초록 ▼

Ⅳ. 연구개발결과
1) 농산물 중 내분비계장애추정물질 잔류실태 및 위해성평가 연구
엽채류, 과채류, 과일류, 곡류 22개 작물을 통한 다이옥신 1일섭취량은 0.0230~0.2748pg-TEQ/kg b.w./day 범위이며 평균 0.0858 pg-TEQ/kg b.w./day 이었다. 이는 다이옥신의 내용1일섭취량 (Tolerable Daily Intake, TDI) 4 pg-TEQ/kg b.w./day의 0.58~6.86% 범위이며 평균 2.15%로서 농산물을 통한 다이옥신 섭취량은 안전한 수준인 것으로 사료된다.
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Ⅳ. 연구개발결과
1) 농산물 중 내분비계장애추정물질 잔류실태 및 위해성평가 연구
엽채류, 과채류, 과일류, 곡류 22개 작물을 통한 다이옥신 1일섭취량은 0.0230~0.2748pg-TEQ/kg b.w./day 범위이며 평균 0.0858 pg-TEQ/kg b.w./day 이었다. 이는 다이옥신의 내용1일섭취량 (Tolerable Daily Intake, TDI) 4 pg-TEQ/kg b.w./day의 0.58~6.86% 범위이며 평균 2.15%로서 농산물을 통한 다이옥신 섭취량은 안전한 수준인 것으로 사료된다.
2) 농경지 중 내분비계장애추정물질 오염실태조사
농경지 200점의 시료 중 endosulfan 등 6종의 농약이 검출되어 29%의 검출율을 보였으며, 농경지별 검출율은 밭>시설재배>과수>논 순이었다. 용탈실험을 수행한 결과 대부분의 농약은 가수분해 등으로 인해 용탈량과 토층별 잔류량이 감소하였다. Metribuzin은 토층 전체에 분포하였고 미량 용출 되었으며, metribuzin을 제외한 나머지 농약은 토층 상부에 잔류하였으며, methomyl의 경우 전량 분해되어 검출되지 않았다.
3) 내분비계장애추정농약의 작물체내 흡수, 이행 및 잔류특성 연구
EDs 추정농약의 고유 극성을 지표화하기 위하여 HPLC법에 의하여 표준화합물 22종을 공시, log Pow 측정을 위한 보정곡선을 작성한 후 EDs 농약에 대한 log Pow를 실측하였다. EDs 추정농약의 토양 고상/액상 간 분포 특성 평가를 위하여 batch equilibrium법에 의하여 토양흡착상수인 Koc와 Freundlich 흡착상수를 실측하였으며 실험의 편이성 측면에서 Koc 값을 이용하는 것이 더 유리하였다. 실측 Log Pow와 Koc로부터 EDs 추정농약의 환경화학적 이동성을 예측하였다.
토양수 중 농약 잔류분의 흡수/이행성 규명을 위하여 수도 30일 유묘 2본/구 또는 고추 40일 유묘 1본/구를 대상으로 표준적 수경재배 시험법을 개발하고 약제처리 후 시험기간 7일간의 환경 및 작물 생육인자를 조사한 결과, 정상적 작물재배 조건에서 흡수 이행성을 평가하는 것이 가능하였다.
수경액 처리 농약의 작물체 부위별 잔류량을 경시적으로 조사한 결과, 수도 및 고추체 지상부/근부 잔류량 비율로부터 0.1이하, 0.1～1.0 그리고 1.0 이상을 각각 비이행성, 반이행성 및 이행성으로 흡수 이행성을 등급화하였다. 대상 성분들의 log Pow 및 Koc와 흡수 이행성 간상관관계를 평가하고 잔류 소실속도를 보정인자로 부여함으로써 흡수 이행성의 등급을 판정할수 있었다. Log Pow와 Koc 값으로부터 예측되는 이동성은 수경액 처리 농약의 작물체로의 흡수/이행 결과와 잘 일치하는 양상을 나타내었으나 화합물에 따라 그 흡수/이행 비율에는 다소차이를 보이므로 의심 성분에 대해서는 수경액 실험 실측 및 잔류소실 속도에 의한 보정이 요구되었다.
수도의 경우 수경액 처리 시에 비하여 담수토양 처리 시의 흡수 이행성이 낮게 실측되므로 수경액 실험으로부터 이행성으로 판정 또는 생육이상을 초래하는 농약에 대해서는 담수토양조건에서의 실측이 추가로 필요하였다. 고추의 경우 수경액 처리 시에 비하여 습윤토양 처리 시의 흡수 이행성이 대체로 낮게 실측되었으나 일부 성분에 대해서는 그 흡수/이행 비율에는 다소 차이를 보이므로 이행성 판정이 명확하지 않거나 생육이상을 초래하는 농약에 대해서는 습윤토양 조건에서의 실험적 실측이 추가로 요구되었다.
EDs 추정농약에 대한 log Pow, Koc 값과 수도 및 고추의 수경액 및 토양재배 모델시험으로부터 일반 농약의 작물체로의 흡수 이행성 평가를 위한 tier system이 제안될 수 있었다.
