Dog 혈장 중 HPLC-ICP/MS를 이용한 비소 화학종 분석법 검증

김종환(Jong-Hwan Kim),권영상(Young Sang Kwon),신민철(Min-Chul Shin),김수정(Su Jong Kim),서종수(Jong-Su Seo) 한국분석과학회 2016 분석과학 Vol.29 No.5

LC-MS/MS와 GC-MS/MS를 이용한 사과와 쌀 시료에서 320종 농약의 다성분 분석

김종환(Jong-Hwan Kim),김영진(Yeong-Jin Kim),권영상(Young-Sang Kwon),서종수(Jong-Su Seo) 한국농약과학회 2016 농약과학회지 Vol.20 No.2

A new analytical method has been developed to determine 320 pesticides in apple and rice. The extraction of pesticides was carried out based on QuEChERS sample extraction, and determination was performed using LC-MS/MS and GC-MS/MS. 320 pesticides were selected for experiments. 251 and 110 pesticides among them were analysed by LC-MS/MS and GC-MS/MS, respectively. 41 pesticides of them were analyzed by both GC-MS/MS and LC-MS/MS. Among pesticides analysed by LC, 242 pesticides (96% of total number) in apple and 237 pesticides (94% of total number) in rice showed recoveries in the range of 70~120% with RSD ≤ 20%. In case of pesticides analyzed by GC-MS/MS, 103 pesticides (94% of total number) in apple and 83 pesticides (76% of total number) in rice were successfully validated. These results indicated that LC-MS/MS and GC-MS/MS analysis with the QuEChERS sample preparation can be partly applied to multi-residue pesticides in agricultural products.

국내 농약방제복의 솔기(seam)의 침투성 평가

김종환 ( Jong-hwan Kim ),조유진 ( Yu-jin Cho ),송종욱 ( Jong-wook Song ),서종수 ( Jong-su Seo ) 한국환경농학회 2016 한국환경농학회 학술대회집 Vol.2016 No.-

농약 살포용 방제복은 농작업자의 노출을 감소시키는 가장 중요한 요인이며 농약 방제복에 대한 침투저항성 시험법으로는 분무법, 피펫법, Gutter법, 가압조건 측정법이 있다. 미국 및 유럽 등은 ASTM F-2669, JIST 8126, DIN 32781 및 EN/ISO 27065의 농약 방제복 성능기준 표준시험방법에 따라 침투저항성 및 투과저항성을 측정하고 있다. 하지만 국내에서는 농약 방제복에 대한 측정시험법이 마련되어 있지 않는 실정이다. 본 시험에서는 국내에 시판되고 있는 농약 방제복이 국제적인 지침서에 요구하는 성능시험에 만족하는지 확인하기 위해 다양한 시험법 중에서 피펫법에 대한 시험법을 확립하고 국내 농약 방제복에 대한 농약 침투성을 측정하였다. 국내에 시판되는 농약 방제복 중 다양한 재질로 구성된 9개의 제품을 선정하여 방제복 솔기(seam)부분의 침투성을 확인하였으며 ISO-22608 지침서 내 피펫법의 분석법과 중량측정법을 적용하여 측정하였다. 5% EC pendimethalin을 이용하여 침투성을 확인하였으며, GC/MS 분석법 확립을 위한 시험편과 흡습지에 대한 회수율은 95.2~106.2%로 매우 우수하였다. 중량측정법의 경우에는 시험편과 흡습지의 mass balance가 92.5~97.7%로 지침서에서 요구하는 기준에 만족하였다. 9개 제품에 대한 GC/MS 분석법에 의한 침투성은 0.2~18.9%였으며, 중량측정법에 의한 침투성은 0.0~31.9%였다. 서로 다른 2종류의 측정결과를 비교하였을 때, 유사한 값을 나타내는 제품이 있는 반면, 중량측정법에서 상대적으로 높은 침투성을 나타내는 제품도 있었다. 이는 측정방법에 따라 발생되는 침투성 차이와 방제복 원단의 수분 보유력 및 솔기부분의 벤딩방식에 따른 차이인 것으로 판단된다. 농약 방제복의 침투성을 측정하는 시험 중의 하나인 피펫법에 의한 시험을 통해서, 국내에 시판되는 농약 방제복중에서 국제적인 지침서에서 요구하는 침투성 허용기준을 초과하는 제품이 있는 것으로 확인이 되었으며, 국내에서도 농약 방제복에 대한 성능기준을 측정하고 판단하는 정책지침이 필요할 것으로 판단된다.

