臺灣博碩士論文加值系統

本研究探討三種不同奈米金屬微粒（奈米氧化鋅、奈米銀及奈米四氧化三鐵），對活性污泥除磷機制之影響。實驗結果顯示，奈米氧化鋅濃度達2 mgl-1已完全抑制磷蓄積菌之除磷能力；奈米銀達10 mgl-1 時除磷能力僅剩7%；奈米四氧化三鐵濃度達100 mgl-1 始抑制除磷。
統計檢定結果顯示，添加三種奈米金屬對於磷蓄積菌之比攝磷率、PHAs合成/分解率及肝醣分解/合成率皆有顯著影響，且對好氧代謝的影響較厭氧代謝明顯，其抑制程度為奈米氧化鋅>奈米銀≥奈米四氧化三鐵。研究亦發現奈米金屬顆粒對除磷的影響，主要來自金屬離子的釋出及活性氧化物種(Reactive Oxygen Species, ROS)的生成，其釋出量與生成量隨奈米金屬濃度增加而增加。

This study explored the impacts of ZnO, Ag, Fe nanoparticles on biological phosphorus removal. Experimental results showed that the phosphorus removal ability of phosphorus accumulating organism (PAO) was completely inhibited when ZnO nanoparticle concentration was 2 mgl-1. Only 7% removal ability remained when Ag nanoparticle concentration was 10 mgl-1. The phosphorus removal ability of PAO was initially inhibited at 100 mgl-1 concentration of Fe nanoparticle
Statistical analysis showed that the three kinds of nanoparticles significantly affected the PAO’s metabolisms, including phosphorus uptake, PHA synthesis/degradation, and glycogen degradation/synthesis. The influence of nanoparticles was greater at aerobic phase than at anaerobic phase. The order of the inhibition degree of nanoparticles for PAO was ZnO>Ag>Fe3O4. This study also found that the influence of nanoparticles on PAO’s metabolisms mainly resulted from the release of ionic metals and the formation of reactive oxidation species (ROS). The concentration of ionic metals and ROS increased with increasing nanoparticle concentration.

目錄
第一章前言 ...................................................................................................................... 1
1.1 研究緣起 ..................................................................................................................... 1
1.2 研究目的 ..................................................................................................................... 2
1.3 研究流程及重點 ......................................................................................................... 2
1.4 研究內容與架構 ......................................................................................................... 3
第二章 文獻回顧 .............................................................................................................. 5
2.1 生物除磷機制探討 ..................................................................................................... 5
2.1.1 生物除磷 .............................................................................................................. 5
2.1.2 生物除磷代謝模式 .............................................................................................. 7
2.1.3 影響生物除磷效率之重要因子 .......................................................................... 9
2.2 重金屬對生物除磷系統之影響 ............................................................................... 15
2.2.1 一般重金屬對生物除磷系統之影響 ................................................................ 15
2.2.2 奈米級金屬對微生物之影響 ............................................................................ 17
2.3 奈米級金屬於環境中發展及潛在問題 ................................................................... 20
2.3.1 奈米級氧化鋅 .................................................................................................... 21
2.3.2 奈米銀 ................................................................................................................ 22
2.3.3 奈米氧化鐵 ........................................................................................................ 24
2.4 奈米材料毒性試驗 ................................................................................................... 26
2.4.1 活性氧化物種 .................................................................................................... 26
2.4.2 乳酸脫氫酶 ........................................................................................................ 27
第三章 實驗設備與方法 ................................................................................................ 29
3.1 研究設備 ................................................................................................................... 29
3.1.1 B-SBR模廠 ....................................................................................................... 29
3.1.2 批次實驗設備 .................................................................................................... 30
3.1.3 奈米金屬物化資料 ............................................................................................ 31
3.2 研究方法 ................................................................................................................... 32
3.2.1 污泥馴養與人工合成基質 ................................................................................ 32
3.2.2 B-SBR模廠操作參數 ....................................................................................... 33
3.2.3 分析方法與設備 ................................................................................................ 35
3.2.3.1 分析方法 ..................................................................................................... 35
3.2.3.2 分析設備 ..................................................................................................... 36
3.2.4 批次實驗設計 .................................................................................................... 37
3.2.4.1 重金屬對活性污泥釋磷/攝磷影響之批次實驗 ........................................ 37
3.2.4.2 生化反應速率之計算 ................................................................................. 39
3.2.4.3 奈米物質毒性試驗 ..................................................................................... 40
第四章結果與討論 ........................................................................................................ 42
4.1 SBR系統對生物營養鹽之去除特性 ...................................................................... 42
4.2 奈米材料毒性試驗結果 ........................................................................................... 45
4.2.1 活性氧化壓力 .................................................................................................... 45
4.2.1 乳酸脫氫酶 ........................................................................................................ 54
4.3 奈米氧化鋅對活性污泥除磷生化反應之影響 ....................................................... 57
4.3.1 生物除磷效果之影響 ........................................................................................ 57
