自然水體中銀之濃度相當低，測定前需將樣品預濃縮處理，過去常用於水中銀測量之預濃縮方法有溶劑萃取法及陰離子交換樹脂法，本研究結合上述兩種預濃縮方法，改良成一種新方法：有機複合-酸萃取法，將樣水調整至適當pH，加入有機螯合劑APDC及DDDC，使之與銀形成帶負電的有機複合物，將水樣通過陰離子交換樹脂(AG-MP 1)管柱，使銀之複合物及凝絮物留滯於樹脂上，再以酸液萃取樹脂上的銀，待萃取完畢後，利用石墨爐式原子吸收光譜儀分析。經過一系列實驗測試後，適合低銀濃度自然水測量的有機複合-酸萃取法之建議步驟如下，取1 L水樣，加入10 mL pH=4之醋酸銨緩衝溶液將pH值調整約為4.5，加入2% APDC及DDDC 各2.5 mL，均勻混合後，將樣水通過裝填有0.2 g AG-MP1樹脂的管柱，依序以6、4及2 N HNO3溶液各萃取兩次，每次0.5 mL，每次萃取以超音波震盪3分鐘，最終體積為3 mL，收取後待上機測量。最終濃縮倍率約為333倍，探測下限為1.03 pM。本研究將此法應用於實測台灣西南海域近岸及大陸坡上之海水樣品，結果顯示離岸越近之測站，銀濃度有越高的情況，印證陸源輸入為近岸海水中銀的重要來源；在不同季節時，近岸海水之銀濃度亦不同，顯示銀濃度隨著河川流量不同而有所改變。此外，大陸坡測站水中銀與矽酸鹽濃度有正相關性，銀矽比除了在夏季高河川逕流量時受到大量沖淡水輸入影響，銀/矽比較低，於乾季時之銀矽比，則與前人研究相符。

Silver concentrations in natural water are very low and generally require preconcentration prior to instrumental analysis. Solvent extraction and anion exchange methods are the most commonly applied techniques for the determination of Ag in water samples. In this study, solvent extraction and anion exchange techniques are combined and modified to an “organic complexation-acid extraction” method. The procedure developed involves four steps: (1) a buffer is added and the pH of the solution is adjusted for optimization purpose; (2) APDC and DDDC chelating agents were added and the silver in the solution is organically complexed; (3) the solution was passed through AG-MP1 anion exchange resins and silver complexes and their flocculant were retained and; and (4) acid solutions were used to extract silver from the column for subsequent determination of sliver by a graphite furnace atomic absorption spectrophotometer. After the experiments, the optimal procedures were established as the following: The pH of a 1-L aqueous sample was adjusted to ~4.5 by adding a buffer solution. Aliquots of 2.5-mL solutions containing chelating agents (2% w/v each of APDC and DDDC) were added. After being mixed, the solution was passed through an anion exchange column (AG MP-1) and silver complexes (and their flocculated particles) retained. Two 0.5–mL aliquots of 6, 4 and 2 N HNO3 were used to extract Ag from the column, aided by sonication for 3 min during each extraction procedure. The final volume is 3 ml, yielding a concentration factor of ~333. Determination of sliver was done by a graphite furnace atomic absorption spectrophotometer. The detection limit is 1.03 pM. This method was suitable for both freshwater and seawater samples, and was successfully applied for the determination of Ag in coastal and off-shore seawaters collected from coastal region off southwestern Taiwan.