4) 내분비계장애추정농약의 농업환경 중 이동성 예측모델 연구
본 연구에서는 고추밭과 논에서의 농약의 이동성을 파악하기 위해 각각 GLEAMS와 RICEWQ 모형을 적용하였다. 고추밭 토양의 alachlor, cypermethrin, endosulfan, fenvalerate의 잔류성분을 조사하였고, 논으로부터 2-4-D와 carbaryl 유출율을 추정하였다. 밭 시료(밭유거수, 밭토양) 중 alachlor, cypermethrin, endosulfan, fenvalerate를 동시분석하기 위하여 밭유거수는 액액추출과 SFE정제방법을 이용하여 분석법을 확립하였고, 밭토양에서는 ultrawave sonication 추출방법을 통하여 간편하고 신속한 분석방법을 개발하였다. 논 시료(논물, 논토양) 중 2,4-D, carbaryl, ethyl-parathion의 분석방법을 확립하였다. 특히 2,4-D의 경우 유도체화를 시키지 않은 간편한 분석방법을 개발하였다. 농약의 시용량에 따른 잔류량 변화를 조사하기 위해 고추밭에 권장사용량과 권장사용량의 2배구를 대상으로 실험을 실시하였다. GLEAMS 수문모형 적용을 위해 온도, 관개량, 풍속 등의 기상자료는 실측하였으며 고추밭의 토양층별 잔류농약을 조사하여 GLEAMS 모형의 모의값과 비교하여 보정 및 검증하였다. GLEAMS 모형의 유기탄소흡착계수(KOC)와 엽농약 강우세척 비율(WSHFRC) 값이 토양 중 잔류농도에 영향을 미치는 주요 매개변수로 조사되었으며 모의된 alachlor 농도는 KOC에 비교적 예민하게 반응하였는데, fenvalerate 는 KOC 값에 영향을 받지 않았다. 작물의 잎에서 농약이 강우에 씻겨나가는 정도를 나타내는 WSHFRC값은 fenvalerate 토양잔류량에 큰 영향을 미쳤다. 토양 내 반감기를 나타내는 SOLLIF는 토양 잔류 농약 모의 발생에 민감하게 반응하였다. 하지만 토양 흡착이 크고 이동성이 적은 fenvalerate의 경우에는 영향이적었다. 수용해도를 나타내는 H₂OSOL값은 잔류농약 모의 발생에 영향을 미치지 않았다. cypermethrin과 fenvalerat는 엽반감기 HAFLIF에 민감하게 반응하였다. 검증 과정의 토양중 잔류농약의 모의 발생한 결과와 실측값을 비교한 결과 alachlor, cypermethrin, fenvalerate가 endosulfan보다 잘 모의 발생된 것으로 나타났다. 통계적 분석결과 또한 GLEAMS 모형의 적용가능성을 시사 하였다. 비 가림 조건에서 관개량에 따른 토양 내 잔류농약 특성을 살피기 위해 alachlor, endosulfan, cypermethrin fenvalerate을 대상으로 현재 관개량의 1배, 2배, 3배, 5배 조건에 대해 모의 발생 결과 alachlor를 제외하고는 관개량이 토양잔류 농약 농도에 크게 영향을 미치지 않음을 알 수 있다. alachlor의 경우 관개량 증가에 따라 초기 농도가 감소함을 나타냈다. RICEWQ 모형에 적용하기 위해 실측된 강우량, 관개량,증발산량 등을 이용 물수지 모형을 보정하였으며, 항온실험 결과를 이용 농약모형을 보정하여 유출율을 산정하였다. 농약 살포 일시를 6월 1일로 입력하고 농약에 관련된 매개변수는 항온 실험 결과를 이용 보정된 매개변수를 이용하였다. 초기 농도에 영향을 미치는 RREAC값이 carbaryl에서 더 높게 나타났고 이에 따라서 carbaryl의 초기 농도는 2,4-D보다 높았으나 carbaryl의 휘산 속도(VVOL)가 2,4-D 보다 높아 시간이 지남에 따라 carbaryl의 농도가 급격하게 감소하였다. 각 농약별 살포 날짜의 변경에 따른 영향을 검토하기 위해 살포시기를 다르게 하여 모의 발생된 결과를 통해 산정된 2,4-D, carbaryl의 농약 배출율 범위는 각각 3.2∼5.4%, 1.2∼12.1%로 나타났다. 살포 날짜마다 농도의 감소 형태는 비슷하였으나, 날짜별로 차이가 나타났다. 이는 강우와 유출이 발생한 시기와 농약을 살포한 시기가 겹칠 경우 농약 배출율에 영향을 미친 것으로 판단된다. 그리고 carbaryl의 배출율 변화가 살포시기에 더큰 영향을 받는 것으로 나타나, 강우가 있는 날에 carbaryl의 적용 관리에 주의해야 하는 것으로 나타났다. 논 물꼬 변화에 따른 농약 관리 시나리오 효과를 모의 발생하여 분석하였다. 논 담 수심 4, 6, 8cm로 관리할 경우 배수농도와 담수농도는 거의 차이를 보이지 않았으나, 농약 배출율에는 영향을 미쳤다. 농약 배출율은 물꼬 높이와 반비례하는 관계를 나타내었으며, 이를 통해 논의 물꼬 높이를 조절 하는 것만으로도 농약 배출율 감소의 효과를 볼 수 있는 것을 알 수 있었다. 관개량을 90%, 80%, 70%로 변경하여 모의함으로써 관개량 변화에 따른 농약 거동 특성을 분석하였다. 농약 배출율은 관개량이 줄어들수록 감소하는 추세를 보였지만 감소하는 양은 크지 않았다. 국내 조건에서 GLEAMS 모형과 RICEWQ 모형을 각각 밭과 논에 적용한 결과 두 모형 모두 영농지역에서 농약의 이동성을 잘 반영한 것으로 나타났으며, 향후 본 연구에서 제시된 보정된 매개변수 값은 국내 조건에서의 농약 관련 모델링을 실행할 경우 적용될 수 있을 것으로 판단된다.
5) 농생태계 서식생물 내분비계장애추정물질 오염실태조사
본 연구는 농업용수의 이화학적 수질조사 분석만으로는 해결하지 못하는 종합적 수환경 평가방법의 하나로 주요 선진국에서 실시하고 있는 바이오모니터링 조사기법을 우리나라 농업용 저수지의 생태계건전성평가에 도입하고자 수행하였다. 어류의 건강지표로서 전장, 체중을 조사하였고 전장빈도분포도를 이용한 연령구조 분석을 통해 조사지점의 개체군의 안정도와 향후 성장여부를 판단할 수 있었다. 어류 개체의 기초 생리학적 특성을 알아보는 지표로서 비만도지수, 간중량지수, 생식소중량지수를 조사하였고 이들 지표는 어류의 영양정도를 평가하는 간접지표로서 유용하게 이용되며 환경변화에 대한 반응지표로 사용될 수 있을 것으로 판단된다. 어체의 눈, 체표면, 아가미덮개, 지느러미의 외형적 이상유무 조사와 외형이상과 아가미, 지라, 신장, 간의 내부장기 이상의 정도를 점수화하여 계산한 건강도지수를 사용한 본 연구의 방법을활용하면 환경오염물질에 대한 수서생태계의 건전성을 보다 과학적으로 파악할 수 있을 것으로 판단된다.
alachlor 송사리 단기번식독성시험결과 산란율, 유정란율, 무정란율, 부화율에는 영향이 관찰되었으나, 치사율과 기형율에는 거의 영향이 관찰되지 않았고 양성대조 물질로 사용된 17 β-estradiol에서는 0.5ppb 수준에서 산란율, 유정란 및 무정란에 영향이 관찰되었으나 부화율, 치사율 및 기형율에서는 영향이 관찰되지 않았다. Alachlor의 에스트로겐성을 검정하기 위해 수행된 vitellogenin 측정결과 양성대조물질에서는 저농도에서도 상당한 활성이 관찰된 반면 alachlor는 거의 활성이 관찰되지 않아 최근 미국 EPA(2009)가 내분비계장애물질 검색프로그램(EDSP) 우선검색물질 리스트에 alachlor를 삭제한 것도 이와 같은 결과가 반영된 것으로 사료된다.