4.3.2 對生物除磷釋/攝磷能力之影響 ....................................................................... 65
4.3.3 對PHAs合成/分解代謝之影響 ....................................................................... 70
4.3.4 對肝醣分解/合成代謝之影響 ........................................................................... 73
4.3.5 鋅金屬離子釋出之影響 .................................................................................... 76
4.4 奈米銀對活性污泥除磷生化反應之影響 ............................................................... 78
4.4.1 生物除磷效果之影響 ........................................................................................ 78
4.4.2 對生物除磷釋/攝磷能力之影響 ....................................................................... 86
4.4.3 對PHAs合成/分解代謝之影響 ....................................................................... 91
4.4.4 對肝醣分解/合成代謝之影響 ........................................................................... 94
4.4.5 銀金屬離子釋出之影響 .................................................................................... 97
4.5 奈米鐵對活性污泥除磷生化反應之影響 ............................................................. 100
4.5.1 生物除磷效果之影響 ...................................................................................... 100
4.5.2 對生物除磷釋/攝磷能力之影響 ..................................................................... 107
4.5.3 對PHAs合成/分解代謝之影響 ...................................................................... 112
4.5.4 對肝醣分解/合成代謝之影響 .......................................................................... 115
4.5.5 鐵金屬離子釋出之影響 ................................................................................... 117
4.6 三種奈米金屬毒性比較 .......................................................................................... 119
4.6.1 釋/攝磷率比較 .................................................................................................. 119
4.6.2 PHAs合成/分解率比較 .................................................................................. 121
4.6.3 肝醣分解/合成率比較 ..................................................................................... 123
第五章 結論與建議 ...................................................................................................... 125
5.1 結論 ......................................................................................................................... 125
5.1.1 奈米氧化鋅 ...................................................................................................... 125
5.1.2 奈米銀 .............................................................................................................. 126
5.1.3 奈米鐵 .............................................................................................................. 127
5.1.4 綜合比較 .......................................................................................................... 128
5.2 建議 ......................................................................................................................... 128
參考文獻 .......................................................................................................................... 129
附錄 .................................................................................................................................. 141

圖目錄
圖1.1 研究流程與主要工作內容 .................................................................................... 2
圖1.2 研究架構圖 ............................................................................................................ 4
圖2.1 生物除磷機制(PHB, poly-β-hydroxybutyrate，聚-β-羥丁酸) (游氏, 2001) ........ 6
圖2.2 Comeau/Wentzel之厭氧代謝模式(Fillipe and Daigger, 1998) ............................. 8
圖2.3 Adapted Mino之厭氧代謝模式(Fillipe and Daigger, 1998) ................................. 8
圖2.4 環境中奈米微粒進入生物體對環境生態之影響(Navarro et al., 2008) ............ 18
圖2.5 奈米微粒進入細胞之途徑 (Singh et al., 2009) .................................................. 19
圖2.6 奈米材料進入環境水體流佈與環境宿命 (施氏，2011) .................................. 20
圖2.7 銀殺蟲劑中的含銀量以及銀離子釋出量關係 (Nowack et al., 2011) .............. 23
圖2.8 ROS產生及其反應機制 (Bukowska, 2004) ...................................................... 27
圖3.1 B-SBR模廠與監測控制設備連線配置圖 ......................................................... 29
圖3.2 批次實驗反應槽示意圖 ...................................................................................... 30
圖3.3 B-SBR模廠程序流程示意圖 ............................................................................. 34
圖3.4 批次實驗設計流程 .............................................................................................. 38
圖3.5 ROS分析流程 ..................................................................................................... 40
圖3.6 LDH分析流程 ..................................................................................................... 41
圖4.1 SBR系統SRT10天操作條件下生物營養鹽去除特性關係圖 ........................ 43
圖4.2 DAPI染色觀察聚磷酸鹽累積情形 ................................................................... 44
圖4.3 SBR系統單循環pH、DO、ORP監測圖 ......................................................... 44
圖4.4 奈米氧化鋅ROS生成變化圖(*p<0.05) ............................................................. 47
圖4.5 奈米銀ROS生成變化圖(*p<0.05) ..................................................................... 49
圖4.6 奈米四氧化三鐵ROS生成變化圖(*p<0.05) ..................................................... 51
圖4.7 三種奈米金屬之ROS生成比較 ........................................................................ 53
圖4.8 三種奈米金屬之釋出LDH變化圖 .................................................................... 56
圖4.9 奈米氧化鋅濃度與正磷酸鹽趨勢之變化 .......................................................... 59
圖4.10 奈米氧化鋅濃度與DOC趨勢變化 ................................................................. 61
圖4.11 奈米氧化鋅濃度對正磷酸鹽與DOC去除率之比較...................................... 62
圖4.12 不同奈米氧化鋅濃度與SSUR之關係(*p<0.05) ............................................. 64
圖4.13 不同奈米氧化鋅濃度與比釋/攝磷率之比較(*p<0.05) .................................... 67
圖4.14 奈米氧化鋅濃度與總釋/攝磷量及比釋/攝磷抑制率之關係 .......................... 69
圖4.15 不同奈米氧化鋅濃度與PHA合成/分解率之關係 (*p<0.05) ........................ 72
圖4.16 不同奈米氧化鋅濃度與肝醣分解/合成率之關係 (*p<0.05) .......................... 75
圖4.17 奈米氧化鋅釋出鋅離子情形 ............................................................................ 77
圖4.18 奈米銀濃度與正磷酸鹽趨勢之變化 ................................................................ 80
