우리나라에 축산물을 수출한 국가들이 2022년과 2023년 에 제출한 2019-2022년 국가별 잔류물질검사프로그램(NRP) 자료를 바탕으로 축산물 유형별, 국가별로 잔류허용기준 을 위반한 동물용의약품과 환경오염물질의 현황을 분석하 였다. 가장 많이 위반된 잔류물질은 네오마이신 2 4 1건, 페 니실린G 183건, 겐타마이신 151건, 세프티오퍼 113건, 니카 바진 103건 등이였고 축산물별로는 소고기, 돼지고기, 가 금육, 우유, 계란 등의 순서로 나타났다. 잔류 위반이 가 장 많았던 소고기에서는 페니실린G, 세프티오퍼, 플루니신 , 네오마이신, 벤질페니실린, 멜록시캄, 플로르페니콜, 질 파테롤 등 전염병 치료에 사용되는 항생제와 해열제 및 성장 촉진에 사용되는 동물용의약품이 주로 검출되었지만 , 돼지고기에서는 성장촉진을 목적으로 사용되는 락토파민 과 항생제인 독시사이클린, 클로람페니콜, 벤질페니실린, 난드롤론, 티오라실, 스트렙토마이신 및 임신 촉진에 사용 되는 호르몬이 가장 흔하게 검출된 것으로 나타났다. 가 금육에서는 콕시듐증 치료에 사용되는 항생제인 니카바진 이 가장 많이 위반되었으며, 스트렙토마이신, 아미노글리 코사이드 항생제, 벤질페니실린, 독시사이클린 및 기타 항 생제가 그 뒤를 이었다. 동물용의약품의 잔류 위반은 많 은 국가에서 보고되고 있으나, 다이옥신과 PCB와 같은 환 경오염 물질의 잔류는 주로 유럽 국가에서 보고되었다. 국 가별 잔류물질의 차이는 각국에서 사육되는 가축과 사육 관리 방식의 차이에 의한 것으로, 소고기의 잔류 수준이 높은 것은 소는 다른 동물에 비해 질병 발생 시 개체별로 치료되기 때문일 것으로 추정된다. 본 연구 결과는 수입 축산물의 안전성 확보를 위하여 국가별, 축산물별로 중점 적으로 검사가 필요한 물질을 제시함으로써 매년 실시하 는 수입 축산물 잔류물질검사를 보다 과학적이고 효율적 으로 수행할 수 있는 기반을 제공하였다.

In this study, an simultaneous LC-MS/MS multi-residue analytical method was developed and validated for the residues of six neonicotinoid insecticides (acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam) in honey. Sample preparation included a combination of QuEChERS extraction kit and liquid-liquid extraction method to effectively extract pesticide components from the honey matrix and optimized analytical conditions to achieve high sensitivity and selectivity. The limits of detection (LOD) and the limits of quantitation (LOQ) were set in the range of 6-15 ng/mL and 19-44 ng/mL, respectively and the correlation coefficient (R²) was greater than 0.99, confirming good linearity. In addition, the intra-day recoveries for each pesticide were 75-104%, and the coefficient of variation (CV) was less than 20%, which met the guideline recommended by the Ministry of Food and Drug Safety. The LC-MS/MS method developed in this study is expected to be used as a multi-residue analysis method for 6 neonicotinoid pesticides in honey.

From 2020, Korean Animal and Plant Quarantine Agency has reset the withdrawal time (WT) for veterinary drugs typically used in livestock in preparation for the introduction of positive list system (PLS) program in 2024. This study was conducted to reset the MRL for tiamulin (TML) in broiler chickens as a part of PLS program introduction. Forty-eight healthy Ross broiler chickens were orally administered with TML at the concentration of 25 g/L (TML-1, n=24) and 50 g/L (TML-2, n=24) for 5 days through drinking water, respectively. After the drug treatment, tissue samples were collected from six broiler chickens at 1, 2, 3 and 5 days, respectively. According to the previously established analysis method, residual TML concentrations in poultry tissues were determined using LC-MS/MS. In TML-1, TML in all tissues was detected less than LOQ at 2 days after drug treatment. In TML-2, TML in liver and kidney was detected more than LOQ at 2 days after treatment. According to the European Medicines Agency’s guideline on determination of withdrawal periods, withdrawal periods of TML-1 and TML-2 in poultry tissues were established to 0 and 2 days, respectively. In conclusion, the estimated WT of TML in poultry tissues is shorter than the current WT recommendation of 5 days for TML in broiler chickens.

