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Abstract 5
요약문 9
I. 서론 19
1. 문헌연구 및 연구배경 19
가. 과불화화합물의 특성 19
나. 과불화합물의 국제적 대응현황 20
다. 과불화화합물의 유해성 및 축적성 21
라. 암컷 개체로부터의 영향 21
마. 연구배경 22
바. 연구수행 25
과제 1. 과불화화합물의 오염원 주변 생체축적성 평가 26
I/II. 연구내용 및 방법 26
1. 과업의 범위 26
2. 연구내용 28
3. 시료채취 지점 29
4. 분석절차 및 사용기기 37
5. 정성 및 정량분석 41
6. 어류 채집, 분석용 시료 전처리 및 조직학적 분석 48
II/III. 연구결과 및 고찰 53
1. 환경매체 중 과불화화합물의 잔류농도 53
가. 하천수 53
나. 붕어 혈액 및 간 57
다. 하천별 어류 우점종 간 63
라. 송사리 서식지 하천수, 하천퇴적물 및 송사리체내 69
마. 생태계에 잔류하는 과불화화합물의 농도 및 생체 농축성 75
2. 어류 조직학적 분석 결과 87
가. 계측형질 87
나. 성비 87
다. 이성생식세포 발현율 87
라. 생식소중량지수(GSI) 및 간중량지수(HSI) 89
마. 간의 조직학적 특징 91
III/IV. 결론 98
과제 2. 어류의 과불화화합물 축적도 조사 100
I/II. 연구내용 및 방법 100
1. 과업의 범위 100
2. 연구내용 101
3. 시료채취지점 및 시료 정보 101
4. 분석절차 및 사용기기 106
II/III. 연구결과 및 고찰 109
1. 과불화화합물 축적도 109
가. 어류 근육 시료 109
나. 붕어 알(egg) 시료 114
다. 퇴적물 시료 117
라. 과불화화합물 이성질체의 퇴적물, 붕어 근육 및 붕어 알에서의 분포비율 120
마. 과불화화합물의 탄소사슬 길이에 따른 동질체의 분포 특성 123
바. 붕어 근육으로부터 알로 PFCs가 전이되는 비율(MTR, maternal transfer ratio) 125
III/IV. 결론 127
참고문헌 128
Table 1. Physical and Chemical Properties of PFOS and PFOA 24
Table 1-1. Descriptions of sampling sites 30
Table 1-2. Sampling notes of Namhan River 31
Table 1-3. Sampling notes of Nakdong River 33
Table 1-4. Sampling notes of Yeongsan River 35
Table 1-5. Sampling notes of medaka fish habitats 36
Table 1-6. Mobile phase condition 41
Table 1-7. Analysis instrument condition 42
Table 1-8. Precursor and product ions and MS/MS energy values for PFCs analysed using LC-(-) ESI-MS/MS 43
Table 1-9. Analysis result of PFCs in Busan National University 47
Table 1-10 . Analysis result of PFCs in Chonnam National University 47
Table 1-11 . Cross check of analysis results between universities 47
Table 1-12. Number of collected fish species 49
Table 1-13. Distribution of fish species in 6 sampling sites 50
Table 1-14. Concentrations of PFCs in river water 55
Table 1-15. Concentrations of PFCs in the blood of crucian carp 59
Table 1-16. Concentrations of PFCs in the liver of crucian carp 61
Table 1-17. Hepatosomatic Index (HSI), Gonadosomatic Index (GSI), total length and body weight of dominant fish species 65
Table 1-18. Concentrations of PFCs in the liver of dominant fishes 66
Table 1-19. Concentrations of PFCs in water from medaka habitat 70
Table 1-20. Concentrations of PFCs in sediment of medaka habitat 70
Table 1-21. Concentrations of PFCs in medaka wholebody 72
Table 1-22. Bioconcentration factors (BCFs) in carp blood at each river 79
Table 1-23. Bioconcentration factors (BCFs) in carp liver at each river 79
Table 1-24. Bioconcentration factors (BCFs) of PFCs in medaka at each collecting site 83
Table 1-25. Mean bioconcentration factors (BCFs) of PFCs in crucian carp blood, liver, medaka fish and other dominant fish liver 83
Table 1-26. Total length and body weight of crucian carp (Carassius auratus) 87
Table 1-27. Sex ratio and intersexuality of crucian carp (Carassius auratus) 88
Table 1-28. Gonadosomatic index (GSI) of crucian carp (Carassius auratus) 90
Table 1-29. Hepatosomatic index (HSI) of crucian carp (Carassius auratus) 90
Table 2-1. Descriptions of sampling sites 101
Table 2-2. Description of fish samples collected from the three major rivers 103
Table 2-3. Average recovery rates of PFCs in the muscle of the crucian carp 109
Table 2-4. PFCs levels in the muscle of freshwater fish 110
Table 2-5. Average recovery rates of PFCs in the egg of the crucian carp 114
Table 2-6. PFCs levels in the egg of crucian carp 115
Table 2-7. Recovery rates of PFCs in the sediment 117
Table 2-8. PFCs levels in the sediment from the three major rivers 118
Table 2-9. Average PFCs levels in the sediment, muscle and Egg of crucian carp site sample 121
Table 2-10. Maternal transfer ratio of crucian carp 125
Figure 1. Sample collection and analysis scheme 25
Figure 1-1. Map showing sampling sites in rivers and medaka fish habitats 29
Figure 1-2. Sampling sites in Namhan River 31
Figure 1-3. Sampling sites in Nakdong River 33
Figure 1-4. Sampling sites in Yeongsan River 35
Figure 1-5. Map showing sampling sites of medaka fish habitats 36