圖4.19 奈米銀濃度與DOC趨勢變化 ......................................................................... 82
圖4.20 奈米銀濃度對正磷酸鹽與DOC去除率之比較 ............................................. 83
圖4.21 不同奈米銀濃度與SSUR之關係(*p<0.05) ..................................................... 85
圖4.22 不同奈米銀濃度與比釋/攝磷率之比較(*p<0.05) ............................................ 87
圖4.23 奈米銀濃度與總釋/攝磷量及比釋/攝磷抑制率之關係 .................................. 90
圖4.24 不同奈米銀濃度與PHA合成/分解率之關係(*p<0.05) .................................. 93
圖4.25 不同奈米銀濃度與肝醣分解/合成率之關係(*p<0.05) .................................... 96
圖4.26 奈米銀在不同pH下的特性變化 (Elzey and Grassian, 2010) ........................ 97
圖4.27 奈米銀釋出銀離子情形.................................................................................... 99
圖4.28 奈米四氧化三鐵濃度與正磷酸鹽趨勢之變化.............................................. 101
圖4.29 奈米四氧化三鐵濃度與DOC趨勢變化....................................................... 103
圖4.30 奈米四氧化三鐵濃度對正磷酸鹽與DOC去除率之比較........................... 104
圖4.31 不同奈米四氧化三鐵濃度與SSUR之關係(*p<0.05)................................... 106
圖4.32 不同奈米四氧化三鐵濃度與比釋/攝磷率之比較(*p<0.05).......................... 109
圖4.33 奈米四氧化三鐵濃度與總釋/攝磷量及比釋/攝磷抑制率之關係.................111
圖4.34 不同奈米四氧化三鐵濃度與PHA合成/分解率之關係(*p<0.05).................114
圖4.35 不同奈米四氧化三鐵濃度與肝醣分解/合成率之關係(*p<0.05)...................116
圖4.36 奈米四氧化三鐵釋出鐵離子情形...................................................................118
表目錄
表2.1 生物除磷機制(Jenkins, 1992) ................................................................................ 6
表2.2 Comeau/Wentzel Mode及Mino Model之比較................................................... 9
表2.3 溫度對生物除磷影響之相關文獻........................................................................ 10
表2.4 pH 值對生物除磷影響之相關研究....................................................................11
表2.5 碳源和釋磷量之關係.......................................................................................... 13
表2.6 碳源與磷含量比值(C:P) ...................................................................................... 14
表2.7 重金屬允許濃度(歐陽，2003；U.S.EPA, Nitrogen Control) .......................... 17
表3.1 奈米金屬物化特性.............................................................................................. 31
表3.2 PAOs人工合成基質主要成份............................................................................ 32
表3.3 PAOs人工合成基質組成之進流水質理論濃度................................................ 33
表3.4 B-SBR模廠操作參數......................................................................................... 33
表3.5 水質檢驗分析項目.............................................................................................. 35
表3.6 實驗儀器設備型號.............................................................................................. 36
表4.1 SBR系統SRT 10天操作達穩定期間之進放流水水質濃度及去除率(n=40) . 43
表4.2 奈米氧化鋅批次實驗期間SBR母系統進放流正磷酸鹽變化........................ 57
表4.3 奈米氧化銀批次實驗期間SBR母系統進放流正磷酸鹽變化........................ 78
表4.4 奈米四氧化三鐵批次實驗期間SBR母系統進放流正磷酸鹽變化.............. 100
表4.5 比釋/攝磷率毒性比較....................................................................................... 120
表4.6 PHAs合成/分解率毒性比較............................................................................ 122
表4.7 肝醣合成/分解率毒性比較............................................................................... 124

參考文獻
Adams, L.K., Lyon, D.Y., Alvarez, P.J., (2006). Comparative eco-toxicity of nanoscale TiO2 , SiO2 , and ZnO water suspensions, Wat. Res., 40. 3527-3532.
Ahamed, M., Karns, M., Goodson, M., Rowe, J., Hussain, S.M., Schlager, J.J., Hong, Y., (2008). DNA damage response to different surface chemistry of silver nanoparticles in mammalian cells. Toxicology and Applied Pharmacology, 233. 404-410.
Aruoja, V., Dubourguier, H.C., Kasemets, K., Kahru, A., (2009). Toxicity nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata, Science of the Total Environment, 407. 1461-1468.
Baetens, D., Vanrolleghem P.A., van Loosdrecht, M.C.M., and Hosten L.H., (1999). Temperature effects in bio-P removal. Wat. Sci. Tech., 39 (1). 215-225.
Battistoni, P., Fava, G., and Ruello, M.L., (1993). Heavy metal shock load in activated sludge uptake and toxic effects. Wat. Res., 27. 821-827.
Benn, T.M. and Westerhoff, P., (2008). Nanoparticle silver released into water from commercially available sock fabrics. Environ Sci Technol., 42. 4133-4139.
Blaser, S.A., Scheringer, M., MacLeod, M., Hungerbühler, K., (2008). Estimation of cumulative aquatic exposure and risk due to silver: contribution of nano-functionalized plastics and textiles. Sci Total Environ., 390. 396-409.
Blinova, I., Ivask, A., Mortimer, M., Kahru, A., (2010). Ecotoxicity of nanoparticles of CuO and ZnO in natural water. Environ. Pollut., 158. 41-47.
Bradjanovic D., Hooijmans C.M., van Loosdrecht M.C.M., Alaerts G.J., and Heijnen J.J., (1996). The dynamic effects of potassium limitation on biological phosphorus removal. Wat. Res., 30. 2323-2328.
Bradjanovic, D., Slamet A., van Loosdrecht, M.C.M., Hooijmans, C.M., Alaerts, G.J., and Heijnen, J.J., (1998). Impact of excessive aeration on biological phosphorus removal from wastewater. Wat. Res., 32 (1). 200-208.
Brayner, R., Ferrari-Iliou, R., Brivois, N., Djediat, S., Benedetti, M. F., Fi_evet, F., (2006). Toxicological impact studies based on Escherichia coli bacteria in ultrafine ZnO nanoparticles colloidal medium. Nano Letters, 6. 866-870.
Broughton A., Pratt S., Shilton A., (2008). Enhanced biological phosphorus removal for high-strength wastewater with a low rbCOD: P ratio. Bioresour. Technol., 99.
1236-1241.
Bond, P.L., Keller J., Blackall, L.L., (1999a). Bio-P and non-bio-P bacteria identification by a novel microbial approach. Wat.Sci.Tech., 39(6).13-20.
Bond, P.L., R. Erhart, M. Wagner, J. Keller, L.L. Blackall., (1999b). Identification of some of the major groups of bacteria in efficient and nonefficient biological phosphorus removal activated ludgesystems. Appl. Environ. Microbiol., 65(9). 4077-4084.
Bukowska, B., (2004). 2,4,5-T and 2,4,5-TCP induce oxidative damage in human erythrocytes: the role of glutathione. Cell Biology International, 28(7). 557-63.
Cabrero A., Fernandez S., Mirada F.,Garcia J., (1998). Effects of copper and Zinc on the activated sludge bacteria growth kinetic. Wat. Res., 32 (5). 1355-1362.