This study was conducted to reset the maximum residue limit (MRL) for didecyldimethylammonium chloride (DDAC) in broiler chickens. The disinfectant containing DDAC (10%, w/w) was diluted 160 times and evenly sprayed on the bodies of twenty-four broiler chickens at a rate of 15 mL per day per bird for 7 days. After the disinfectant treatment, tissue samples were collected from six broiler chickens at 0.25, 1, 3 and 5 days, respectively. Residual DDAC concentrations in poultry tissues were determined using LC-MS/MS. Correlation coefficient (0.99 >), the limits quantification (LOQ, 2.0~10.0 μg/kg), recoveries (86.9~118.6%), and coefficient of variations (<19.98%) were satisfied the validation criteria of Korean Ministry of Food and Drug Safety. In all tissues except for liver, DDAC was detected more than LOQ at 5 days after the disinfectant treatment. In liver tissues, DDAC was detected more than LOQ at 3 days after treatment. According to the European Medicines Agency’s guideline on determination of withdrawal periods, withdrawal period of DDAC in poultry tissues was established to 26 days. In conclusion, the developed analytical method is sensitive and reliable for detecting DDAC in poultry tissues. When DDAC disinfectant is sprayed on a poultry house in the presence of broiler chickens, it is necessary to keep the disinfectant from contacting the body of the livestock.

This study investigated ethopabate (EPB) residues in edible tissues of broiler chickens given in drinking water and established the withdrawal time (WT) of EPB in poultry tissues. Twenty-four healthy Ross broiler chickens were orally administered with EPB at the concentration of 3.8 mg/L for 14 days (EPB-1, n=24) and 15.2 mg/L for 7 days (EPB-2, n=24) through drinking water, respectively. After the drug treatment, tissue samples were collected from six broiler chickens at 0, 1, 3, and 5 days, respectively. EPB residue concentrations in poultry tissues were determined using LC-MS/MS. Correlation coefficient values ranged from 0.9980 to 0.9998, and the limits of detection and quantification (LOQ) were 0.03~0.09 and 0.1~0.3 μg/kg, respectively. Mean recoveries in muscle, liver, kidney and skin/fat tissues were 95.9~109.8, 108.7~115.3, 89.9~96.6 and 86.7~96.8%, respectively, and coefficient of variations were less than 17.11%. At the end of the drug-administration period (0 day), EPB was detected at levels under the LOQ in all tissues from both the EPB-1 and EPB-2 groups. According to the results of EPB residue in Ross broiler tissues, withdrawal periods of both EPB-1 and EPB-2 in poultry tissues were established to 0 day. In conclusion, the developed analytical method is suitable for the detection of EPB in poultry tissues, and the estimated WT of EPB in poultry tissues will contribute to ensuring the safety of Ross broiler chickens.

