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Abstract 5
요약문 10
I. 서론 22
1. 연구 배경 및 필요성 22
가. 과불화합물의 특성 22
2. 과불화합물 축적성 및 유해성관련 국내외 연구동향 25
3. 국내외 연구동향 및 관리동향 27
4. 연구 목적 33
5. 연구 수행 방법 34
II. 연구내용 및 방법 35
1. 과업의 범위 35
가. 대상 지역 35
나. 대상 시료 36
다. 분석대상 화학종 36
2. 연구 내용 37
3. 시료채취 지점 38
가. 조사지점 38
나. 시료채취 방법 48
4. 분석절차 및 사용기기 49
가. 하천수 49
나. 퇴적물 시료 51
다. 어류조직 시료 분석 54
5. 정성 및 정량분석 55
가. 분석기기의 조건 55
나. 정성 및 정량 57
다. 검량선 61
라. 검출한계 및 회수율 63
III. 연구결과 및 고찰 67
1. 주요하천에서 과불화합물의 환경잔류 특성 67
가. 주요하천의 하천수 중 과불화합물 잔류농도 67
나. 주요하천의 하천 퇴적물 중 과불화합물 잔류농도 71
다. 주요하천의 붕어 체내 과불화합물 잔류농도 75
라. 주요하천의 우점종 체내 과불화합물 잔류농도 89
마. 과불화합물의 환경 중 생물농축특성 및 근육에서 알로의 전이 특성 96
2. 낙동강 수계에서 과불화합물의 환경잔류 특성 119
가. 낙동강 수계 하천수에서 과불화합물 잔류농도 119
3. 송사리 서식지에서 과불화합물의 환경잔류특성 125
가. 송사리 서식지 하천수 및 하천 퇴적물 중 과불화합물 잔류특성 125
나. 송사리 체내 과불화합물 잔류농도 분포 및 패턴 130
4. 과불화합물의 환경잔류 특성 평가(3년간 결과 비교) 137
가. 주요하천 하천수 중 과불화합물 잔류특성 비교평가 137
나. 주요하천 퇴적물 중 과불화합물 잔류특성 비교평가 139
다. 주요하천 붕어 체내 과불화합물 잔류특성 비교평가 143
라. 주요하천 수계에서 과불화합물 잔류특성 종합평가 148
마. 송사리 서식지 환경 중 과불화합물 잔류특성 비교평가 150
Ⅳ. 결론 156
참고문헌 159
Table 1-1. Physical and chemical properties of PFOS and PFOA 24
Table 1-2. Regulated PFASs by REACH 28
Table 1-3. Regulated PFASs by Korean Chemical materials management law 32
Table 1-4. Circulation volume of PFCs as C8~C20 in Korea 32
Table 2-1. Target compounds of PFASs in this study 37
Table 2-2. The number of samples in sampling sites 39
Table 2-3. Sampling notes of Namhan River 40
Table 2-4. Sampling notes of Nakdong River 41
Table 2-5. Sampling notes of Yeongsan River 43
Table 2-6. Sampling notes of medaka fish habitats 45
Table 2-7. Sampling site and basic data in Nakdong River dry and wet seasons survey 47
Table 2-8. Analysis instrument condition(Chonnam Univ.) 56
Table 2-9. PFASs analytical condition for LC-MS/MS(Pusan Univ.) 56
Table 2-10. Precursor and product ions and MS/MS energy values for PFASs analysed using LC-(-) ESI-MS/MS(Chonnam Univ.) 58
Table 2-11. Condition of mass spectrometry for the analysis of PFASs(Pusan Univ.) 59
Table 2-12. Limit of detection (LOD), limit of quantification (LOQ) and recovery rate in water, sediment and biota 65
Table 2-13. Method detection limit in samples 65
Table 2-14. Average recovery of PFASs in samples 66
Table 3-1. Levels of PFASs in river water samples 69
Table 3-2. Comparison of level of PFASs in river water by country 70
Table 3-3. Level of PFASs in sediment samples 73
Table 3-4. Comparison of level of PFASs in river sediment by country 74
Table 3-5. Hepatosomatic Index(HSI), gonadosomatic Index(GSI), total length and total weight of crucian carp and dominant fish 75
Table 3-6. Concentrations of PFASs in the blood of crucian carp 78
Table 3-7. Concentrations of PFASs in the liver of crucian carp 79
Table 3-8. Level of PFASs in crucian carp muscle samples 85
Table 3-9. Level of PFASs in crucian carp egg samples 86
Table 3-10. Comparison of level of PFASs in fish samples by country 88
Table 3-11. Concentrations of PFASs in the liver of dominant fishes 92
Table 3-12. Level of PFASs in dominant species muscle samples 94
Table 3-13. Mean concentration of detected PFASs in each matrices 99
Table 3-14. Average of bioconcentration factor(BCF) in crucian carp 105
Table 3-15. The pervious studies result of BSAF in PFASs and other POPs compounds 106
Table 3-16. Average of biota-sediment accumulation fact(BCAF) in crucian carp 109
