ respectively. Functional group of OCA was determined by IR spectrum $3400cm^{-1}$ and $800cm^{-1}$. Proton peaks of OCA were NMR spectrum $6.7{\delta}$ and $3.7{\delta}$. As the results, the major degradation products of propanil in solution were seperated on TLC plate, and thus identified by the analysis of GC, IR and NMR. Proposed degradation pathway of propanil in solution was from DCA to TCAB.

도로변에 인접한 경작지 토양 및 작물체중의 연오염(鉛汚染) : 제1보 경작지 토양중의 연오염(鉛汚染) 및 화학적 형태 Ⅰ. Pollution of Pb in paddy field soil and its chemical forms

김장억,이석준 한국환경농학회 1991 한국환경농학회지 Vol.10 No.1

自動車 排氣가수에 包含된 鉛化合物의 排出에 의하여 汚染이 되었을 것으로 豫想되는 大邱直轄市를 中心으로 慶尙北道 內의 高速道路 및 主要國道邊에 隣接한 18個 地點을 選定하여 道路로부터 距離에 따른 畓土壤에서 鉛汚染度 및 土壤中 鉛化合物을 KNO₃浸出性(置換態), Na₄P₂O_7 浸出性(有機態), EDTA 浸出性(炭酸態) NHO₃ 浸出性(黃酸態), 非浸出性(不溶態)로 形態別 分布를 調査한 結果는 다음과 같다. 1. 畓土壤中 平均 鉛含量은 淸道에서 30.0 ppm으로 가장 높았고 高靈에서 14.8 ppm으로 가장 낮았으며 平均 21.9 ppm 으로 나타났으며, 交通量과 關聯하여 土壤中 鉛含量은 差異를 發見할 수 없었으나 道路의 開通年度에 따라 약간의 差異를 나타났다. 2. 道路로부터의 距離에 따른 鉛含量은 10m 以內에서 22.2 ppm, 10∼30m에서 22.1 ppm, 30∼50m에서 22.2 ppm, 50m 以上 地域에서 21.3 ppm으로 道路로부터 距離에 따른 畓土壤中의 鉛汚染度는 크게 差異 나지 않았다. 3. 土壤中 鉛化合物을 形態別로 分別 抽出한 結果 여러 가지 土壤特性에 따라 差異가 深하나 18個 地點에서 平均한 鉛化合物의 化學的 形態別 分布比는 有機態 33.6%, 炭酸態 29.8%, 黃酸態 21.5%, 置換態 8.6% 및 不溶態 6.7%의 順으로 나타났다. 4. 土壤中 有機物含量이 增加할수록 有機態 鉛의 分布比는 增加하는 傾向을 나타낸 반면 置換態 鉛의 分布比는 減少하는 傾向을 나타내었다. 5. CEC가 增加할수록 有機態의 鉛의 分布比는 增加하는 傾向을 나타낸 반면 置換態 鉛의 分布比는 減少하는 傾向을 나타내었으며, CEC에 依한 土壤中 鉛化合物의 化學的 形態別 分布比는 有機物에 依한 分布比와 비슷한 傾向을 나타내었다. The object of this stduy was to investigate the pollution of Pb in paddy field soil with different distance from roadside and to find out the relationship between the ratio of chemical fractions of total Pb and soil characteristics. Lead from automobiles is exhausted as particulates composed primarily of halide compounds (PbBrCl, PbBr₂, PbCl₂). The samples of soil were collected directly from the paddy fields with different distance from the roadside of highway and expressway which are located in Kyungpook province. A sequential extraction procedure was used to fractionate Pb in paddy field soil into the disignated forms of water soluable, exchangeable, organically bounded, carbonate, sulfide, and residual Pb. Results obtained are summerized as follows. 1. The content of Pb in paddy field soil was the highest in Chungdo, 30.0 ppm, the lowest in Koryung, 14.8 ppm, and the total average content was 21.9 ppm. The effect of traffic volume was not clear, but a slight difference according to the order of opened year of roads was showed. 2. The effect of distance from roadside was not clear. The content of Pb in paddy field soil with different distance from roadside was 22.2 ppm within l0m, 22.1 ppm in 10∼30m, 22.2 ppm in 30∼50m. and 21.3 ppm beyond 50m. 3. The distribution of Pb fractions in soil showed a wide difference depending on soil properties. The average content of exchangeable. organically bounded, carbonate, sulfide, and residual Pb was 8.6%, 33.6%, 29.8%, 21.5%, and 6.7%, of total Pb in the soil, respectively. 4. The content of organically bounded Pb in soil showed highly positive correlation with organic matter and CEC, while the content of exchangeable Pb was highly negative correlation. 5. With higher soil organic matter and CEC, organically bounded Pb fraction tend to be higher but exchangeable Pb fraction tend to be lower. Other forms of Pb showed no difference with soil organic matter contend and CEC. The distribution of Pb fraction related to CEC showed similiar tendency with that of organic matter content.

Phthalimide系 殺菌劑가 土壤環境中 尿素의 分解에 미치는 影響

金章億 慶北大學校 1992 論文集 Vol.52 No.-

This study was conducted to elucidate the effects of the application of phthalimide fungicides on transformation of urea in soil environment. 1. The degradation ratio of the phthalimide fungicides was accelerated in urea-treated soil than urea-untreated soil. 2. The inhibition effects of phthalimide fungicides on urease activity in soil were largely inhibited in the early stage of experiment but nearly no effect in the late stage. 3. By the application of phthalimide fungicides, the formation of NH_4-N was increased by inhibition of nitrification and the oxidation process of NH_4-N to No_2-N was greatly affected than that of NO_2-N to NO_3-N in urea-treated soil. 4. The total number of bacteria was slightly decreased in the early stage of experiment but afterwards increased by the application of phthalimide fungicides.