From 2020, Korean Animal and Plant Quarantine Agency has reset the withdrawal time (WT) for veterinary drugs typically used in livestock in preparation for the introduction of positive list system (PLS) program in 2024. This study was conducted to reset the MRL for amprolium (APL) in broiler chickens as a part of PLS program introduction. Forty-eight healthy Ross broiler chickens were orally administered with APL at the concentration of 60 mg/L (APL-1, n=24) for 14 days and 240 mg/L (APL-2, n=24) for 7 days through drinking water, respectively. After the drug treatment, tissue samples were collected from six broiler chickens at 0, 1, 3 and 5 days, respectively. Residual APL concentrations in poultry tissues were determined using LC-MS/MS. Correlation coefficient (0.99 >), the limits quantification (LOQ, 0.3~5.0 μg/kg), recoveries (81.5~112.4%), and coefficient of variations (<15.5%) were satisfied the validation criteria of Korean Ministry of Food and Drug Safety. In APL-1, APL in all tissues except for kidney was detected less than LOQ at 3 days after drug treatment. In APL-2, APL in liver and kidney was detected more than LOQ at 5 days after treatment. According to the European Medicines Agency’s guideline on determination of withdrawal periods, withdrawal periods of APL-1 and APL-2 in poultry tissues were established to 3 and 2 days, respectively. In conclusion, the developed analytical method is sensitive and reliable for detecting APL in poultry tissues. The estimated WT of APL in poultry tissues is longer than the current WT recommendation of 2 days for APL in broiler chickens.

This study investigated chlorpheniramine maleate (CPM) residues in milk of intramuscularly dosed dairy cows and established the withdrawal time (WT) of CPM in milk. Sixteen healthy Holstein cows were injected with 10 (CPM-1) and 20 mL (CPM-2) of the drug containing 4 mg/mL of CPM, respectively. After administration of CPM, milk samples were collected from all cows at 12 hour intervals for 5 days. CPM residue concentrations in milk were determined using LC-MS/MS. The correlation coefficient of the calibration curve was 0.9956, and the limits of detection and quantification (LOQ) were 0.6 and 1.0 μg/kg, respectively. Recoveries ranged between 98.5-115.0%, and coefficient of variations were less than 10.96%. After treatment, CPM in CPM-1 and CPM-2 was detected below the LOQ in all milk samples at 12 hours. According to the European Medicines Agency’s guideline on determination of withdrawal periods for milk, withdrawal periods of both CPM-1 and CPM-2 in milk were established to 12 hours. In conclusion, the developed analytical method is sensitive and reliable for detection of CPM in milk, and the estimated WT of CPM in bovine milk will contribute to ensuring the safety of milk.

본 연구는 불법적으로 수산물에 사용될 수 있는 염료 18종에 대한 안전관리 강화를 위해 정량 및 정성 분석이 가능한 LC-MS/MS를 적용하여 검증하기 위해 수행되었다 . 확립된 시험법은 CODEX CAC/GL-71 가이드라인에 따라 직선성, 정밀성 , 정량한계 및 회수율 등을 통해 유효성을 확인하였다 . 대상시료에 1% 아세트산을 함유한 아세토니트릴로 추출 후 C18 과 PSA로 정제하였다 . 본 실험에서 정량한계는 0.002 mg/kg 수준으로 정량한계를 포함한 농도에 따라 검량선을 작성하였고 모두 0.98 이상의 직선성을 확인하였다 . 또한 정확성은 63%-112% 이고, 정밀도는 15% 이하로 재현성이 우수하였다 . 국내 유통 중인 수산물 124 건을 수거하여 개발된 분석법의 적용성 검증과 안전성을 확인하고자 잔류실태조사를 실시 하였고 그 결과 7건이 미량으로 검출 되었고 부적합은 없었다 . 확립된 시험법은 수산물 안전관리에 활용할 수 있을 것으로 사료되는 바이다 .

본 연구에서는 GC-NPD/MS를 이용하여 농산물 중 국내 사용금지 고독성 유기인계 살충제 phosphamidon의 잔류 분석법을 확립하였다. 대표 농산물은 배추, 고추, 감귤, 현미 및 콩을 사용하였고, acetone으로 추출된 phosphamidon은 n-hexane 및 dichloromethane 액-액 분배법을 순차적으로 이용하고 silica gel 흡착크로마토그래피법으로 정제하여 GC-NPD/MS 의 분석시료로 사용하였다. Phosphamidon의 정량분석을 위한 최적 GC-NPD 분석조건을 확립하였으며, 정량한계(LOQ)는 0.02 mg/kg 이었다. 각 대표 농산물에 대해 정량한계, 정량한계의 10배, 50배 및 100배 수준에서 회수율을 검토한 결과, 모든 처리농도에서 84.9~100.7% 수준의 회수율을 나타내었으며, 반복 간 변이계수(CV)는 최대 4.9%를 나타내어 잔류분석 기준인 회수율 70~120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였으며, GC/MS SIM을 이용하여 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규 phosphamidon의 GC-NPD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량분석법으로 사용 가능할 것이다.