6) 미꾸리의 다중 생물지표를 이용한 내분비계장애추정물질의 독성반응 평가 및 수생태계 건강성지수 개발
본 연구 과제의 최종 결과물로서 1) 미꾸리(Misgurnus anguillicaudatus)를 이용한 내분비계장애(추정)물질의 독성시험법 매뉴얼 및 2) 미꾸리(Misgurnus anguillicaudatus)를 이용한 내분비계 장애(추정)물질의 수생태계 건강성 평가 매뉴얼을 작성하였다.
미꾸리(Misgurnus anguillicaudatus)를 이용한 내분비계 장애(추정)물질의 독성시험법 확립을 위하여 7가지 농약을 선정하여 21일 내분비계 장애추정물질의 검색 시험을 수행하였다. 시험법은 OECD Draft Test Guideline (2008) “The Fish Screening Assay for Endocrine Active Substance”와 OECD Test Guideline No. 230 (2009) “21-day fish: A Short-term Screening for Oestrogenic and Androgenic Activity, and Aromatase Inhibition”을 기초로 하였으며, 본 연구에서 사용한 농약은 endosulfan, alachlor, 2,4-D acid, benomyl, methomyl, carbaryl metribuzin의 총 7가지의 원제이다. 미꾸리의 생체분자 및 생화학적 지표 분석을 위하여 21일 내분비계 장애추정물질의 검색 시험 중간과 시험 마지막 날짜에 미꾸리를 샘플링 하였다. 분석된 생물지표는 생화학적 생물지표인 vitellogenin(VTG), acetylcholinesterase (AChE),7-ethoxyresorufin-O-deethylase(EROD), comet assay의 4가지와 개체수준의 생물지표인 condition factor(CF), gonado-somatic index(GSI), liver-somatic index(LSI)의 3가지로 총 7가지이며, 생물지표 분석방법 또한 매뉴얼에 포함되었다. 21일의 시험기간 동안 endosulfan 0.002 mg/L에서 50%, alachlor 1 mg/L에서 35%의 치사율이 관찰되었으나, 그 외 모든 시험의 대조군 및 농도군에서는 미꾸리의 치사가 관찰되지 않았다. 분석된 생물지표 가운데 개체수준의 생물지표인 CF, GSI, 및 LSI는 모든 시험에서 농약에 의한 영향을 받지 않는 것으로 나타났으며, 그 외의 생물지표들 가운데 대조군에 비해 농도군에서 통계적으로 유의한 차이를 나타낸 연구 결과는 표 1과 같이 요약하였다(p<0.05).
내분비계 장애물질에 대한 수생태계 건강성 평가 기법을 적용하고 확립하기 위해서는, 농약 사용량이 많은 농경지를 선정한 후 미꾸리를 채집하여 생체분자 및 생화학적 지표들을 분석하였다. 건강성 평가 대상 지점은 대조지점(reference site)으로서 부여군 충화면 상천곡제 인근의 산간계류형 소하천을, 농약의 영향을 받을 것으로 기대되는 연구지점(study site)으로서 서천군 기산면의 평야에 위치한 농수로를 선정하였다. 대조지점에서 68 마리, 연구지점에서 56 마리의 미꾸리를 각각 채집하였다. 외형적 기형 및 건강상태를 확인하기 위하여 DELT(deformation, erosion, fin lesion, tumor)이상 증상을 관찰한 결과, 대조지점과 연구지점에서 채집된 미꾸리에서 DELT 비율이 각각 0%와 12.5%로 나타났다. 또한 생물지표들을 측정한 결과, VTG 농도는 암컷과 수컷 모두에서 두 지점 사이에 차이가 나타나지 않은 반면, AChE 활성도, EROD 활성도, DNA damage(comet assay) 분석에서는 대조지점과 연구지점 사이에 유의한 차이가 있는 것으로 관찰되었다(p<0.05). 한편, 개체수준의 생물지표인 CF,GSI, 및 LSI는 두 지점 간에 통계적으로 유의한 차이가 보이지 않았다(p<0.05).
7) 내분비계장애추정농약의 농작업자 위해성 평가 및 노출량 예측 연구
농약 살포자에 대한 위해성 평가를 하기 위해 사과 과수원에서 살충제 fenvalerate 유제와 수화제를 SS(Speed Sprayer)와 PS(Power Sprayer)를 이용하여 살포하면서 피부, 호흡노출을측정하였다.
피부노출을 측정하는데 피부노출 측정용 패치와 장갑, 양말, 마스크를 이용하였으며 개인용 공기펌프와 XAD-2 레진을 이용하여 호흡노출을 측정하였다.
SS로 수화제를 살포 할 경우 피부노출량은 2032.34 μg(전체 살포량의 0.0081 %), 호흡노출량은 2.16 μg(8.65×10-6%)이였으며 PS로 수화제를 살포 할 경우에는 피부노출량은 1087.93μg(0.0145 %), 호흡노출량은 1.252 μg(1.67×10-5%)이였다.
또한 SS로 유제를 살포 할 경우 피부노출량은 3804.60 μg(0.0152 %), 호흡노출량은 2.45μg(9.81×10-6%)이였으며 PS로 수화제를 살포 할 경우에는 피부노출량은 4054.99μg(0.0541%), 호흡노출량은 3.73 μg(4.97×10-5%)이였다.
주요 피부노출부위는 SS의 경우 허벅지와 상박이였고, PS는 허벅지와 손이였다. 위해성평가 을 위해 PDE(potential dermal exposure), PIE(potential inhalation exposure), AQE(absorbable quantity of exposure), MOS(margin of safety)값을 산출하였다. 그 결과 위해성을 나타내는MOS값이 4가지 경우에서 모두 1보다 훨씬 큰 값이 나와 위해 가능성이 적은 것으로 나타났다.