Table 3-17. The pervious studies result of BSAF in PFASs and other POPs compounds 110
Table 3-18. Comparison of MTR of PFASs and other POPs 117
Table 3-19. Concentrations of PFAS in Nakdong River survey in wet season 122
Table 3-20. Concentrations of PFAS in Nakdong River survey in dry season 123
Table 3-21. Concentration of PFCs in surface water from Nakdong River and tributary(Cho et al., 2010) 124
Table 3-22. Concentrations of PFASs in water of medaka habitate 128
Table 3-23. Concentrations of PFASs in sediment of medaka habitate 129
Table 3-24. Concentrations of PFASs in medaka whole body 132
Table 3-25. Bioconcentration factors(BCFs) of PFASs in medaka whole body 136
Table 3-26. Total concentration of PFASs in medaka habitat according to year 150
Figure 1-1. Structure of main PFASs 22
Figure 1-2. Sample collection and analysis scheme 34
Figure 2-1. Map showing sampling sites in rivers 38
Figure 2-2. Sampling sites in Namhan River 40
Figure 2-3. Sampling sites in Nakdong River 42
Figure 2-4. Sampling sites in Yeongsan River 43
Figure 2-5. Sampling sites of medaka fish habitats 44
Figure 2-6. Sampling sites in Nakdong River dry and wet seasons survey 46
Figure 2-7. Analytical procedure of PFASs in water(Chonnam Univ.) 50
Figure 2-8. Flow chart of analytical method for PFASs in Sediment(Pusan Univ.) 51
Figure 2-9. Analytical procedure of PFASs in sediment and fish tissues(Chonnam Univ.) 53
Figure 2-10. Flow chart of analytical method for PFASs in fish egg/muscle(Pusan Univ.) 54
Figure 2-11. LC-MS/MS chromatogram of target PFASs standards and surrogate materials 60
Figure 2-12. Calibration curve of target PFASs(Chonnam Univ.) 61
Figure 2-13. Calibration curve of target PFASs(Pusan Univ.) 62
Figure 3-1. Concentration of PFASs in river water 68
Figure 3-2. Relative%-composition of individual PFASs in total PFASs concentration in water from river 68
Figure 3-3. Level of total PFASs in sediment samples 72
Figure 3-4. Distribution of PFASs in sediment samples 72
Figure 3-5. Concentration of PFASs in blood of crucian carp 80
Figure 3-6. Concentration of PFASs in liver of crucian carp 81
Figure 3-7. Contamination patterns of PFASs in blood and liver of crucian carp 82
Figure 3-8. Distribution of PFASs in crucian carp blood and liver samples 83
Figure 3-9. Level of total PFASs in crucian carp muscle and egg samples 87
Figure 3-10. Distribution of PFASs in crucian carp muscle and egg samples 87
Figure 3-11. Concentration of PFASs in liver of dominant fishes 93
Figure 3-12. Level of total PFASs in dominant species muscle samples 95
Figure 3-13. Distribution of PFASs in dominant species muscle samples 95
Figure 3-14. Mean total concentration of detected PFASs in survey matrices 98
Figure 3-15. 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] Cho et al., 2009 100
Figure 3-16. Comparing PFOS concentration in biota with other countries. References: [1] Li et al., 2008; [2] Naile et al., 2010 100
Figure 3-17. PCA plot of PFASs by river and sample type. 101
Figure 3-18. Distribution of BCF for PFASs in crucian carp; Scenario 1. 103
Figure 3-19. Distribution of BSAF for PFASs in crucian carp; Scenario 1 108
Figure 3-20. Correlation between total weight and PFASs concentrations in the muscle of crucian carp; (a) Namhan river, (b) Nakdong river, (c) Yeongsan river 111
