본 연구에서는 농산물 시료 중 GC-ECD/MS 분석법을 이용 하여 국내에서 사용금지된 잔류성 유기염소계 살충제 19종 (aldrin, α-BHC, β-BHC, γ-BHC, δ-BHC, cis-chlordane, trans-chlordane, p,p'-DDT, o,p'-DDT, p,p'-DDE, p,p'-DDD, dieldrin, endrin, δ-keto-endrin, heptachlor, heptachlor epoxide, α-endosulfan, β-endosulfan 및 endosulfan sulfate)에 대해 동시분석법을 확립하였다. 농산물 시료에 acetone을 가하여 추출된 대상농약 19종의 잔류분은 n-hexane 분배법과 florisil 흡착 크로마토그래피법으로 정제하여 분석대상 시료로 하였다. DB- 5 capillary column을 이용한 GC-ECD 분석 시 불순물의 간섭은 없었으며, 사과, 고추, 배추, 현미 및 콩을 포함한 5종의 대표 농산물 중 대상농약 19종 각각의 정량한계(LOQ)는 각 0.003~0.01 mg/kg 수준이었다. 5종의 대표 농산물에 대한 대상농약 전체의 회수율은 76.5~116.0%를 나타내었으며, 농산물 시료 및 처리수준에 관계없이 10% 미만의 분석오차를 나타내어 잔류분석기준 이내를 만족하였다. 본 연구에서 확립된 국내 사용금지 잔류성 유기염소계 살충제 19종의 동시분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족할 뿐만 아니라, GC/MS SIM을 이용한 잔류분의 재확인 과정의 결과를 종합해 볼 때 분석과정의 편이성 및 신뢰성이 확보된 동시분석법으로 국내·외 수출입 및 유통 농산물의 잔류농약 검사에 사용 가능할 것이다.

An attempt was made to determine the residual distribution of organochlorine and organophosphorus pesticides in the various kinds of Korean tea which were purchased from the market. The organochlorine pesticides investigated in this study were BHC, DDT and dicofol and the organophosphorus pesticides were diazinon, EPN, fenitrothion and parathion. The pesticide residues were determined by GC-ECD and NPD. Only BHC was detected in all the samples and it's level were ranged from 0.00064 ppm to 0.05995 ppm and it's average was 0.00682 ppm and DDT, dicofol and organophosphorus pesticides were not detected in all samples. The organophophorus pesticides were detected(0.0035-0.0983 ppm) in raw materials but were not in the manufactured material and it is considered that the largely components of the pesticides is removed by drying and high temperature while the tea was manufactured. The recovery tests of the pesticides gave satisfactory results showing an average yield of 97.6% with organochlorine pesticides and 92.5% with organophosphorus pesticides and the detection limits level were 0.00008 ppm to 0.0010 ppm.

Polychlorinated Biphenyls (PCBs)는 유기염소계 농약잔류성분의 GLC분석에 간섭하는 물질이다. 본 실험에서는 PCBs의 존재하에 대표적인 유기염소계 농약 및 이들의 주요대사물의 분석을 목저르오 Florisil column상에서 PCBs와 농약성분의 분리를 시도하였다. 활성화한 Florisil column에서 , Heptachlor, epoxide, Dielerin, p.p'-DDD, p.p'-DDT와 Aroclor 1254는 완전히 그리고 정량적으로 분리하여 GLC로 분석할 수 있었다. Heptachlor와 Aldrin은 Aroclor와 함께 elution되나 Chromatogram 상에서 정량이 가능하였다. 본 시험에서 사용한 Florisil column chromatography는 많은 시료를 대상으로 한 잔류농약의 효과적 분석에 사용될 수 있다.