방제복에 대한 농약의 체류성, 발수성 및 침투성 측정

김종환 ( Jong-hwan Kim ),조유진 ( Yu-jin Cho ),송종욱 ( Jong-wook Song ),김정한 ( Jeong-han Kim ),서종수 ( Jong-su Seo ) 한국환경농학회 2016 한국환경농학회지 Vol.35 No.4

BACKGROUND: The personal protective equipments (PPEs) is the most important factor for reducing the pesticide exposure during the preparation and spraying of pesticides. This study was to investigate the retention, repellence and penetration of protective clothing of PPEs according to the ISO 22608 `Liquid penetration resistance-pipette test. Protective clothing for agriculture worker is very important for their health. However, test method for measurement of protective clothing is not presented in Korea. METHODS AND RESULTS: In order to measure the retention, repellence and penetration of protective clothing, a apparatus for pipette method in accordance with the ISO Guideline was prepared. The test was conducted at 25±5℃, 60±10% of relative humidity and pipette applied to a apparatus was validated to take exact amount(0.2 mL). The retention, repellence and penetration of five types of protective clothing and one type of shirt were analyzed by GC/MS. Pendimethalin(5% a.i, emulsion) was used as a test pesticide to measure above factors. The retention were less than 11.0% with the exclusion of two types(F4 and shirt) and the repellency was more than 67.0% with the exclusion of shirt material. The penetration was less than 5.4%, however, that of shirt was 66.7%. CONCLUSION: This results indicated that all protective clothing were suitable to use as PPEs according to the criteria specified by ISO Guide 22608. However, shirt was not suitable due to high penetration. This test method established for measurement the retention, repellence and penetration of protective clothing will help to establish the test notice of pipette method.

풋고추 농약다성분분석 정도관리용 분석표준물질 개발

김종환(Jong-Hwan Kim),최성길(Sung-Gil Choi),오영곤(Young-Gon Oh),권영상(Young-Sang Kwon),홍수명(Su-Myeong Hong),성문현(Mun-Hyun Sung),이세자(Se-Ja Lee),황선영(Sun-Young Hwang),서종수(Jong-Su Seo) 한국농약과학회 2016 농약과학회지 Vol.20 No.3

This study was to develop the analytical reference material of green-pepper for multi-residue analysis of pesticides. According to the ISO Guide 35, ISO Guide 13528 and EURL-PT protocol, the homogeneity, stability, assigned value and uncertainty were calculated to assess if it was suitable to be used as the proficiency test or quality control. The values of the within-bottle standard variation (s<SUB>wb</SUB>) and the between-bottle standard variation (s<SUB>bb</SUB>) were 1.7~3.7% of assigned value according to the requirement of the ISO guide 35. And, the uncertainty (u<SUP>*</SUP><SUB>bb</SUB>) due to inhomogeneity was 0.8~1.1% for all pesticides. The storage stabilities of ten-pesticides at various conditions were assessed. For all target pesticides, the slop (b<SUB>1</SUB>) values were smaller than the corresponding values of [t<SUB>0.95,n-2</SUB>×s(b<SUB>1</SUB>)] specified by the ISO guide 35, indicating that there were no statistically significant decreases in the concentration of the target pesticides when the analytical reference material was stored at room temperature (20~30℃) for 7 days, freezing (-20℃) for 30 days and deep freezer (-80℃. except for bifenthrin, fenpropathrin) for 245 days. For proficiency test by using it developed by Korea Institute of Toxicology, inter-lab test was performed with eight organization performing the residual pesticide analysis. We found that there were some different results among them. Some were assessed as questionable or unacceptable for two pesticides and one organization didn’t analyze the six pesticides. From these results, this green-pepper analytical reference material containing ten-pesticides could be used as a tool for the proficiency test to improve the reliability or consistency for pesticide residue’s results.