인체 간 마이크로좀을 이용한 fenvalerate의 대사 실험 결과 2-OH-CPIA(4-chloro-(2-hydroxy-1-methylethyl)benzeneacetic acid)를 포함한 6개의 대사물을 GC-MS를 이용하여 확인하였으며, 또한 Stereoisoform인 2-OH-CPIA 1과 2의 상대적인 비율이 시간이 지남에 따라 변하는것을 확인하였다.
10개의 재조합 인체 cytochrome P450을 이용하여 대사 실험결과 CYP 2C8, 2C9, 2C19는 2-OH-CPIA 2를 1 보다 더 많이 생성하는 반면 CYP 2B6는 2-OH-CPIA 1을 더욱 많이 생성하는 것을 확인하였으며, fenvaerate의 대사에 기여하는 isozyme은 CYP 2B6, 2C8, 2C9, 2C19였다. 농작업자 노출 및 위해성 연구를 위해 환경호르몬으로 의심되고 있는 methomyl과 benomyl을 선택하였다.
Methomyl은 카바메이트계 광범위 살충제로서 다양한 해충에 대해 접촉독 및 경구독으로 작용하며, 제제는 수화제와 액제를 사용하였다.
Benomyl은 보호 및 치료 효과를 가진 침투성 살균제로서 분해물인 carbendazim이 약효물질이며 수화제를 사용하였다. 실험은 사과 과수원에서 수행하였고 살포방법은 SS(Speed Sprayer), PS(Power Spray)를 이용하였다. 피부노출 측정은 patch, 마스크, 양말, 장갑을 이용하였고, 호흡노출 측정은 XAD-2 resin이 장착된 personal air monitor를 사용하였다.
Methomyl 노출 시험은 살포액 조제 시와 살포 시에 수화제와 액제 그리고 SS, PS의 노출특징을 비교하였다. Benomyl 노출시험의 경우는 대규모 조제 및 살포를 수행하였는데 수화제 한가지 제형을 SS로 살포하였다. 검출한계, 정량한계, 회수율, 재현성, 검량선의 직선성, 포집효율, 파과시험등 분석/시험방법의 검증을 통해 노출 시험 수행에 적합한 합리적인 결과를 얻었다.
Methomyl 살포액 조제 시 수화제의 경우 수화제 분진의 비산으로 인해 얼굴을 포함하여 액제 보다 더 많은 신체 부위가 오염되었고 손이 대부분이었으며(전체 노출량의 56 ~ 100%), 특히 동력분무기용 액제의 경우 농약병 뚜껑을 이용해서 살포액을 조제하는 과정에 장갑에 흘려서 오염되어 100% (330mg)가 관찰되었다. Methomyl 살포시 전체 살포량의 6 × 10-3 ~ 26 ×10-3%의 피부 노출이 관찰되었고, 제제별 차이는 거의 나타나지 않았지만, SS보다 PS로 살포시 전체 피부노출량이 3~4배 높은 것으로 나타났다. 주요 노출부위는 팔, 허벅지, 가슴이었다. 호흡노출은 미량이었지만 SS보다 PS로 살포시 2~6배 더 높은 것으로 나타났다.
Benomyl의 살포액 조제 시 전체 조제액의 7.3 × 10-4%(10.9mg)의 피부노출이 검출되었고, 살포시(1ha) 살포 약량에 대한 피부노출 비율은 약 0.05%(814.1mg) 이었다. 주요 노출 부위는 허벅지, 상박, 정강이 순으로 나타났다. 호흡 노출은 역시 미량 검출되었으며 피부 노출에 비해 약 4,000배가량 낮은 수준이었다. 노출 결과를 4ha로 환산하여 위해성 평가를 한 결과MOS값이 1이상으로 위해성이 발생할 가능성이 적었다.
Cypermethrin은 우리나라의 사과, 복숭아, 배, 배추, 감귤 등에 진딧물 및 나방류 방제에 사용되고 있는 합성 피레스로이드계 살충제이며, 유제를 SS기를 이용하여 사과 과수원에 살포하였다. Cypermethrin은 살포자에 따른 차이를 보기 위하여 조제자, 살포자 4명으로 시험을 실시하였으며 총 반복수는 15반복 시행하였다. 살포액 조제 시 노출은 조제 횟수와는 큰 영향이없었으며, 각 조제자의 평소 농약 조제 습관 및 환경에 많은 영향이 있다고 판단하였다. 총 15 반복의 살포 시 피부노출량의 비율은 다리(허벅지, 정강이, 발)이 41 ~ 48%로 가장 많이 차지하였고 몸통(머리, 앞목, 가슴, 뒷목, 등, 얼굴)은 27 ~ 31%였다. 팔(상박, 하박)은 21 ~ 28%로 나타났다. 각 부위별로는 허벅지(33.5%), 상박(15.9%), 정강이(13.4%), 가슴(11.5%), 등(10.5%)이었으며, 앞목, 뒷목, 얼굴, 발은 1%이하로 노출됨을 확인 하였다. 호흡노출은 관찰되지 않았으며, 위해성 평가 결과 위해성이 낮은 것으로 확인하였다.

Abstract ▼

This report was carried out to survey the residual characteristics and evaluate the dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in agricultural products collected major producing area. Leafy vega

This report was carried out to survey the residual characteristics and evaluate the dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in agricultural products collected major producing area. Leafy vegatables were collected in 2008, 30 fruiting vegetables in 2009, 35 fruits in 2010 and 48 grains in 2011. Seventeen congeners of dioxins and twelve congeners of PCBs were analyzed by gas chromatography coupled with high resolution mass spectrometry.
The TEQ levels were 0.0044 pg-TEQ/g f.w. in chinese cabbage, 0.0052 pg-TEQ/g f.w. in lettuce, 0.0092 pg-TEQ/g f.w. in spinach, 0.0004 pg-TEQ/g f.w. in perilla leaf, and 0.0153 pg-TEQ/g f.w. in Korean leek. The estimated daily intake from leafy vegetables was 0.0032 pg-TEQ/kg b.w./day, which was 0.08% of tolerable daily intake (TDI) based on 60 kg body weight. The TEQ levels were 0.0022 pg-TEQ/g f.w. in green pepper, 0.0187 pg-TEQ/g f.w. in tomato, 0.0022 pg-TEQ/g f.w. in watermelon, 0.0006 pg-TEQ/g f.w. in cucumber, 0.0027 pg-TEQ/g f.w. in young pumkin, 0.0015 pg-TEQ/g f.w. in strawberry, 0.0036 pg-TEQ/g f.w. in egg plant, and 0.0057 pg-TEQ/g f.w. in melon. The estimated daily intake from fruiting vegetables was 0.0086 pg-TEQ/kg b.w./day, which was 0.22% of TDI based on 60 kg body weight. The TEQ levels were 0.0060 pg-TEQ/g in rice, 0.0092 pg-TEQ/g in barley, and 0.0034 pg-TEQ/g in brown rice. The estimated daily intake from rice was 0.0182 pg-TEQ/kg b.w./day, which was 0.16% of TDI based on 60 kg body weight. The TEQ levels were 0.0266 pg-TEQ/g f.w. in apple, 0.0265 pg-TEQ/g f.w. in pear, 0.0449 pg-TEQ/g f.w. in mandarin orange, 0.0288 pg-TEQ/g f.w. in grape, 0.0328 pg-TEQ/g f.w. in persimmon, and 0.0173 pg-TEQ/g f.w. in peach. The estimated daily intake from fruits was 0.0546 pg-TEQ/kg b.w./day, which was 1.37% of TDI based on 60 kg body weight.