The Stockholm Convention, which was adopted in Sweden in 2001 to protect human health and the environment, includes regulations for Persistent Organic Pollutant Rotors such as toxic and bioaccumulatives. Currently, there are 28 types of materials. This prohibits and limits the production, use, and manufacture of products. Korea is a member of the Convention, and it is necessary to prepare management and treatment plans to address the POP trends. Thus, we experimentally investigate whether the environmentally stable incineration is achieved when the sample is thermally treated using the Lab-scale (1 kg/hr). The target samples is pesticides in liquid phase and solid phase. In this study, organic chlorinated pesticides and their thermal characteristics were analyzed. We calculated the theoretical air volume based on the element analysis results. Because the interior of the reactor is small, more than 10 times of the air ratio was injected. The retention time was set to at least 4 seconds using a margin. The incineration temperature was 850℃ and 1100℃. Thus, we experimentally investigated whether the environmentally stable incineration was achieved when the sample was thermally treated using the Lab-scale (1 kg/hr). We analyzed five types of exhaust gas; the 02 concentration was high, but the CO amount decreased. Complete combustion is difficult because of the small size of the furnace due to the nature of Lab-scale. The organic chlorine-containing pesticide had an average decomposition rate of 99.9935%. Considering the decomposition rates of organic chlorine-containing pesticide in this study, the incineration treatment at over 2 ton/hour, which is typical for a conventional incinerator, is possible. Considering the occurrence of dioxins and unintentional persistent organic pollutants, it can operate at more than 1,100℃.

Annex A and Annex B of the Stockholm Convention define POPs as unintentional releases to Annex C, as well as organochlorine pesticides, polychlorinated biphenyls and hexachlorobenzen which are intentionally produced and used. These pesticides are very stable in the atmosphere due to insecticides, fungicides, herbicides, etc., and are likely to accumulate in living organisms due to residues in crops. There are 15 substances listed in POPs. These materials are widely used due to their high chemical stability, low solubility in water, high volatility, strong insecticidal effect and relatively low production costs. Aldrin-containing pesticides are known to have a combustion method for incineration in a chemical incinerator equipped with a reheat-burner device and a gas scrubber, and a solidification isolation method for solidifying and filling with cement mixed with a combustible material in waste treatment. In the case of solid-phase pesticides, HCB was 421.8 ng/g, Endosolfan-2 73.044 ng/g, PeCB 53.972 ng/g and Endosolfan-1 43.649 ng/g. In the case of liquid pesticides, HCB concentration was the highest at 167.489 ng/g similar to that of the solid phase, followed by PeCB at 23.462 ng/g. B-HCH, g-HCH, d-HCH and the like were detected as a small amount of other substances. It is judged that it is not necessary to set separate operating conditions or preventive facility standards since the material is decomposed sufficiently at 850℃ or more. However, considering the possibility of dioxin or unintentional persistent organic pollutants, it is considered appropriate to operate at above 1,100℃.

As a result of analyzing the contents of organic chlorine pesticide-containing wastes, HCB 421.8 ng/g, Endosolfan- 2 73.044 ng/g, PeCB 53.972 ng/g, Endosolphan-1 43.649 ng/g respectively. In the case of liquid pesticides, the HCB concentration was the highest at 167.489 ng/g, similar to that of the solid phase, followed by PeCB at 23.462 ng/g. As a result of decomposition experiments on total OCPs among the pesticide liquid and solid phase components, initial concentrations were 597.384 ng/L for liquid pesticides and 198.176 ng/L for solid pesticides. However, the final effluent gas after decomposition showed a decomposition rate of more than 99.99% at a minimum of 0.005 ng/L and a maximum of 0.055 ng/L. Degradation test results for 25 species of OCPs such as PeCB, HCB, and Endosolfan for pesticide solid phase and liquid phase at reaction temperatures of 850℃ and 1,100℃. Of the 25 OCPs in the exhaust gas, trace amounts of PeCB and HCB were detected in the range of 0.006 to 1.025 ng/L at 1,100 ℃ and 850 ℃, and 23 OCPs were not detected. In the case of pesticides, the method of high temperature incineration and high temperature melting is proposed as the designated waste, but detailed methods of treatment conditions such as incineration conditions are not presented. Organochlorine pesticides were decomposed smoothly at 850 ℃ as well as incineration temperature of 1,100 ℃. However, since the dioxin concentration in exhaust gas exceeds 850 ℃, it is safe to operate at more than 1,100 ℃ in order to prevent the possibility of dioxin in advance.