잔류농약 다성분 동시분석 숙련도평가용 방울토마토 분석표준물질의 개발

김종환(Jong-Hwan Kim),안지영(Ji-Young Ahn),최성길(Sung-Gil Choi),권영상(Young-Sang Kwon),신민철(Min-Chul Shin),홍수명(Su-Myeong Hong),서종수(Jong-Su Seo) 한국농약과학회 2018 농약과학회지 Vol.22 No.3

This study was conducted to develop an analytical reference material of cherry tomato containing ten pesticides (acetamiprid, buprofezin, carbendazim, diethofencarb, tebuconazole, tebufenozide, tetraconazole, pyraclostrobin, pridaben, pyriproxyfen) for proficiency test of pesticide multi-residue analysis. According to the KS A ISO Guideline 35 (2005)/KS Q ISO Guideline 13528 (2009) and EURL-PT (IUPAC), homogeneity, within-bottle/between-bottle standard variations and standard uncertainty were calculated and assessed, resulting that between-sample standard deviations were lower than 0.3σ (0.3 × target standard deviation) and there were no statistical differences within and between bottles for each pesticide on statistical analysis using ANOVA test. Also, standard uncertainty (u<SUP>*</SUP><SUB>bb</SUB>) ranged from 0.98% to 3.36%. These results indicated that all pesticides were distributed homogeneously in the analytical reference material. Therefore, it was considered that the cherry analytical reference material developed for the proficiency test could be used as a tool to evaluate the reliability and consistency of laboratories.

개인보호장구(PPE)의 사용현황 조사 및 Atomizer 측정에 의한 국내 농약 방제복의 침투성 평가

송종욱(Jong-Wook Song),김종환(Jong-Hwan Kim),조유진(Yu-Jin Cho),김정한(Jeong-Han Kim),박경훈(Kyung-Hun Park),서종수(Jong-Su Seo) 한국농약과학회 2017 농약과학회지 Vol.21 No.4

This study was carried out to investigate the use of Personal Protective Equipments (PPEs) and evaluate the penetration of nine commercially available personal protective clothing and one general shirt based on the ISO 22608 guideline and EN14786 guideline. From the results of the survey, the use of the mask was highest as 67.1% and the goggles was the lowest as 20.7% when they use and handle the pesticides, indicating that most of farm workers did not use PPEs for their heath. In the measurement of penetration using the Atomizer test, the results for the penetration of pendimethalin showed that the penetration of the shirt, F6 (cotton 35%+polymer 65%, porous material, twill weave) and F7 (polyester 100% (polymer coating), porous material) were greater than 51.9%, and for tebuconazole, that of the shirt was 48.1%. Other results were lower than 5.5% and 0.1% of the penetration. This study showed that some clothing were not suitable for use since the ISO guideline requests penetration of 5% as suitable for personal protective clothing. Therefore, it is likely to be necessary to perform penetration measurement methods for the use of suitable protective clothing.

토마토 농약다성분분석 정도관리용 분석표준물질 개발

김종환 ( Jong Hwan Kim ),오영곤 ( Young Gon Oh ),최성길 ( Sung Gil Choi ),홍수명 ( Su Myeong Hong ),김선배 ( Sun Bae Kim ),우인덕 ( In Duk Woo ),김준영 ( Jun Young Kim ),서종수 ( Jong Su Seo ) 한국환경농학회 2016 한국환경농학회지 Vol.35 No.3

BACKGROUND: This study was to develop a analytical reference material including twenty pesticides in tomato. To use it for proficiency test, the suitability of homogeneity, storage stability, assigned values and uncertainty for analytical reference material were important. METHODS AND RESULTS: In order to develop a analytical reference material of tomato for multi-residue analysis of pesticides, twenty-pesticides were treated in tomato and the samples were frozen and homogenized. The homogeneity, stability, assigned value and uncertainty were calculated according to the requirements of the KS A ISO Guide 35, KS Q ISO 13528 and EURL-PT protocol. The values of the within-bottle standard variation(s_wb) and the between-bottle standard variation(s_bb) were 0.9~6.5% of assigned value and the uncertainty(u*_bb)) due to inhomogeneity was also calculated as 0.6~1.9% for all pesticides. This indicated that it was satisfactory to be used as a analytical reference material. The storage stabilities of twenty-pesticides at room temperature and freezing conditions were assessed according to the requirement of the KS Q ISO Guide 35. All pesticides were stable at room temperature (20~30℃) for 8 days and freezing (-20℃) for 23 days. CONCLUSION: The feasibility of analytical reference material for pesticide multi-residue analysis in a tomato matrix was investigated. Homogeneity of within/between-bottle, uncertainty and stabilities at room temperature and freezing condition were satisfactory for a use of proficiency test and quality control. From these results, a analytical reference material would be applicable to monitor the proficiency test of pesticide analysis organizations to improve the reliability and consistency.