Total estimated daily intake of dioxins from the twenty tow agricultural products was calculated at 0.0858 pg-TEQ/kg b.w./day, which is 2.15% of Korean tolerable daily intake based on 60 kg body weight. All the fresh vegetables and fruits used in this report were analyzed with whole parts, so the total estimated daily intake amount might be smaller when the inedible parts would be removed. This result showed that agricultural products of Korea might be safe.
This study was carried out to survey the residual characteristics and evaluate the leaching potential of the endocrine disruptor (ED)-suspected pesticides in agricultural soils collected from greenhouse, upland, orchard, and rice paddy soils. Agricultural soils were collected from 40 sites of greenhouse soil in 2008, of upland soil in 2009, of orchard soil in 2010 and of paddy soil in 2011 in Korea. Sixteen ED-suspected pesticides which are using in Korea, such as alachlor, benomyl, carbaryl, cypermethrin, 2,4-D, dicofol, endosulfan, fenvalerate, malathion, mancozeb, metribuzin, metiram, methomyl, parathion, trifluralin, and vinclozolin, in the soils, were analyzed by chromatographic methods using GLC-ECD and HPLC-DAD/FLD. LOD (limit of detection) of the test pesticides ranged from 0.0004 to 0.005 mg/kg and LOQ (limit of quantitation) were from 0.0013-0.0165 mg/kg. Recoveries of the target pesticides from soil ranged from 72.69 to 115.72%. Detection rate of the pesticides from each soil was 65% in case of greenhouse soil, 42.5% in case of upland soil, 35% in case of orchard soil and 1.3% in case of rice paddy soil. The numbers of site which ED-suspected pesticides were detected were 2 sites for cypermethrin and fenvalerate, 12 sites for endosulfan, and 10 sites for vinclozolin in case of greenhouse soil. Those were 15 sites for endosulfan, 1 site for parathion and trifluralin in case of upland soil, 7 sites for endosulfan and fenvalerate in case of orchard soil and 1 site for cypermethrin in case of paddy soil. The highest detection rate was observed from endosulfan which was detected from 34 site soils of the total samples, indicating that endosulfan is persistent in soils because of its very low mobility and adsorption characteristics in soil. As a results of soil leaching test, no pesticides were detected from leachates except metribuzin which was widely distributed in all layers of the soil columns, suggesting that no leachabilities of most pesticides were obtained because of dissipation by hydrolysis in soil-water system.
Tier system for evaluation of the carry-over potential of soil or water residues to plants was proposed by a series of studies on absorption and translocation of various pesticides to rice and pepper plants. Total of 14 pesticides, classified as suspected endocrine disruptors which comprised alachlor, carbaryl, carbendazim, cypermethrin, 2,4-D, dicofol, endosulfan, fenvalerate, malathion, methomyl, metribuzin, parathion, trifluralin and vinclozolin were subjected to parametric and empirical experiments to stepwise evaluate the degree of upward movement to plants. Environmental parameters of pesticides, including log POW and soil adsorption coefficients, were measured to predict the relative mobility and availability of soil/water residues. Simplified culture systems of rice and pepper plants under hydroponic solution and submerged/moist soils were newly designed to clarify the actual absorption and translocation of pesticides to plants, respectively.
As a polarity parameter of compound, n-octanol/water partition coefficients(log POW) of 12 neutral pesticides comprising 16 compounds and 2 ionizable pesticides were measured using a high-performance liquid chromatographic(HPLC) method in compliance with OECD Test Guidelines. Total of 22 pesticidal compounds covering log POW range of -0.1∼6.9 were carefully selected as reference standards for calibration. While HPLC parameters were precisely controlled, log POW of reference compounds was linearly correlated with logarithm of capacity factors(k') on a C18 column, empirically showing the formula, Log POW = 2.407 · Log k' + 2.499 (r² = 0.970^**). Compared with the values reported in the literature or predicted by a commercial simulation software, log POW values of the pesticides measured in the method deviated in the range of 0.14∼0.99 or 0.12∼1.05, respectively. Ionizable compounds, carbendazim and 2,4-D, showed dramatic change in log POW values as the compound was ionized or ion-suppressed.
To predict relative upward mobility of pesticides by the environmental parameter, soil adsorption coefficients were also estimated using a batch equilibrium method in compliance with OECD Test Guidelines. Total of 13 neutral compounds covering log POW range of 0.23 ∼5.9 as well as two ionizable compounds, 2,4-D and carbendazim, were subjected to estimation of adsorption to a standard Korean soil. Derived from pesticide concentrations in soil-water phase at 9 equilibrated levels, soil sorption constant(K_OC) and Freundlich adsorption coefficient(K_F) were calculated. K_OC and K_F values showed in the wide range of 2.5×10¹∼1.4×10⁵ and 0.09∼1.6×10³, respectively, as reflected by relative adsorptivity of pesticides. 2,4-D and carbendazim which existed as ionized and neutral species at pH 5∼7, respectively, exhibited K_OC and K_F values corresponding to compounds with log POW of 1.5 ∼1.6. Log POW values were correlated with logarithms of K_OC more closely than those of K_F, while large deviations in some compounds were found. To estimate soil mobility of a compound, it is considered that K_OC values to corresponding soils, in addition to intrinsiclog POW should be also compared.