Carucci A., Kuhni.M., Brun R., Carucci G., Koch G., Majone M., and Siegrist H., (1999). Microbial Competition for the organic substrates and its impact on EBPR system under conditions of changing carbon feed. Wat. Sci. Tech. 39 (1), 75-85.
Cheng M.H., Patterson J.W., Minear R.A., (1975). Heavy metals uptake by activated sludge. J. Water Pollut. Control Fed., 47 (2). 362-376.
Chen Y., Chen H., Zheng X., Mu H., (2012). The impacts of silver nanoparticles and silver ions on wastewater biological phosphorous removal and the mechanisms. Journal of Hazardous Materials, 239-240. 88- 94.
Chen, Y.C., Hsiao, J.K., Liu, H.M., Lai, I.Y., Yao, M., Hsu, S.C., Ko, B.S., Che, Y.C., Yang, C.S., Huang, D.M., (2010). The inhibitory effect of superparamagnetic iron oxide nanoparticle (Ferucarbotran) on osteogenic differentiation and its signaling mechanism in human mesenchymal stem cells. Toxicol. Appl. Pharmacol., 245. 272-279.
Christiane S.N., Bauer H.D., Roske I., (2001). Stability of enhanced biological phosphorus removal and composition of polyphosphate granules. Wat. Res., 35 (13). 3190-3196.
Chuang S.H., Chang W.C., Huang Y.H., Tseng C.C., Tai C.C., (2011). Effects of different carbon supplements on phosphorus removal in low C/P ratio industrial waste water. Bio. Tech., 102. 5461-5465.
Chun, C.L., Park, J.W., (2001). Oil spill remediation using magnetic separation. Journal of Environmental Engineering, 127(5). 443-449.
Choi, O., Deng, KK., Kim, N.J., Ross, L., Surampalli, R.Y., Hu, Z.Q., (2008). The inhibitory effects of silver nanoparticles, silver ions, and silver chloride colloids on microbial growth, Water Res., 42. 3066-3074.
Choi, O., Clevenger, T.E., Deng, B.L., Surampalli, R.Y., Ross, L., Hu, Z.Q., (2009). Role
of sulfide and ligand strength in controlling nanosilver toxicity. Water Res., 43. 1879-1886.
Comeau Y., Rabinowitz B., Hall K.J., and Oldham W.K., (1987). Phosphate release and uptake in enhanced biological phosphorus removal from wastewater. J.WPCF 59, 707-715.
Decker, T., Lohmann-Matthes M. L., (1988). A quick and simple method for the quantitation of lactate dehydrogenase release in measurements of cellular cytotoxicity and tumor necrosis factor (TNF) activity. J. Immunol. Methods,. 115. 61-69.
Dilek F.B. and Gokcay C.F., (1996). Microbiology of activatfed sludge treating wastewater containing Ni(II) and Cr(VI). Wat. Sci. Tech., 34 (5-6). 183-191.
Dufour, E.K., Kumaravel, T., Nohynek, G.J., Kirkland, D. Toutain, H., (2006). Clastogenicity, photo-clastogenicity or pseudo-photo-clastogenicity: genotoxic effects of zinc oxide in the dark, in pre-irradiated or stimultaneously irradiated Chinese hamster ovary cells. Mutat. Res., 607. 215-224.
Elzey, S. and Grassian, V.H., (2010). Agglomeration, isolation and dissolution of commercially manufactured silver nanoparticles in aqueous environments. J. Nanopart. Res., 12. 1945-1958.
Erdal U.G., Erdal Z.K., Randall C.W., (2003). The competition between PAOs and GAOs in EBPR system at different temperatures and the effects on system performance. Wat. Sci. Tech., 47 (11). 1-8.
Fabrega, J., Fawcett, S. R., Renshaw, J. C., Lead, J. R., (2009a). Silver nanoparticle impact on bacterial growth: effect of pH, concentration, and organic matter, Environ. Sci. Technol., 43. 7285-7290.
Feng, D.C., Aldrich, H. Tan, (2000). Removal of heavy metal ions by carrier magnetic separation of adsorptive particulates. Hydrometallurgy,56 (3). 359-368.
Filipe, C.D.M., Daigger, G.T., Grady, C.P.L., (2001). Effects of pH on the rates of aerobic metabolism of phosphate-accumulating and glycogen-accumulating organisms. Water Environment Research, 73. 213-222.
Fillipe and Daigger, (1998). Development of a revised metabolic model for the growth of phosphorus-accumlating organisms. Wat. Env. Res., 70. 67-79.
Fikret K., Ahmet U., Hu S.S., Bas K., (2005). Phosphate uptake and release rates with different carbon sources in biological nutrient removal using a SBR. Journal of Environmental Management, 76. 71-75.
Foldbjerg, R. Olesen P., Hougaard M., Dang D.A., Hoffmann H.J., Autrup H., (2009). PVP-coated silver nanoparticles and silver ions induce reactive oxygen species, apoptosis and necrosis in THP-1 monocytes, Toxicol. Lett., 190. 156-162.
Franklin N.M., Rogers N.J., Apte, S.C., Batley, G.E., Gadd, G.E., Casey, P.S., (2007). Comparative toxicity of nanoparticulate ZnO, bulk ZnO, and ZnCl2 to a freshwater microalga (Pseudokirchneriella subcapitata): The importance of particle solubility. Environmental Science & Technology, 41(24). 8484-8490.
Georgios, A.S. and Sotiris, E., (2010). Antibacterial activity of nanosilver ions and particles, Environ. Sci. Technol., 44. 5649-5654.
Gottschalk, F., Sonderer, T., Scholz, R. W., Nowack, B., (2009). Modeled environmental concentrations of engineered nanomaterials (TiO2, ZnO, Ag, CNT, fullerenes) for different regions, Environ Sci Technol., 43. 9216-9622.
Griffitt, R.J., Luo, J., Gao, J., Bonzongo, J. C., Barber, D.S., (2008). Effects of particle composition and species on toxicity of metallic nanomaterials in aquatic organisms. Environ. Toxicol. Chem., 27. 1972-1978.