[<SUP>14</SUP>C]Butachlor를 이용한 호기성 토양대사 시험법 확립

김주혜(Ju-Hye Kim),김종환(Jong-Hwan Kim),김대욱(Dae-Wook Kim),이봉재(Bong-Jae Lee),김찬섭(Chan Sub Kim),임양빈(Yangbin Ihm),서종수(Jong-Su Seo) 한국농약과학회 2014 농약과학회지 Vol.18 No.4

The test method of aerobic transformation in soil has established based on international test guideline (OECD TG 307). And then, the case study was conducted with [<SUP>14</SUP>C]butachlor. Butachlor is commonly used herbicide in Korea. [<SUP>14</SUP>C]Butachlor was treatrd 6.83 mgKg?1 in loamy soil. The treated soil was incubated in flow-through system for 60 days. The mass balance of applied radioactivity (AR) ranged from 91.1 to 95.5% and from 93.0% to 97.7% for non-sterile and sterile soils, respectively. In non-sterile soil, the concentration of [<SUP>14</SUP>C]butachlor was declined from 94.4% AR at 0 day to 8.4% AR at 60 days after treatment. 2-Chloro-2,6-diethylacetanilide was the major degradation product detected in soil extract. The calculated DT50 and DT90 of butachlor were 10.4 days and 34.6 days, respectively. <SUP>14</SUP>CO₂ and non-extractable soil residue were increased up to 3.5% and 43.5% AR at 60 DAT. There is no significant decrease of the [<SUP>14</SUP>C]butachlor through the incubation period in sterile soil.

쌀시료의 농약다성분 분석표준물질의 개발

오영곤 ( Young-gon Oh ),김종환 ( Jong-hwan Kim ),최성길 ( Sung-gil Choi ),서종수 ( Jong-su Seo ) 한국환경농학회 2017 한국환경농학회 학술대회집 Vol.2017 No.-

국민의 건강과 생명에 직접적으로 연결된 안전한 먹거리에 대한 관심이 지대해지고 있는 요즘 먹거리의 생산단계인 농장에서 사용하는 농약의 독성과 잔류성으로 인한 문제가 대두되고 있다. 농약은 육안으로 확인할 수 없기 때문에 농약 분석을 수행하는 기관의 결과만을 의존 할 수밖에 없기 때문에 잔류농약 분석을 수행하는 각 기관 및 시험소의 신뢰성이 요구되어지고 있다. 각 기관 및 시험소마다 다른 시험법, 장비, 기술력을 보유하고 있기 때문에 잔류농약분석을 수행하는 기관에서는 분석결과에 대한 신뢰성 검증하기 위하여 노력하고 있다. 최근 국내에서는 단성분 위주 의 표준물질을 사용한 정도관리평가를 수행하고 있지만, 다성분으로 이루어진 농약의 분석은 현재 이루어지고 있지 않기 때문에 본 연구에서는 10종의 농약성분이 포함된 쌀 분석표준물질를 조제하여 정도관리 및 숙련도시험의 적용여부를 판단하였다. 쌀 분석표준물질의 균질성은 국제적인 지침 서인 ISO 35 Guide에서 제시하는 병간(between-bottle)과 병내(within-bottle)의 균질성 확인과 EURL-PT(European Union Reference Laboratories-Proficiency Test)의 일원분산분석법(ANOVA test) 그리고 ISO 13528 Guide의 F-test 모델에 따라 확인하였다. ISO 35 Guide기준으로 평가하였을 때, 10여종 농약성분의 병내 균질성 표준불확도가 1.3~4.4%였으며, 병간 균질성 표준불확도는 0.7~4.3%로 매우 낮았으며, 10종의 농약성분 모두 EURL-PT에서 요구하는 병간의 variance이 병내의 variance보다 낮아, 매우 균질한 것으로 확인하였다. 또한, ISO 13528 Guide의 병간균질도(sb)가 인증값의 허용표준편차 σ의 0.3배 이하로 모든 성분이 매우 균질하게 분포되어 있는 것으로 확인하였다. 따라서, 본 연구를 통해서 개발된 10종이 함유된 쌀 분석표준물질은 잔류분석을 수행하는 각 시험소에 적 용하여 잔류분석 결과의 신뢰성 확인과 평가에 활용할 수 있을 것으로 판단된다.