A simple and fast analytical method based on liquid chromatography-tandem mass spectrometry was developed for detection of the veterinary drugs acetanilide, anthranilic acid, antipyrine, cyproheptadine, diphenhydramine, DLmethylephedrine, and phenacetin in bovine milk. The target analytes were extracted from milk samples by using acetonitrile followed by clean-up with C18 and liquid-liquid purification with saturated n-hexane. A reverse-phase analytical column was employed with a mobile phase comprising (A) 0.1% formic acid in distilled water and (B) 0.1% formic acid in acetonitrile to achieve the best chromatographic separation. Matrix-matched calibration curves (r2 ≥ 0.9986) were constructed using six concentrations (1, 2, 5, 10, 20, and 40 μg/kg) of drugs in the milk matrix. Recoveries at three drug-spiking levels (5, 10, and 20 μg/kg) ranged from 71.2% to 103.8% with intra-day and inter-day relative standard deviation (RSD) values of ≤ 8.6%. The calculated limits of quantification (LOQ) were 0.19-7.1 μg/kg.

본 연구는 HPLC-DAD/MS를 이용하여 농산물 중 triazine 계 제초제인 cyanazine의 잔류 분석법을 확립하였다. 대표 농산물은 사과, 배추, 고추, 현미 및 콩을 선정하였고, 아세톤을 첨가하여 추출된 cyanazine 성분을 dichloromethane 액-액 분배법과 florisil 흡착크로마토그래피법으로 정제하여 HPLCDAD/ MS 분석대상의 시료로 사용하였다. Cyanazine의 정량적 분석을 위한 최적 HPLC-DAD/MS 분석조건을 확립하였으며, 정량한계(LOQ)는 0.02 mg/kg 이었다. 각 대표 농산물에 대해 정량한계, 정량한계의 10배 및 50배 수준에서 회수율을 검토한 결과, 모든 처리농도에서 83.6~93.3% 수준을 나타내었으며, 반복 간 변이계수(CV)는 최대 2.8%를 나타내어 잔류분석 기준인 회수율 70~120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였고, 또한 LC/MS SIM을 이용하여 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규 cyanazine의 HPLC-DAD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로 사용 가능할 것이다.

Macrophomina phaseolina균(菌)을 이용(利用)하여 살균제 Triadimefon의 밀 품종 Kharchia와 Lal Bahadur에 있어서 수확후의 잔류량을 조사한 결과 살포식물의 밀짚에서는 Triadimefon이 검출되었으나 밀 종자에서는 검출되지 않았다. 잔류량 조사를 위해 개발된 박층(薄層) 크로마토그라피에 의하여도 동일한 결과를 얻었다. 기주체내에서 Triadimefon은 Triadimenol로 전환되었다.