Han-Jurgen, (1990). Elimination of nitrogen and phosphorus by microorganism. 450-454.
Haslam, G., Wyatt, D., Kitos, P.A., (2000). Estimating the number of viable animal cells in multi-well cultures based on their lactate dehydrogenase activities. Cytotechnology, 32. 63-75.
Heinlaan, M., Ivask, A., Blinova, I., Dubourguier, H. C., Kahru, (2008). Toxicity of nanosized and bulk ZnO, CuO and TiO2 to bacteria Vibrio fischeri and crustaceans Daphnia magna and Thamnocephalus platyurus, Chemosphere, 71. 1308-1316.
Helmer C. and Kunst S., (1998). Low temperature effects on phosphorus release and uptake by microorganisms in EBPR plants. Wat. Sci. Tech., 37 (4-5). 531-539.
Henglein, A., (1993). Physicochemical properties of small metal particles in solution: “microelectrode” reactions, chemisorption, composite metal particles, and the atom-to- metal transition. J. Phys. Chem., 97. 5457-5471.
Henglein, A. (1998). Colloidal silver nanoparticles: photochemical preparation and interaction with O2 , CCl4 , and some metal ions, Chem. Mater., 10. 444-450.
Hirano, S. (2009). A current overview of health effect research on nanoparticles. Environ Health Prev. Med., 14. 223-225.
Hsin, Y.H., Chen, C.F., Huang, S., Shih, T.S., Lai, P.S., Chueh, P.J., (2008). The apoptotic effect of nanosilver is mediated by a ROS- and JNK-dependent mechanism involving
the mitochondrial pathway in NIH3T3 cells. Toxicol Lett., 179. 130-139.
Hussain, S.M., Hess, K.L., Gearhart, J.M., Geiss, K.T., Schlager, J.J., (2005). In vitro toxicity of nanoparticles in BRL 3A rat liver cells. Toxicol. In Vitro, 19. 975-983.
Hwang, E.T., Lee, J.H., Chae, Y.J., Kim, Y.S., Kim, B.C., Sang, B.I., Gu, M.B., (2008). Analysis of the toxic mode of action of silver nanoparticles using stress-specific bioluminescent bacteria, Small, 4. 746-750.
Jeng, H. A., Swanson, J., (2006). Toxicity of metal oxide nanoparticles in mammalian cells. J. Environ. Sci. Health A Tox. Hazard Subst Environ. Eng., 41. 2699-2711.
Jenkins, D., and Tandoi, V., (1991). The applied microbiology of enhanced biological phosphate removal-accomplishment and needs. Wat.Res., 25. 1471-1478
Jiang, W., Mashayekhi, H., Xing, B.S., (2009). Bacterial toxicity comparison between nano-and micro-scaled oxide particles. Environ. Pollut., 157. 1619-1625.
Juliastuti SR, Baeyens J, Creemers C., (2003). Inhibition of nitrification by heavy metals and organic compounds: the ISO 9509 test. Environ Eng. Sci., 20. 79-90.
Jun H.B. and Shin H.S., (1997). Substrates transformation in a biological excess phosphorus removal system. Wat. Res., 31(4). 893-899.
Kaegi R., Voegelin A., Sinnet B., Zuleeg S., Hagendorfer H., Burkhardt M., Siegrist H., (2011). Behavior of metallic silver nanoparticles in a pilot wastewater treat-ment plant, Environ. Sci. Technol., 45. 3902-3908.
Kang, S., Mauter, M. S., Elimelech, M., (2009). Microbial cytotoxicity of carbon-based nanomaterials: implications for river water and wastewater effluent. Environ Sci Technol., 43. 2648-2653.
Kargi F., Uygur A., and Baskaya H.S., (2005). Phosphate uptake and release rates with different carbon sources in biological nutrient removal using a SBR. Journal of Environmental Management., 76, 71-75.
Kawata, K., Osawa, M., Okabe, S., (2009). In vitro toxicity of silver nanoparticles at noncytotoxic doses to HepG2 human hepatoma cells, Environ. Sci. Technol., 43. 6046-6051.
Kim, B., Park, C-S., Murayama, M., Hochella, M.F., (2010). Discovery and haracterization of silver sulfide nanoparticles in final sewage sludge products, Environ. Sci. Technol., 44. 7509-7514.
Korzeniewski, C. and Callewaert, D., (1983). An enzyme-release assay for natural cytotoxicity. J. Immunol. Methods., 64. 313-320.
Koch F.A. and Oldham W.K., (1985). Oxidation-reduction potential-A tool for monitoring control and optimization of biological nutrient removal system. Wat. Sci. Tech., 17. 259-281.
Laban, G., Nies, L. F., Turco, R. F., Bickham, J. W., Sepulveda, M.S., (2010). The effects of silver nanoparticles on fathead minnow (Pimephales promelas) embryos. Ecotoxicology, 19. 185-195.
Latour, C. D., (1973). Magnetic separation in water pollution control. IEEE Transactions on Magnetics, 9(3). 314-316.
Latour, C. D., (1975). Magnetic separation in water pollution control - II”, IEEE Transactions on Magnetics, 11(5). 1570-1572.
Law, N.; Ansari, S.; Livens, F. R.; Renshaw, J. C.; Lloyd, J. R., (2008). Formation of nanoscale elemental silver particles via enzymatic reduction by Geobacter sulfurreducens. Appl Environ Microbiol, 74, (22), 7090-3.
Lim P.E., Ong S.A., and Seng C.E., (2002). Simultaneous adsorption and biodegradation processes in sequencing batch reactor (SBR) for treating copper and cadmium-containing wastewater. Wat. Res., 36. 667-675.
Lin, D.H., and Xing, B.S., (2007). Phytotoxicity of nanoparticles: Inhibition of seed germination and root growth, Environ. Pollut., 150. 243-250.