The Stockholm Convention is an agreement to reduce POPs use, production and emissions. POPs are highly toxic substances and can not be decomposed in their natural state. It has the characteristic of long distance movement. In this study, we calculated the theoretical air volume based on the result of element analysis. Considering that the inside of the reactor is small, more than 10 times of the air ratio was injected. Also, the retention time was set to 4 seconds or longer by giving a margin. The incineration temperature was 850℃ and 1,100℃ degrees. As a result of thermogravimetric method analysis, the weight of chlorine-based flame retardant-containing wastes was 300∼600℃, and that of organic chlorine-based pesticides was 200∼400℃. On the basis of this, it was experimentally investigated whether the environmentally stable incineration is achieved when the sample is thermally treated using lab-scale, 1 kg/hr. As a result of analyzing five kinds of exhaust gas, the concentration of O2 was high, but the amount of CO was decreased. It is considered that complete combustion is difficult because of the small size of the furnace due to the nature of lab-scale. The chlorinated flame retardants had a decomposition rate of 100 % and the average organochlorine pesticides were 99.9935%. Considering the decomposition rates of chlorinated flame retardants and organochlorine containing pesticide derived wastes derived from this study, incineration treatment at over 2 tons/hour, which is a conventional incinerator, is considered to be possible. Considering the occurrence of dioxins and unintentional persistent organic pollutants, it is considered possible to operate at more than 1,100℃.

To obtain the risk assessment of hazardous materials in ginseng, the residues of heavy metals and organochlorine pesticides in samples on the Yeungju and Sangju are surveyed. Cd and Hg in ginseng on Yeungju and Sangju is not detected. 0.21 mg/kg of As, 0.39 mg/kg of Cr, 0.14 mg/kg of Pb, 1.83 mg/kg of Cu, 3.93 mg/kg of Zn and 0.43 mg/kg of Ni in ginseng on Sangju are shown. 0.25 mg/kg of Cr, 0.08 mg/kg of Pb, 1.11 mg/kg of Cu, 8.99 mg/kg of Zn and 1.15 mg/kg of Ni in ginseng on Yeungju are detected. As and Pb in ginseng on Sangju are 7.0% and 2.8% for Korea Food & Drug Administration(KFDA) advisory level, respectively. Pb in ginseng on Yeongju are 1.6% for Korea Food & Drug Administration(KFDA) advisory level. The heavy metals such as AS, Cr, Cd, Pb, Cu, Zn, Hg, Ni in soil on Yeongju and Sangju are range of 0-20% for with Korea Food & Drug Administration (KFDA) level. BHC isomer, DDT isomer and endosulfan isomer are not detected in ginseng and soil on Yeongju and Sangju, respectively. Finally, the assessment of hazardous materials of the heavy metals and organochlorine pesticides in ginseng on the Youngju and Sangju are verified the safety the level compare with tolerances level for Korea