Figure 1-6. Analytical procedure of PFCs in water 38
Figure 1-7. Analytical procedure of PFCs in sediment and fish tissues 40
Figure 1-8. LC-MS/MS chromatogram of target PFCs standard and surrogate materials 44
Figure 1-9. Calibration curve of target PFCs 45
Figure 1-10. Target fish species 50
Figure 1-11. Pretreatment process of fish samples 52
Figure 1-12. Process of light microscopy 52
Figure 1-13. Concentrations of PFCs in river water 56
Figure 1-14. Concentration of PFCs in blood of crucian carp 60
Figure 1-15. Concentration of PFCs in liver of crucian carp 62
Figure 1-16. Concentration of PFCs in liver of dominant fishes 68
Figure 1-17. Concentration of PFCs in the water from medaka habitat 69
Figure 1-18. Concentration of PFCs in medaka whole bodies 73
Figure 1-19. Comparing concentration of PFCs in water and biota 73
Figure 1-20. Distribution of ΣPFSAs and ΣPFCAs in the water, sediment of medaka habitate and medaka whole body 74
Figure 1-21. Mean total concentration of detected PFCs in survey matrices 76
Figure 1-22. Comparing PFOS concentration in river water with other countries. References: [1] So et al., 2007; [2] Saito et al., 2003; [3] Sinclai et al., 2004; [4] Senthikumar et al., 2007; [5] Naile et al., 2010; [6] Yamashita et al., 2005 76
Figure 1-23. Comparing PFOS concentration in biota with other countries. References: [1] Li et al., 2008; [2] Naile et al., 2010; [3] Sinclai et al., 2004 77
Figure 1-24. Distribution of ΣPFSAs and ΣPFCAs in the water, Crucian Carp Liver, blood and dominant fish liver 77
Figure 1-25. Bioconcentration factors of PFCs in blood of crucian carp 80
Figure 1-26. Bioconcentration factors of PFCs in liver of crucian carp 80
Figure 1-27. BCF trend of PFCAs (C9-C13) in crucian carp tissues 81
Figure 1-28. Bioconcentration factors in medaka wholebody 84
Figure 1-29. Mean bioconcentration factors of PFOS in biota 84
Figure 1-30. Correlation between PFCs concentrations in crucian carp blood and liver 86
Figure 1-31. Ovary (left) and testis (right) of crucian carp (Carassius auratus) 88
Figure 1-32. Photomicrographs of intersex gonad of crucian carp(Carassius auratus). A: Danyang. B: Yeoju. C: Andong. D: Waegwan. E: Damyang. F: Gwangju. Oc, oocyte; Tt, testicular tissue. H-E stain 88
Figure 1-33. Gonadosomatic index (GSI) of crucian carp (Carassius auratus) 89
Figure 1-34. Hepatosomatic index (HSI) of crucian carp (Carassius auratus) 90
Figure 1-35. Photomicrographs of liver of crucian carp (Carassius auratus) : Namhan River (Danyang). H-E stain. 92
Figure 1-36. Photomicrographs of liver of crucian carp (Carassius auratus) : Namhan River (Yeoju). H-E stain. 93
Figure 1-37. Photomicrographs of liver of crucian carp (Carassius auratus) : Nakdong River (Andong). H-E stain. 94
Figure 1-38. Photomicrographs of liver of crucian carp (Carassius auratus) : Nakdong River (Waegwan). H-E stain 95
Figure 1-39. Photomicrographs of liver of crucian carp (Carassius auratus) : Yeongsan River (Damyang). H-E stain 96
Figure 1-40. Photomicrographs of liver of crucian carp (Carassius auratus) : Yeongsan River (Gwangju). H-E stain 97
Figure 2-1. Locations of sampling sites 102
Figure 2-2. Average levels of PFCs in the muscle of freshwater fishes Carp: crucian carp, DS: other dominant fish at the site 113
Figure 2-3. Average levels of PFCs in the egg of crucian carp 116
Figure 2-4. PFCs levels in the sediment of the three major rivers 119
Figure 2-5. Distribution of PFCs congeners in the muscle and egg of carp and sediment 120
Figure 2-6. Distribution of ΣPFSAs and ΣPFCAs in the sediment, and muscle and egg of crucian carp 122
Figure 2-7. Average levels of ΣPFSAs and ΣPFCAs in the sediment, and muscle and egg of crucian carp 122
Figure 2-8. Congener distributions of PFCAs in the sediment, and muscle and egg of crucian carp 123
Figure 2-9. Congener distributions of PFCAs in the muscle of other dominant species from each site 124
Figure 2-10. Maternal transfer ratio according to the body weight of crucian carp 126
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