This study evaluated the heating value derived from waste trees generated by thinning in Daejeon Metropolitan City. These trees are generated and stored in the forest without being handled separately after thinning. They can be used as a source of energy as they have a high heating value and, to avoid landslides during heavy rain, must be taken away from the forests properly. In 2014, statistical data of waste trees in Daejeon showed there were 2,152,352 m3 of conifers, 924,836 m3 of broad-leaved trees, and 662,914 m3 of mixed forest. The moisture content of conifers was 15.8%, that of broad-leaved trees was 11.5%, and that of mixed forest was 13.7%. The ash content of conifers was 7.0%, that of broadleaved trees was 4.0%, and that of mixed forest was 11.4%. All three types of tree satisfy the moisture and ash content criteria for fluff type Bio-SRF, i.e., 25% and 15%, respectively. Therefore, they are deemed sufficiently valuable as a source of energy. The heavy metal (Hg, Cd, Pb, As, Cr) content of conifers, broad-leaved trees and mixed forests each satisfies the heavy metal content criteria for Bio-SRF, i.e., 0.6 mg/kg, 5.0 mg/kg, 100 mg/kg, 5.0 mg/kg, and 70 mg/kg, respectively. The lower heating value of conifers was 5,070 kcal/kg, that of broad-leaved trees was 4,660 kcal/kg, and that of mixed forest was 4,820 kcal/kg. All three types of tree satisfy the lower heating value criteria for Bio-SRF, which is 3,000 kcal/kg, and, therefore, are deemed sufficiently valuable as a source of energy.

This study was conducted to investigate the content of sulfur dioxide residues in medicinal herbs in Seoul in 2009. Sulfur dioxide in the samples were determined by Monnier-Williams's modified method. A total of 1,821 samples of 205 different types of herbs were collected from Kyung-Dong Herb markets and Oriental medicine hospitals in Seoul. Of these samples, 642 samples were domestic, and 1,179 samples were imported. Of the 1,821 samples, 61 (3.3%, 31 types) failed to meet the regulations for sulfur dioxide residues of KFDA in medicinal herbs. Among these 61 unsuitable samples, 17 (7 types) were domestic, and 44 samples (26 types) were imported. The content of sulfur dioxide in the domestic medicinal herbs ranged from 0 to 809 mg/kg, while those in imported medicinal herbs ranged from 0 to 4,481 mg/kg. Approximately 84.6% of the samples contained less than 10 mg/kg of sulfur dioxide and about 10.0% of samples contained more than 30 mg/kg of sulfur dioxide.

Sea water samples collected in August, 1994 from 20 stations in the Kwangyang Bay were analyzed by gas chromatography/mass spectrometry-selected ion monitoring (GC/MS-SIM) to investigate persistence and distribution pattern of four organophosphorus pesticides (DDVP, Diazinon, IBP, EDDP). Except for IBP, the contamination by DDVP, Diazinon, and EDDP in marine aquatic environment in Korea has not been reported previously. In this study, however, all these four pesticides were detected in all stations (except DDVP) and their concentrations were in ng/L level. The concentrations ranged from detection limit to 15.3ng/L for DDVP, 1.8-27.7ng/L for Diazinon, 7.3-63.5ng/L for IBP, and 22.2-1100.1ng/L for EDDP. It is noteworthy that the measured concentrations of IBP and EDDP in this study would be much lower than usual, since the use of IBP and EDDP was less than 50% of average annual consumption due to unusually dry and hot weather condition in the summer of 1994. It was very surprising to find that the highest concentrations of organophosphorus pesticides were observed at stations near Daesa Streamlet instead of Seomjin River, which has more point source of the pesticides. This result suggests that the small river discharge during heavy rain period in summer can give harmful effect on marine biota (both wild and aqua-cultured) with its organophosphorus pesticide residue, despite of their short residence time in aquatic environment. In order to protect the marine life properly from acute toxicity of the organophosphorus pesticides, it needs to be emphasized that monitoring the level of agricultural pesticides in river run-off should be done during active consumption period rather at regular intervals.

Pesticide residues were extracted with 70% acetone and transferred to dichloromethane. Extracts were applied to open-column chromatography with florisil and alumina-N. The final extract was analyzed by gas chromatography with electron-capture detector(GC/ECD) and nitrogen-phosphorus detector(GC/NPD). Recoveries of the 17 organochlorine pesticides were ranged from 60.8 to 84.9% and those of 15 organophosphate pesticides, from 70.5% to 100.0%(except phosmet and azinphos-methyl). The minimum detectable levels of this analytical method were low(0.021-0.058㎎/㎏).