Rice and pepper plants were chosen as model species to estimate the degree of plant absorption of pesticide residues in soil or water. Simplified growth systems under hydroponic solution or submerged/moist soil were newly designed to actually estimate the systemic property. In the hydroponic culture system, pesticides were treated each in the 20% Hoagland solution in which two 30 day-old rice or one 40 day-old pepper seedlings were transplanted. While normal growth of rice and pepper plants was maintained for 7 days, pesticide residues in shoot, root and hydroponic solution were analyzed at specified time interval. In the soil culture system, defined portions of soil were treated with pesticides and submerged by pouring hydroponic solution for rice plants. In the soil culture of pepper plants, portions of soil treated with pesticides were moistened to be 60% field-moisture capacity.
In nonpolar pesticides with the log POW range of 3.0∼5.9, which include alachlor, cypermethrin, dicofol, endosulfan, fenvalerate, malathion, parathion, trifluralin and vinclozolin, their concentration in the hydroponic solution decreased more rapidly than the volume of solution by transpiration. Even though some translocation and accumulation of pesticides were observed, total amount of pesticides in the shoot was less than 5% of the applied dose at maximum except 8.3% of vinclozolin in pepper plants. Much higher residues were found in the root showing 4∼63% of the dose applied dose, presumably indicating that the root acted as adsorption site of the pesticides. Alachlor and malathion residues in rice and pepper plants were quite lower than those of other pesticides due to rapid dissipation in plants and/or hydroponic solution. Formation of endosulfan sulfate from endosulfan, even though relatively low the oxidative activity might be, was evident both in plants and hydroponic solution.
For polar pesticides, total of 3 neutral pesticides including methomyl, carbaryl and metribuzin with log POW range of 0.23∼2.11 as well as two ionizable compounds, 2,4-D and carbendazim, were also subjected to hydroponic culture system. While normal growth of plants was maintained for 7 days, translocation and accumulation of pesticides in plants were observed. Total amount of pesticides in rice and pepper plants ranged 4.2∼10.3% and 3.0∼26.2% of the applied dose at 7 days, respectively. As time elapsed, higher residues were remarkably found in the shoot than those in the root. Unlikely to nonpolar pesticides, the root part was merely acted as the temporary site during absorption process of the pesticides. When methomyl, carbaryl, metribuzin and carbendazim were treated, shoot/root ratio in residues gradually increased and reached to 3∼14 and 7∼27 at 7 days in rice and pepper plants, respectively. Even though both plants were severely damaged by 2,4-D, absorption pattern showed quasi-systemic nature of the compound. Polar and ionizable pesticides subjected to the study seemed to be systemic and readily translocated to the plant from the water phase.
Involving soil component to simulate the field condition, absorption and translocation of nonpolar pesticides by rice plants were also quite limited. Compared with hydroponic culture condition, much less absorption and translocation to rice shoot were observed in all the pesticides tested. Total amount of pesticides in the shoot was less than 1% of the applied dose at maximum. No residue was found in malathion and only 1/5 to 1/20 portions in recovery of hydroponic culture were observed in soil culture. While high recovery in root part under hydroponic culture was no more found, most of pesticides resided in soil, indicating that the soil was acted as adsorption site of the pesticides. Dissipation rates of pesticides in soil culture were higher than those in hydroponic culture. Vinclozolin could be still evaluated to be quasi-systemic, whereas parathion is estimated to be non-systemic mainly due to fast dissipation rate.
In case of polar pesticides, similar tendency was observed in soil culture, that is, lower absorption and faster dissipation compared with hydroponic culture. As rapidly dissipated, methomyl recovery in shoot was only 0.5% of the dose applied and, as a result, carry-over potential was evaluated to be low. Carbaryl, carbendazim and metribuzin appeared still to be systemic in soil culture, even though 1/2 to 1/5 portions in recovery of hydroponic culture were observed. Unlikely to hydroponic culture, rice plants survived in soil culture treated with 2,4-D and its absorption rate to shoot part was almost same. Among 14 pesticides tested, there was no exception that absorption and translocation rates in soil culture were lower than those in hydroponic culture. Therefore, hydroponic system is not only simple to operate but also could provide highest carry-over potential, in other sense, highest possibility of hazardous residues in plants. However, soil culture testing was also needed to precisely evaluate and confirm the systemic property of the pesticides.
When moist soil component was involved during pepper culture, absorption and translocation of pesticides by pepper plants were mostly similar to the tendency of differences between hydroponic and soli cultures found in rice plants. However, some exceptions were also observed in selected pesticides. Therefore, rice and upland plants cultivated under different soil moisture conditions should be separately evaluated for carry-over potential of pesticides.
Coupling parametric and empirical experiments conducted in this study, Tier system for evaluation of carry-over potential of pesticides to plants could be proposed. At first, parametric prediction intrinsic to molecular properties could be applied to the initial step of Tier system for categorization of mobility. Timely distribution and dissipation of pesticides in plant parts and hydroponic media could be employed as empirical stage of Tier system for practical estimation of carry-over potential. Using soil culture system, systemic characteristics of pesticides could be finally evaluated or confirmed. Tier system of 3-step estimation could be used as a component in pesticide registration system as well as to classify and manage currently registered pesticides on the basis of carry-over possibility to plants.
Endocrine disruptors(EDs) which are absorbed within the organism and do biochemical reactions which interfere the normal action of hormones, is also known as environmental hormones. The main sources of endocrine disruptors include various plastics, coatings, and chemicals such as pesticides. Meanwhile, researches on EDs were focused on industrial organic compounds and systematic studies on pesticides is lacking.
Some of the pesticides sprayed in agricultural environments is lost via volatilization, decomposition, and absorption by the target organism, but the substantial amount of them eventually comes into the surrounding water through rainfall runoff, soil erosion, and leaching to ground water. Especially, direct runoff from agricultural land was known as the major cause of pesticide residues in water.
Water pollution by pesticides brings secondary problems such as harm to agricultural production, inhibition of the growth of crops, destruction of aquatic ecosystems, and ground water contamination. The secondary issues has been underestimated compared to the immediate problem of crop residual toxicity.
However, recently pesticide and its secondary products are detected in the aquatic environment around the pesticides spraying area resulted in environmental damage extensively. Therefore, agricultural non-point source pollution has been growing concern. Most of the pesticide runoff sources are orchards, paddy fields, greenhouse, golf courses, etc. And the current pesticide use in rice fields is low-level than in the past due to acreage reduction of rice field, but still more than 40 percent of the total has been used in rice fields. Spraying pesticides in paddy fields is expected impact on water larger than spraying orchards or upland since sprayed on ponding conditions, and water hydrologically connected directly to the watershed. Therefore, precise investigation on the load characteristics from paddy field (pesticide type, timing, load) is required. However, research related to the pesticide as agricultural non-point source pollution has been conducted under very limited circumstances. After spraying pesticide, it is lost via photolysis, biodegradation, adsorption, volatilization, leaching loss and through surface runoff water.