致謝 i
中文摘要 ii
英文摘要 iv
目錄 vi
圖目錄 viii
表目錄 x
第一章、前言 1
第二章、材料與方法 5
2.1銀之預濃縮方法原理及步驟介紹 5
2.2藥品配製及實驗流程 8
第三章、有機複合-酸萃取法之建立 14
3.1實驗流程 14
第四章、台灣西南海域海水樣品之應用 27
4.1研究區域 27
4.2現場採樣 27
4.3水文資料來源及分析 29
4.4海水樣品總溶解態銀分析方法 29
4.5結果與討論 30
4.6以有機複合-酸萃取法分析認證參考樣品 33
第五章、結論 42
參考文獻 43
中文部分 43
英文部分 44
附錄 49
圖2-1 APDC及DDDC溶劑萃取法流程示意圖，此圖係參考(Kinrade and Vanloon, 1974)所敘述之實驗流程 12
圖2-2陰離子交換樹脂法流程示意圖，此圖係參考(Yang and Sturgeon, 2002)所述之實驗流程 12
圖3-1不同pH值之樣品對樹脂沖堤銀之效率影響，結果顯示需最小沖堤液體積的最佳pH值為4.5 22
圖3-2調整樹脂用量進行沖堤之效率，結果顯示需最小沖堤液體積的樹脂用量為0.2 g 22
圖3-3使用不同濃度之HNO3及HCl作為沖堤液的效率，結果顯示需最小沖堤液體積的最佳沖堤液為6 N HNO3 23
圖3-4延長萃取時間之回收率，結果顯示萃取效果最佳的最小震盪時間為3分鐘 23
圖3-5改變同一樣品之萃取液強度之萃取變化。結果顯示萃取效果最佳的酸液變化情況為6、6、4、4、2、2 N HO3 24
圖3-6不同鹽度水樣之累計回收率。結果顯示添加APDC及DDDC(圖示中鹽度後有+A之樣品)之樣品，銀回收率皆可達100%，而未添加APDC及DDDC之水樣，銀回收則有隨海水比例降低而回收率遞減之趨勢 24
圖3-7調整各控制因素後所得之建議實驗步驟 25
圖4-1各航次採樣站位，OR3-1519 (2011/03/23-24，藍色)、OR3-1553 (2011/07/19-22，黑色)及OR3-1571 (2011/10/25-29，綠色)航次 35
圖4-2本研究於2011年3、7及10月航次之各測站表水鹽度分布 36
圖4-3本研究於2011年3、7及10月航次之各測站表水矽酸鹽分布 36
圖4-4本研究於2011年3、7及10月航次之各測站表水總溶解銀分布 37
圖4-5 2011年3月(藍色點)、7月(黑色點)及10月航次(綠色點)，各航次之測站表水銀與鹽度對比 37
圖4-6 2011年3月、7月及10月航次大陸坡測站、南海水、西菲律賓海水溫鹽圖 38
圖4-7(a) 2011年3月、7月及10月航次，大陸坡測站矽酸鹽之垂直剖面 38
圖4-7(b) 2011年3月、7月及10月航次，大陸坡測站250 m以上矽酸鹽之垂直剖面 39
圖4-8 2011年3月、7月及10月航次，大陸坡測站總溶解銀之垂直剖面 39
圖4-9前人研究之大洋測站及本研究之大陸坡測站(G4及S1站)銀濃度對矽酸鹽濃度作圖 40
表2-1溶解態銀在河流、河口灣及大洋之濃度比較 13
表3-1標準樣品添加之各金屬含量 26
表3-2樣品通過不同樹脂量置換後，DOC量測之實驗結果 26
表4-1前人研究及本研究依不同方法分析SRM之銀數據 41

中文部分： 李承軒，2008，淡水河流域銀之物種變化與時空分布。台灣大學理學院海洋研究所碩士論文，共92頁。 王俊凱，2008，西太平洋邊緣海銀之分布研究。台灣大學理學院海洋研究所碩士論文，共43頁。 何芃，2011，台灣西南沿岸與河口微量元素物種變化及其控制因子。國立中山大學海洋地質及化學研究所碩士論文，共95頁。 中央氣象局網站(http：//www.cwb.gov.tw)
44
英文部分：
American Public Health Association Standard methods for the examination of water and wastewater: 15th edition. 1981. American Public Health Association, Washington, D.C.
Andren, A. and Bober, T.W., 2002. Silver in the environment : transport, fate, and effects. SETAC Press, Pensacola, Fla., xxii, 169 p. pp.
Barriada, J.L., Tappin, A.D., Evans, E.H. and Achterberg, E.P., 2007. Dissolved silver measurements in seawater. Trac-Trends in Analytical Chemistry, 26(8): 809-817.
Barriada, J.L., Truscott, J.B. and Achterberg, E.P., 2003. Automation of a flow injection system for the determination of dissolved silver at picomolar concentrations in seawater with inductively coupled plasma mass spectrometry. Journal of Automated Methods & Management in Chemistry, 25(4): 93-100.