Lin, D.H. and Xing, B.S., (2008). Root uptake and phytotoxicity of ZnO nanoparticles, Environ. Sci. Technol., 42. 5580-5585.
Liu W. T., Mino T. and Nakamura K., (1996). Biological phosphorus removal processes - effect of pH on anaerobic substrate metabolism. Wat. Res., 34(1-2), 25-32.
Liu W.T., Mino T., Nakamura K., and Matsuo T., (1997). Internal Energy-Based Competition Between Polyphosphate- and Glycogen-Accumulation Bacteria in Biological phosphorus Removal Reactors—Effect of P/C Feeding Ratio. Wat. Res., 31 (6). 1430-1438.
Liu, Y., He, L., Mustapha, A., Li, H., Hu, Z. Q., Lin, M., (2009). Antibacterial activities of zinc oxide nanoparticles against Escherichia coli O157: H7, J. Appl. Microbiol., 107. 1193-1201.
Lok, C., Ho, C., Chen, R., He, Q., Yu, W., Sun, H., (2006). Proteomic analysis of the mode of antibacterial action of silver nanoparticles, J. Proteome. Res., 5. 916-924.
Lok, C. N.; Ho, C. M.; Chen, R.; He, Q. Y.; Yu, W. Y.; Sun, H.; Tam, P. K.; Chiu, J. F.;
Che, C. M., (2007). Silver nanoparticles: partial oxidation and antibacterial activities. J Biol Inorg Chem, 12 (4). 527-34.
Louzeiro N.R., Mavinic D.S., Oldham W.K., Meisen A., and Gardner I.S., (2002). Methanol-induced biological nutrient removal kinetics in a full-scale sequencing batch reactor. Wat. Res., 36 (11), 2721-2732.
Luther, G.W. and Rickard, D.T., (2005). Metal sulfide cluster complexes and their biogeochemical importance in the environment. J. Nanopart. Res., 7. 389-407.
Madoni, P., Davoli, D., Guglielmi, L., (1999). Response of Sour and AUR to metal contamination in activated sludge. Wat. Res., 33. 2459-2464.
Magder, S., (2006). Reactive oxygen species: toxic molecules or spark of life? Crit Care 10, 208.
Mahmoud, F.A. and G. Kiriakidis, (2009). Nanocrystalline ZnO thin film for gas sensor application. Journal of Ovonic Research., 5(1). 15-20.
Mates. J. M., (2000). Effects of antioxidant enzymes in the molecular control of reactive oxygen species toxicology. Toxicology, 153. 83-104.
McGrath J. W., Cleary S., Mullan A. and Quinn J.P., (2001). Acid-stimulated phosphate uptake by activated sludge microorganisms under aerobic laboratory conditions. Wat. Res., 35 (18). 4317-4322.
Meinhold J., Arnold E., and Isaacs S., (1999). Effect of nitrite on anoxic phosphate uptake in biological phosphorus removal activated sludge. Wat. Res., 33 (8), 1871-1883.
Mejare, M. and Bulow L., (2001). Metal-binding proteins and peptides in bioremediation and phytoremediation of heavy metals. Trends Biotechnol. 19, 67-73.
Miao, A.J., Schwehr, K.A., Xu, C., Zhang, S.J., Luo, Z.P., Quigg, A., Santschi, P.H., (2009). The algal toxicity of silver engineered nanoparticles and detoxification by exopolymeric substances. Environ. Pollut., 157. 3034-3041.
Mino T., van Loosdrecht M.C.M., Heijnen J.J., (1998). Microbiology and biochemistry of the enhanced biological phosphate removal process. Wat. Res., 32 (11). 3193-3207.
Moulton, E .Q. and E.S. Shumate, (1963). The Physical and Biological Effects of Copper-on Aerobic Biological. Waste Treatment Processes, 18th Purdue Ind. Waste Conf., 602.
Navarro, E., Baun, A., Behra, R., Hartmann, N.B., Filser, J., Miao, A.J., (2008a). Environmental behavior and Tecotoxicity of engineered nanoparticles to algae, plants, and fungi, Ecotoxicology, 17. 372-386.
Navarro, E., Piccapietra, F., Wagner, B., Marconi, F., Kaegi, R., Odzak, N. Sigg, L., Behra R., (2008b). Toxicity of silver nanoparticles to chlamydomonas reinhardtii, Environ. Sci. Technol., 42. 8959-8964.
Navarro, E. and Baun, A., (2008). Environmental behavior and ecotoxicity of engineered nanoparticles to algae, plants, and fungi, Ecotoxicology, 17. 372-386.
Nowack, B.; Bucheli, T. D., (2007). Occurrence, behavior and effects of nanoparticles in the environment. Environ Pollut., 150 (1). 5-22.
Nowack, B., Krug, H.F., Height, M., (2011). 120 Years of Nanosilver History: Implications for Policy Makers, Environ. Sci. Technol., 45. 1177-1183
Oa S. W. and Choi E., (2012). Phosphorus removal from nightsoil wuth sequencing batch reactor. Wat. Sci. Tech., 36(12). 55-60.
Oehmen, A., Vives, M.T., Lu, H., Yuan, Z., Keller, J., (2005). The effect of pH on the competition between polyphosphate accumulating organisms and glycogen accumulating organisms. Water Research, 39 (15). 3727-3737
Panswad and Anan, (1999). Specific oxygen, ammonia, and nitrate uptake rates of a biological nutrient removal process treating elevated salinity wastewater. Bioresource Technology 70, 237-243.
Panswad T., Doungchai A., and Anotai J., (2003). Temperature effect on microbial community of enhanced biological phosphorus removal system. Wat. Res. 37, 409-415.
Pattarkine V.M. and Randall C.W., (1999). The requirement of metal cations for enhanced biological phosphorus removal by activated sludge. Wat. Sci. Tech., 40 (2). 159-165.