Since degradation and mobility of pesticides vary according to weather conditions and farming practices, a lot of time and effort are required to obtain wide range of basic data to set environmental standards. Therefore, computer model that can simulate effects of wide range of environment and farming methods on pesticide degradation and mobility, can save a lot of time and effort to establish appropriate environmental standard setting.
The reason why less modeling studies on pesticides compared to those for nutrients such as nitrogen and phosphorus is that there was not enough field data for calibration and validation of model. Since chemical analysis for pesticide is expensive and difficult, there are not many studies conducted on pesticide modeling even other countries. To get information on behavior of pesticides in environment, establishment of a technology analysis multiple pesticides quickly and simultaneously is needed.
The objective of the this study was to establish modeling technology for pesticide behavior from upland and paddy field. Alacholar, Carbaryl, Cypermethrin, 2,4-D, Endosulfan and Ethyl-parathion, and Fenvaleratein wer studied.
1) Development methods and determination of pesticides
2) Information acquisition by literature review and experiment on studying pesticides behavior on environment
3) DB development on parameter of agricultural land
4) Field monitoring from plot and paddy field
5) Pesticide residue modeling with GLEAMS model
6) Runoff ratio estimation with RICEWQ model with lab test data
7) Pesticide DB development (application rate, application timing, characteristics of pesticide)
8) Best management practice evaluation with RICEWQ model
9) Water quality monitoring of adjacent area to cultivation field
○ Results of the research
Residue of Alacholar and Endosulfan in soil significantly increased in double rate application treatment compared to those of single rate application treatment. Alacholar showed higher concentration in 20-40 cm layer than surface layer. Endosulfan showed sharp decrease concentration in subsurface layer. Cypermethrin and Fenvalerate show minimal residue due to volatilization and water solubility.
○ Application plan for research outcome
☐ Pesticide residue in pepper plot
Temporal and spatial variations of the residue of Alacholar, Cypermethrin, Endosulfan and Fenvaleratein in soil were identified.
☐ GLEAMS and RICEWQ model application
Climate change affect rainfall amount and pattern which result in flood, loss of agricultural land, reduction of crop production, acceleration of pesticide lost from watershed and environment problem. Computer model, simulate effects of wide range of environment and farming methods on pesticide degradation and mobility, calibrated in this study could be used to predict pesticide behavior in environment and identify best management practice protect environment.
A number of pesticides including atrazine, DDT, lindane, vinclozolin are known as endocrine disrupting chemicals (EDCs). They could interfere with the endocrine system and thereby impair fertility and the development of animals and possibly of humans. However, it would be difficult to predict the adverse effects and exposure pathway due to widespread use of pesticides. The physiologically and biologically active nature of pesticides raised concerns about their potential impacts to non-target species when they were inadvertently discharged into ecosystem. The present study was conducted to develop the sensitive biomarkers on EDCs, the method of 21-day endocrine screeing assay, and the health index to ecological health assessment in aquatic ecosystem using Misgurnus anguillicaudatus.
In this study, 21day exposure tests to alachlor, benomyl, carbaryl, endosulfan, methomyl, metribuzin, 2,4-D were performed using M. anguillicaudatus, which inhabit widely rice paddy in Korea, under continuous flow-through system. Following range-finding test, test concentrations for 21d exposure test were determined below the lethal level as much as possible. We also observed various indicators and biomarkers such as condition factor (CF), gonado-somatic index (GSI), liver-somatic index (LSI), vitellogenin (VTG), DNA damage using comet assay, acetylcholinesterase (AChE), and ethoxyresorufin-O-deethylase (EROD) at middle and end of the test for identifying the effect of endocrine disruption and sub-lethal toxicity. VTG in blood plasma was significantly greater in male fish exposed to 0.002 mg/L endosulfan, in female and male fish exposed to 0.4 and 2 mg/L methomyl, in male fish exposed to 5 mg/L carbaryl, and in female fish exposed to 10 mg/L metribuzin for 21d than in control (p<0.05, Table 1). While CF, GSI, and LSI weren't affected by exposure to test chemicals, DNA were damaged in fish exposed all test pesticides (p<0.05). AChE and EROD activity in M. anguillicaudatus were also influenced by exposure of carbaryl, endosulfan, methomyl and alachlor, endosulfan, 2,4-D, respectively (p<0.05, Table 1).
In addition, screening level ecological assessment was conducted using multiple biomarkers as described above in M. anguillicaudatus. Sexually mature M. anguillicaudatus were sampled in agricultural irrigation canal of Gisan-myun, Seocheon (Study site), which have possibility of pesticides exposure, and in valleys water of Chunghwa-myun, Buyeo (Reference site) during May-June 2011. The indicators were compared between reference and agriculture area from each other. In molecular level biomarker, AChE, EROD, and DNA damage were statistically different (p<0.05) between two groups except VTG. In addition, physiological bioindicators, eg., CF, GSI, LSI, didn’t show the distinction.
Consequently, two protocols, (a) Toxicity test method for Endocrine disrupting chemicals (EDCs) using Misgurnus anguillicaudatus, and (b) Ecosystem health assessment method for endocrine disrupting chemicals (EDCs) using the indicator fish, Misgurnus anguillicaudatus, based on these results was made. These products could be utilized in M. anguillicaudatus as means of ecological health assessment and regulation.
Dermal and inhalation exposure of the aplicator was measured for risk assessment during the application of insecticide fenavalerate in an apple orchard. EC (Emulsifiable Concentrate) and WP (Wettable powder) formulation were sprayed with SS (Speed Sprayer), PS (Power Sprayer). Dermal patches, gloves, socks and masks were used to monitor the potential dermal exposure, and personal air samplers with XAD-2 resins were used to monitor the potential inhalation exposure.