Benoit, G. et al., 1994. Partitioning of Cu, Pb, Ag, Zn, Fe, Al, and Mn between Filter-Retained Particles, Colloids, and Solution in 6 Texas Estuaries. Marine Chemistry, 45(4): 307-336.
Bruland, K.W., Coale, K.H. and Mart, L., 1985. Analysis of Seawater for Dissolved Cadmium, Copper and Lead - an Intercomparison of Voltammetric and Atomic-Absorption Methods. Marine Chemistry, 17(4): 285-300.
Bruland, K.W., Franks, R.P., Knauer, G.A. and Martin, J.H., 1979. Sampling and Analytical Methods for the Determination of Copper, Cadmium, Zinc, and Nickel at the Nanogram Per Liter Level in Sea-Water. Analytica Chimica Acta, 105(1): 233-245.
Buck, N.J., Gobler, C.J. and Sanudo-Wilhelmy, S.A., 2005. Dissolved trace element concentrations in the east River-long Island Sound System: Relative importance of autochthonous versus allochthonous sources. Environmental Science & Technology, 39(10): 3528-3537.
Farris, A., Wimbush, M., 1996. Wind induced Kuroshio intrusion into the South China Sea. Journal of Oceanography 52: 771-784.
Flegal, A.R. et al., 2007. Spatial and temporal variations in silver contamination and toxicity in San Francisco Bay. Environmental Research, 105(1): 34-52.
Flegal, A.R., Sanudowilhelmy, S.A. and Scelfo, G.M., 1995. Silver in the Eastern Atlantic-Ocean. Marine Chemistry, 49(4): 315-320.
Kinrade, J.D. and Vanloon, J.C., 1974. Solvent-Extraction for Use with Flame Atomic-Absorption Spectrometry. Analytical Chemistry, 46(13): 1894-1898.
Kramer, D., Cullen, J.T., Christian, J.R., Johnson, W.K. and Pedersen, T.F., 2011. Silver in the subarctic northeast Pacific Ocean: Explaining the basin scale distribution of silver. Marine Chemistry, 123(1-4): 133-142.
Kramer, J.R., Adams, N.W.H., Manolopoulos, H. and Collins, P.V., 1999. Silver at an old mining camp, cobalt, Ontario, Canada. Environmental Toxicology and Chemistry, 18(1): 23-29.
Liu, C.S., Lundberg, N., Reed, D.L. and Huang, Y.L., 1993. Morphological and Seismic Characteristics of the Kaoping Submarine-Canyon. Marine Geology, 111(1-2): 93-108.
Liu, J.T., Liu, K.J. and Huang, J.C., 2002. The effect of a submarine canyon on the river sediment dispersal and inner shelf sediment movements in southern Taiwan. Marine Geology, 181(4): 357-386.
Martin, J.H., Knauer, G.A. and Gordon, R.M., 1983. Silver Distributions and Fluxes in Northeast Pacific Waters. Nature, 305(5932): 306-309.
Martin, J.M. and Meybeck, M., 1979. Elemental Mass-Balance of Material Carried by Major World Rivers. Marine Chemistry, 7(3): 173-206.
Martinez-Gutierrez, F. et al., 2012. Antibacterial activity, inflammatory response, coagulation and cytotoxicity effects of silver nanoparticles. Nanomedicine-Nanotechnology Biology and Medicine, 8(3): 328-336.
Ndung'u, K., Franks, R.P., Bruland, K.W. and Flegal, A.R., 2003. Organic complexation and total dissolved trace metal analysis in estuarine waters: comparison of solvent-extraction graphite furnace atomic absorption spectrometric and chelating resin flow injection inductively coupled plasma-mass spectrometric analysis. Analytica Chimica Acta, 481(1): 127-138.
Ndung'u, K., Ranville, M.A., Franks, R.P. and Flegal, A.R., 2006. On-line determination of silver in natural waters by inductively-coupled plasma mass spectrometry: Influence of organic matter. Marine Chemistry, 98(2-4): 109-120.
Ndung'u, K., Thomas, M.A. and Flegal, A.R., 2001. Silver in the western equatorial and South Atlantic Ocean. Deep-Sea Research Part Ii-Topical Studies in Oceanography, 48(13): 2933-2945.
Purcell, T.W. and Peters, J.J., 1998. Sources of silver in the environment. Environmental Toxicology and Chemistry, 17(4): 539-546.