Poynton, H. C., Lazorchak, J. M., Impellitteri, C. A., Smith, M. E., Rogers, K., Patra, M., Hammer, K.A., Allen, H.J., Vulpe, C.D., (2011). Differential gene expression in Daphnia magna suggests distinct modes of action and bioavailability for ZnO nanoparticles and Zn ions, Environ. Sci. Technol., 45. 762-768.
Pulskamp, K., Diabate, S., Krug, H.F., (2007). Carbon nanotubes show no sign of acute toxicity but induce intracellular reactive oxygen species in dependence on contaminants. Toxicol. Lett., 168, 58-74.
Randall A.A. and Liu Y.-H., (2002). Polyhydroxyalkanoates form potenially a key aspect of aerobic phosphorus uptake in enhanced biological phosphorus removal. Wat. Res., 36. 3473-3478.
Randall A.A., Chen Y., McCue T., (2004). The efficiency of enhanced biological phosphorus removal from real wastewater affected by different ratios of acetic to
propionic acid. Wat. Res., 38. 27-36
Reddy, K. M., Feris, K., Bell, J., Wingett, D. G., Hanley, C. Punnoose, A. (2007). Selective toxicity of zinc oxide nanoparticles to prokaryotic and eukaryotic systems, Appl. Phys. Lett., 90. 2139021-2139023.
Rensink J.H., Ven J.V.D., Pamelen G.V., Fedder F., Majoor E., (1997). The Modified Renphosystem: A High Biological Nutrient Removal System. Wat. Sci. Tech., 35 (10). 137-146
Sahoo, S. and A.K. Bhowmick, (2007). Influence of ZnO nanoparticles on the cure characteristics and mechanical properties of carboxylated nitrile rubber. Journal of Applied Polymer Science, 106 (5). 3077-3083.
Sakai, Y., Takahiro M., Fujio T., (1997). Simultaneous removal of organic and nitrogen compounds in intermittently aerated activated sludge process using magnetic separation. Water Research, 31 (8). 2113-2116.
Sayes, C.M., Reed, K.L., Warheit, D.B., (2007). Assessing toxicity of fine and nanoparticles: comparing in vitro measurements to in vivo pulmonary toxicity profiles. Toxicol Sci., 97. 163-180.
Schon G., Geywitz S., and Mertens F., (1993). Influence of dissolved oxygen and oxidation-reduction potential on phosphate release and uptake by activated sludge from sewage plants with enhanced biological phosphorus removal. Wat. Res., 27 (3). 349-354.
Shehab O., Deininger R., Porta F., and Wojewski T., (1996). Optimizing Phosphorus Removal at The Ann Arbor Wastewater Treatment Plant. Wat. Sci. Tech., 34 (1-2). 493-499.
Singh, N., Manshian, B., Jenkins, G.J.S., Griffiths, S.M., Williams, P.M., Maffeis, T.G.G., Wright, C.J., Doak, S.H. (2009). Nanogenotoxicology: the DNA damaging poptential of engineered nanomaterials. Biomaterials 30, 3891-3914.
Smolders G.L.F., van der Meij J., van Loosdrecht M.C.M., Heijnen J.J., (1994). Model of the anaerobic metabolism of the biological phosphorus removal process： stoichiometry and H influence. Biotechnol. Bioeng., 43. 461-470.
Sudiana I. M., Mino T., Satoh H., Nakamura K., and Matsuo T., (1999). Metabolism of enhanced biological phosphorus removal and non-enhanced biological phosphorus removal sludge with acetate and glucose as carbon source. Wat. Sci. Tech. 39 (6), 29-35.
Suska, F., Gretzer, C., Esposito, M., Tengvall, P., Thomsen, P., (2005). Monocyte viability
on titanium and copper coated titanium. Biomaterials, 26. 5942-5950.
Tsai Y.P., You S.J., Pai T.Y., and Chen K.W., (2005). Effect of cadium on composition and diversity of bacterial communities in activated sludge. Internation Biodeterioration & Biodegradation, 55, 285-291.
Tsou, T.C., Yeh, S.C., Tsai, F.Y., Lin, H.J., Cheng, T J., Chao, H R., Tai, L.A., (2010). Zinc oxide particles induce inflammatory responses in vascular endothelial cells via NF-kB signaling. J. Hazard. Mater., 183. 182-188.
Tiede, K., Boxall, A.B.A., Wang, X.M., Gore, D., Tiede D., Baxter, M., (2010). Application of hydrodynamic chromatography–ICP-MS to investigate the fate of silver nanoparticles in activated sludge. J. Anal. At. Spectrom., 25. 1149-1154.
Valko M., Leibfritz D., Moncol J., Cronin M.T.D., Mazur M., Telser J., (2007). Free radicals and antioxidants in normal physiological functions and human disease. Int. J. Biochem. Cell Biol., 39. 44-84.
Wagner, A. J., Bleckmann, C.A., Murdock, R.C., Schrand, A.M., Schlager, J.J., Hussain, S. M., (2007). Cellular interaction of different forms of aluminum nanoparticles in rat alveolar macrophages. J. Phys. Chem. B., 111. 7353-7359.
Wang, B., Feng, W. Y., Wang, M., Wang, T., Gu, Y., Zhu, M., Ouyang, H., Shi, J., Zhang, F., Zhao, Y., Chai, Z., Wamg, H., Wang, J., (2008). Acute toxicological impact of nano and submicro-scaled zinc oxide powder on healthy adult mice. J. Nanopart. Res., 10. 263-276.
Wang, G.S., Y.A. Deng, L. Guo, (2010). Single-Crystalline ZnO Nanowire Bundles:Synthesis, Mechanism and Their Application in Dielectric Composites. Chemistry-a European Journal, 16 (33). 10220-10225.
Whang L.M. and Park J.K., (2002). Competition between polyphosphate- and glycogen- accumulating organisms in biological phosphorus removal systems-effect of temperature. Wat. Sci. Tech., 46 (1-2). 191-194.