본 연구에서는 식품의약품안전청고시에서 규제한 유기염소계 농약을 포함하여 다성분 동시분석법을 확립하였으며, 경상북도 상주지역 인삼자원의 재배토양 및 인삼 시료 중에서 유기염소계 농약의 잔류성을 검토하였다. α-BHC의 유지시간은 21.455분이었는데 이를 1.00으로 하였을때 β-BHC, δ-BHC, Quintozene, γ- BHC, Aldrin, Captan, o,p-DDE 및 α-Endosulfan의 상대적인 유지시간은 각각 1.025, 1.034, 1.038, 1.056, 1.143, 1.183, 1.199 및 1.218이었다. 또한 p,p-DDE, o,o-DDD, Dieldrin, Fenhexamid, Endrin, β- Endosulfan, o,p-DDT, o,p-DDD, p,p-DDT 및 Endosulfan-sulfate의 상대적인 유지시간은 각각 1.230, 1.242, 1.246, 1.261, 1.279, 1.283, 1.286, 1.329, 1.333, 1.338이었다. 피이크 분리가 정량분석하기에 지장이 없었으며, 따라서 19가지 유기염소계열 농약을 동시 다성분 분석 할 수 있었다. 최소검출농도는 α-BHC, Quintozene, Aldrin, Captan, α-Endosulfan, Dieldrin이 각각 0.95ng/g, 0.27ng/g, 1.04ng/g, 0.63ng/g, 0.55ng/g 및 0.62ng/g이었다. 또한 Fenhexamid, Endrin, β-Endosulfan, o,p-DDT, Endosulfan-sulfate도 각각 5.71ng/g, 0.61ng/g, 0.48 ng/g, 0.44ng/g 및 0.51ng/g이었다 상주지역의 인삼자원은 식품의약품안전청고시에서 생약의 잔류농약 허용기준으로 제시된 BHC, Aldrin, Dieldrin, Endrin 및 DDT가 불검출되었다. 또한 재배토양에서도 불검출 되었다. 따라서 경상북도 상주 인삼 재배환경은 유기염소계 농약으로 오염되지 않았다.

To obtain the residual organochlorine pesticides in the coastal environment, the methods of analysis for BHC's isomer, Kelthane, Orthocide and Endrin by GC-ECD are surveyed. The relative retention time for α-BHC, β-BHC, γ-BHC and δ-BHC is 1.00, 1.18, 1.24, 1.31 and it's of Kelthane, Orthocide, Endrin is 1.56, 1.70, and 2.02, respectively. The BHC isomers, Kelthane, Orthocide and Endrin are separated on the base line. The plate height(H) for α-BHC, β-BHC, γ-BHC and δ-BHC is 50mm, 35mm, 32mm and 29mm, and it's of Kelthane, Orthocide, Endrin is 81mm, 68mm and 48mm, respectively. The qualified defection concentration for α-BHC, β-BHC, γ-BHC and δ-BHC is 0.26, 0.36, 0.37 and 0.39ng/g and it's of Kelthane, Orthocide, Endrin is 0.55, 1.39 and 0.56ng/g, respectively. BHC's isomer, Kelthane, Orthocide and Endrin are not detected in soil environment on South Cheju Island. Also residual organochlorine pesticides are not detected in the sea water and sediment in the ocean environment.

Pesticides were extracted from samples with 70% acetone and methylene chloride in order, and then cleaned up via open-column chromatography apparatus packed with florisil, and finally analyzed simultaneously the organochlorine and pyrethroid pesticides using GC(ECD). An ultra-2 fused silica capillary column was used to separate and identify the products. The resolution between the last isomeric peak of cypermethrin(59.987min) and the first isomeric peak of flucythrinate(60.043min) was not satisfactory. The last isomeric peak of fenvalerate(62.344min) and the first isomeric peak of fluvalinate(62.397min) were overlapped. Recoveries of soybean sample for the most pesticides were 73.3% to 102.4%. Detection limits were between 0.004 and 0.063㎍/㎎ when this method was used.

본 실험은 1998년 1월부터 2001년 12월가지 4년간 경기도와 인천지역에 납품된 군납 농산물 17종(배추, 무, 오이, 감자, 사과, 양파, 파, 양배추, 고추, 당근, 상추, 호박, 마늘, 미나리, 시금치, 쑥갓, 부추)을 대상으로 유기염소계 농약 10종 (BHC, captafol, captan, chlorobenzilate, chlorothalonil, DDT, dicofol, endosulfan, folpet, tetradifon)을