For WP the amount of dermal and inhalation exposure were 2032.34μg (0.0081% of total applied amount) and 2.16μg (8.65Ⅹ10-6%), repectively, with SS while 1087.93μg (0.0145%) and 1.25μg (1.67Ⅹ10-5%), repectively, with PS. In case of EC, 3804.60μg (0.0152%) and 2.45μ g (9.81Ⅹ10-6%), repectively, for with SS while 4054.99μg (0.0541%) and 3.73μg (4.97Ⅹ10-5%), repectively, with PS. The main body parts of exposure were thigh and upper arm with SS or thigh and hand with PS. For risk assessment, the potential dermal exposure (PDE), the Potential inhalation exposure (PIE), the absorbable quantity of exposure (AQE) and the Margin of safety (MOS) were calculated. The MOSs of all four cases was much larger than 1, indicating least possibility of risk.
In viro metabolism of fenvalerate was conducted with human liver microsome. Six metabolites were identified or characterized including 2-OH-CPIA (4-chloro-(2-hydroxy- 1-methylethyl) benzeneacetic acid) isomers by GC-MS. The relative amount of 2-OH-CPIA 1 and 2 were changed by metabolic reaction time.
The screening test for identifying which CYP isoform involved with metabolism of fenvalerate was conducted with 10 human cDNA-expressed CYP isoforms. Isoform CYP 2B6 produced 2-OH-CPIA 1 much more than 2. However, CYP 2C8, 2C9 and 2C19 showed opposite results. Four isozymes (CYP 2B6, 2C8, 2C9, 2C19) mainly contributed to metabolism of fenvalerate.
For pesticde exposure and risk assessment studies, methomyl and benomyl were chosen as subject pesticides because they are known as the suspected edocrine disruptors. Methomyl (WP; Wettable powder and SL; Soluble liquid formulations) is a broad spectrum carbamate insecticide with both contact and oral toxicity to various insects and benomyl (WP formulations)is a systemic fungicide with both protective and curative activities while its degradation product, carbendazim, is the biologically active component. Experiment was performed in apple orchard, and SS (Speed sprayer) and PS (Power sprayer) were used for application of pesticides. Dermal patches, gloves, socks and masks were used to monitor the potential dermal exposure, and personal air samplers with XAD-2 resins were used to monitor the potential inhalation exposure.
In methomyl exposure study, exposure characteristics between WP and SL formulations, and between SS and PS were compared during mixing/loading and application. In benomyl exposure study only one WP formulation and one application methods, SS, were used to evaluate exposure and risk during larger scale mixing/loading and application.
Method validation for LOD, LOQ, recovery, reproducibility, linearity and range of calibration, trapping efficiency and breakthrough tests were performed and the results were reasonable for exposure study of methomyl and benomyl.
During mixing/loading of methomyl, more contaminatiom body parts for WP, including face, were observed than those of SL probably due to drift of powder of WP fromualtion. The most of exposure was observed on hand (56 ~ 100% of total exposure), especially, 100% hand exposure of about 330 mg was observed for SL formulation in case of PS. This contamination was resulted from spill of methomyl liquid on gloves during preparation of spray mixture using of bottle cap. When methomyl was applied on apple orchard using PS or SS, the dermal exposure ratio to total spraying amount was within the range of 6 × 10-3 ~ 26 × 10-3%. There was not significant difference between two formulations however, PS resulted more exposure rates (3~4 times) than SS. Major exposured parts of body were arms and thigh, then chest for both cases. In case of PS, more contamination was observed on hand than SS. Eventhough inhalation exposure of methomyl during mixing/loading and application was very low, more exposure (2~6 times) was observed for PS than for SS in case of application.
In exposure study of benomyl the amount of dermal exposure to benomyl (WP) during mixing/loading was 10.9 mg with the ratio to total prepared amount of 7.3 × 10-4 %. Inhalation exposure of benomyl during mixing/loading was observed at very low level. The amount of dermal exposure to benomyl (WP) during application for 1 ha was 814.1 mg. The exposure ratio to total spraying amount was the range of 0.05%. The primary body parts of exposure were mainly thigh, upper arms and shins. Inhalation exposure of benomyl during mixing/loading and application was also observed at very low level. In case of application it was about 4,000 times less than dermal exposure. For risk assessment of benomyl exposure the margin of safety (MOS) was calculated by extrapolating those results to 4 ha treatment and it was found that the exposure level is considered to be safe (MOS > 1).

목차 Contents

• 제출문 ... 1
• 요약문 ... 3
• SUMMARY ... 14
• 제 1 장 서 론 ... 24
• 제 2 장 국내외 기술개발 현황 ... 35
• 제1절 농산물 중 내분비계장애추정물질 잔류실태 및 위해성평가 연구 ... 35
• 제2절 농경지 중 내분비계장애추정물질 오염실태 조사 ... 38
• 제3절 내분비계장애추정농약의 작물체내 흡수, 이행 및 잔류특성 연구 ... 41
• 제4절 내분비계장애추정농약의 농업환경 중 이동성 예측모델 연구 ... 42
• 제5절 농생태계 서식생물 내분비계장애추정물질 오염실태 조사 ... 44
• 제6절 미꾸리의 다중 생물지표를 이용한 내분비계장애추정물질의 독성반응 평가 및 수생태계 건강성지수 개발 ... 46
• 제7절 내분비계장애추정농약의 농작업자 위해성 평가 및 노출량 예측 연구 ... 48
• 제 3 장 연구개발수행 내용 및 결과 ... 51
• 제1절 농산물 중 내분비계장애추정물질 잔류실태 및 위해성평가 연구 ... 51
• 제2절 농경지 중 내분비계장애추정물질 오염실태 조사 ... 79
• 제3절 내분비계장애추정농약의 작물체내 흡수, 이행 및 잔류특성 연구 ... 95
• 제4절 내분비계장애추정농약의 농업환경 중 이동성 예측모델 연구 ... 177
• 제5절 농생태계 서식생물의 내분비계장애추정물질 오염실태 조사 ... 276
• 제6절 미꾸리의 다중 생물지표를 이용한 내분비계장애추정물질의 독성반응 평가 및 수생태계 건강성지수 개발 ... 321
• 제7절 내분비계장애추정농약의 농작업자 위해성 평가 및 노출량 예측 연구 ... 370
• 제 4 장 연구개발목표 달성도 및 대외기여도 ... 466
• 제1절 목표대비 달성도 ... 466
• 제2절 정량적 성과 ... 471
• 제 5 장 연구개발결과의 활용계획 ... 476
• 제 6 장 중요 변동사항 ... 478
• 제 7 장 참고문헌 ... 479
• 참고 1 연차평가 지적사항 및 조치결과 ... 502
• 참고 2 주요연구 성과 ... 503
• 끝페이지 ... 559