Whang L.M. and Park J.K., (2006). Competition between polyphosphate- and glycogen-accumulating organisms in enhanced biological phosphorus removal systems： effect of temperature and sludge age. Water Environ Res, 78 (1). 4-11.
Wijnhoven, S.W.P., Peijnenburg, W.J.G.M., Herberts, C.A., Hagens, W.I., Oomen, A.G., Heugens, E.H.W., Roszek, B., Bisschops, J., Gosens, I., Van De Meent, D., Dekkers, S., De Jong, W.H., van Zijverden, M., Sips, A.J.A.M., Geertsma, R.E., (2009).
Nano-silver-A review of available data and knowledge gaps in human and environmental risk assessment. Nanotoxicology, 3. 109-138.
Wong, S.W.Y., Leung, P.T.Y., Djurisic, A.B., Leung, K.M.Y., (2010). Toxicities of nano zinc oxide to five marine organisms: influences aggregate size and ion solubility, Anal. Bioanal. Chem., 396. 609-618.
Xia, T., Kovochich, M., Liong, M., Madler, L., Gilbert, B., Shi, H., Yeh, J.I., Zink, J.I., NEl, A.E. (2008). Comparison of the mechanism of toxicity of zinc oxide and cerium oxide nanoparticles based on dissolution and oxidative stress properties. ACS Nano, 2. 2121-2134.
Wu, B., Wang, Y., Lee, Y.H., Horst, A., Wang, Z.P., Chen, D.R., SurEHSkumar, R., Tang, Y.J.J., (2010). Comparative eco-toxicities of nano-ZnO particles under aquatic and aerosol exposure modes, Environ. Sci. Technol., 44. 1484-1489.
Yang, C. Y., Hsiao, J. K., Tai, M. F., Chen, S. T., Cheng, H. Y., Wang, J. L., Liu, H. M., (2010). Direct labeling of hMSC with SPIO: the long-term influence on toxicity, chrondrogenic differentiation capacity, and intracellular distribution. Mol. Imag. Biol. Doi:10.1007/s11307-010-0360-7.
Zheng X., Wu R., Chen Y., (2011). Effects of ZnO Nanoparticles on Wastewater Biological Nitrogen and Phosphorus Removal. Environ. Sci. Technol., 45. 2826-2832
Zhang, L. Jiang Y., Ding Y., Povey M., York D., (2007). Investigation into the antibacterial behaviour of suspensions of ZnO nanoparticles (ZnO nanofluids). Journal of Nanoparticle Research., 9(3). 479-489.
Zhang, L., Jiang, Y., Ding, Y., Daskalakis, N., Jeuken, L., Povey, M., O’Neill, A.J., York, D.W., (2010). Mechanistic investigation into antibacterial behaviour of suspensions of ZnO nanoparticles against E. coli. Journal of Nanoparticle Research, 12(5). 1625-1636.
Zhou, J., N.S. Xu, Z.L. (2006). Wang, Dissolving behavior and stability of ZnO wires in biofluids: A study on biodegradability and biocompatibility of ZnO nanostructures. Advanced Materials., 18 (18). 2432.
Zhu, X., Wang, J., Zhang, X., Chang, Y. Chen, Y., (2009).The impact of ZnO nanoparticle aggregates on the embryonic development of zebrafish (Danio rerio). Nanotechnology, 20. 195-103.
Zhu, Y.F., Zhou, G.H., Ding, H.Y., Liu, A.H., Lin, Y.B., Li, N.L., (2010). Synthesis of highly-ordered hierarchical ZnO nanostructures and their application in dye-sensitized solar cells. Crystal Research and Technology. 45(10). 1075-1078.
林威龍(2005)，何謂活性含氧物種，勞工安全衛生簡訊，雙月刊，第71期，ISSN：1561-9729。
陳珮紋 (2004)，利用Fe3O4磁性顆粒處理化學機械研磨廢水，碩士論文，中央大學，環境工程研究所，中壢。
徐玉杜，簡弘民 (2006)，奈米氧化鋅粉體分級與收集設備開發.化工技術，14 (12)，155-166。
王綉雲 (2008)，在人類上皮癌細胞A431細胞中PHGPx對EGF所誘導c-Jun表現的影響，碩士論文，中華醫事科技大學，生物科技研究所，台南。
陳群方 (2007)，奈米銀在老鼠纖維母細胞造成的細胞凋亡機制，碩士論文，中興大學生物醫學研究所。
游勝傑 (2001)，併同生物膜與活性污泥程序之硝化及脫硝攝磷特性研究，博士論文，國立中央大學環境工程研究所，中壢。
袁又罡、張銘仁(2003)，生物膜處理重金屬銅之研究，工業污染防治論文集，第88期，58-78。
張家修 (1994)，重金屬污染的生物處理技術，化工技術第四十一卷第三期，52-59。
歐陽嶠暉，下水道工程學，三版再修訂，長松文化公司 (2003) 。
胡皪元 (2008)，不同溫度下重金屬突增負荷對生物除磷機制之影響，碩士論文，國立暨南國際大學土木工程研究所。
蘇志翔(2010)，穩定化奈米零價鐵及其氧化產物對青鱂魚的毒性效應，碩士論文，國立台灣大學生物資源暨農學院農業化學系。
蔡春進、陳佩貞、連興隆(2011)， 100年度「環境奈米科技知識管理及整合計畫」，行政院環境保護署委辦計畫，EPA-100-U1U1-02-105。
闕斌如、蘇盈甄(2010)，「配合即時監測環境樣品奈米微粒細胞毒性篩選技術」委託研究案，行政院環境保護署，EPA-99-U1U1-02-104。
施養信、覃偉民、賴彥君，(2012)，水環境介質中奈米微粒量 粒量 測、轉換及宿命研究，環境奈米科技論壇論文集，13-30。
闕斌如、莊秀美、曾咨銘、李怡慧、梁瑞岳(2012)，奈米微粒對細胞毒性及生物標記之篩選技術建立，環境奈米科技論壇論文集，1-13。