Figure 3-21. Correlation between sample species of ΣPFASs concentration; (a) ΣPFASs in sediment vs ΣPFASs in river, (b) ΣPFASs in sediment vs ΣPFASs in fish muscle (c) ΣPFASs in river vs ΣPFASs in fish muscle 112
Figure 3-22. Correlation between sediment concentration and fish muscle of PFASs concentration; (a) PFOA in sediment vs PFOA fish muscle, (b) PFOS in sediment vs PFOS in fish muscle (c) ΣPFCAs in sediment vs ΣPFCAs in fish muscle, (d) ΣPFSAs... 114
Figure 3-23. Correlation between fish muscle and other fish tissue of PFASs concentration; (a) ΣPFASs in fish muscle vs ΣPFASs in fish egg, (b) ΣPFASs in fish muscle vs ΣPFASs in fish liver (c) ΣPFASs in fish muscle vs ΣPFASs in fish blood 115
Figure 3-24. Correlation between PFASs concentrations in crucian carp blood and liver 116
Figure 3-25. MTR according to the total body weight of crucian carp 118
Figure 3-26. PFASs concentration in water collected from upstream to downstream of Nakdong River in wet season 119
Figure 3-27. PFASs concentration in water collected from upstream to downstream of Nakdong River in dry season 120
Figure 3-28. A comparison of PFCAs, PFSAs and sum PFASs concentrations in water from Nakdong River in dry and wet season 121
Figure 3-29. Concentration of PFASs in the water from medaka habitate 126
Figure 3-30. Relative %-composition of individual PFASs in total PFASs concentration in water from medaka habitat 126
Figure 3-31. Concentration of PFASs in the sediment from medaka habitat 127
Figure 3-32. Concentration of PFASs in medaka whole body 131
Figure 3-33. Relative %-composition of individual PFASs in total PFASs concentration in medaka whole body 134
Figure 3-34. Bioconcentration factors in medaka 135
Figure 3-35. Sum PFASs concentration in surveyed rivers in each sampling year 138
Figure 3-36. Loading plot of principal component analysis for detected PFASs in water from river and medaka habitat 138
Figure 3-37. Comparison of total PFASs level in sediment samples according to sampling years 140
Figure 3-38. Comparison of PFOA and PFOS level in sediment samples according to sampling years 140
Figure 3-39. Comparison of total PFASs level in sediment samples according to years and river site 141
Figure 3-40. Comparison of PFOA and PFOS level in sediment samples according to years and river site 142
Figure 3-41. Comparison of total PFASs level in crucian carp of blood and liver according to years. 143
Figure 3-42. Comparison of total PFASs level in crucian carp according to years. 144
Figure 3-43. Comparison of PFOA, PFOS level in crucian carp according to years. 145
Figure 3-44. Comparison of total PFASs level in crucian carp according to years and river site. 146
Figure 3-45. Comparison of PFOA, PFOS level in crucian carp according to years and river site. 147
Figure 3-46. PCA plot of PFASs by years. 148
Figure 3-47. PCA plot of PFASs by river. 149
Figure 3-48. PCA plot of PFASs by sample type. 149
Figure 3-49. Comparison of PFASs level in medaka habitat water according to years. 151
Figure 3-50. Comparison of PFASs level in medaka habitat sediment according to year. 152
Figure 3-51. Comparison of PFASs level in medaka whole body according to year. 154
Figure 3-52. Comparison concentration of PFASs in water and biota(2013). 155
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