Ranville, M.A. and Flegal, A.R., 2005. Silver in the North Pacific ocean. Geochemistry Geophysics Geosystems, 6.
Ratte, H.T., 1999. Bioaccumulation and toxicity of silver compounds: A review. Environmental Toxicology and Chemistry, 18(1): 89-108.
Rivera-Duarte, I., Flegal, A.R., Sanudo-Wilhelmy, S.A. and Veron, A.J., 1999. Silver in the far North Atlantic Ocean. Deep-Sea Research Part Ii-Topical Studies in Oceanography, 46(5): 979-990.
Rozan, T.F., Benoit, G. and Luther, G.W., 1999. Measuring metal sulfide complexes in oxic river waters with square wave voltammetry. Environmental Science & Technology, 33(17): 3021-3026.
Rozan, T.F. and Hunter, K.S., 2001. Effects of discharge on silver loading and transport in the Quinnipiac River, Connecticut. Science of the Total Environment, 279(1-3): 195-205.
Rozan, T.F., Lassman, M.E., Ridge, D.P. and Luther, G.W., 2000. Evidence for iron, copper and zinc complexation as multinuclear sulphide clusters in oxic rivers. Nature, 406(6798): 879-882.
Sanders, J.G. and Abbe, G.R., 1987. The Role of Suspended Sediments and Phytoplankton in the Partitioning and Transport of Silver in Estuaries. Continental Shelf Research, 7(11-12): 1357-1361.
SanudoWilhelmy, S.A., RiveraDuarte, I. and Flegal, A.R., 1996. Distribution of colloidal trace metals in the San Francisco Bay estuary. Geochimica Et Cosmochimica Acta, 60(24): 4933-4944.
Shafer, M.M., Overdier, J.T. and Armstong, D.E., 1998. Removal, partitioning, and fate of silver and other metals in wastewater treatment plants and effluent-receiving streams. Environmental Toxicology and Chemistry, 17(4): 630-641.
Smith, G.J. and Flegal, A.R., 1993. Silver in San-Francisco Bay Estuarine Waters. Estuaries, 16(3A): 547-558.
Squire, S., Scelfo, G.M., Revenaugh, J. and Flegal, A.R., 2002. Decadal trends of silver and lead contamination in San Francisco Bay surface waters. Environmental Science & Technology, 36(11): 2379-2386.
Tappin, A.D. et al., 2010. Dissolved silver in European estuarine and coastal waters. Water Research, 44(14): 4204-4216.
VandeVoort, A.R. and Arai, Y., 2012. Chapter two - Environmental Chemistry of Silver in Soils: Current and Historic Perspective. In: L.S. Donald (Editor), Advances in Agronomy. Academic Press, pp. 59-90.
Wen, L.S., Santschi, P.H., Gill, G.A., Paternostro, C.L. and Lehman, R.D., 1997. Colloidal and particulate silver in river and estuarine waters of Texas. Environmental Science & Technology, 31(3): 723-731.
Wen, L.S., Santschi, P.H., Gill, G.A. and Tang, D.G., 2002. Silver concentrations in Colorado, USA, watersheds using improved methodology. Environmental Toxicology and Chemistry, 21(10): 2040-2051.
Wen, L.S., Stordal, M.C., Tang, D.G., Gill, G.A. and Santschi, P.H., 1996. An ultraclean cross-flow ultrafiltration technique for the study of trace metal phase speciation in seawater. Marine Chemistry, 55(1-2): 129-152.
Yang, L. and Sturgeon, R.E., 2002. On-line determination of silver in sea-water and marine sediment by inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry, 17(2): 88-93.
Zhang, Y., Amakawa, H. and Nozaki, Y., 2001. Oceanic profiles of dissolved silver: precise measurements in the basins of western North Pacific, Sea of Okhotsk, and the Japan Sea. Marine Chemistry, 75(1-2): 151-163.
Zhang, Y., Obata, H. and Gamo, T., 2008. Silver in Tokyo Bay estuarine waters and Japanese rivers. Journal of Oceanography, 64(2): 259-265.
Zhang, Y., Obata, H. and Nozaki, Y., 2004. Silver in the Pacific Ocean and the Bering Sea. Geochemical Journal, 38(6): 623-633.