本論文以二仁溪河口地區為對象進行研究，利用交錯流動過濾系統突破膠態物種分離技術之瓶頸，期能建立二仁溪河口地區重金屬存在物種模式，以提升重金屬物種研究之深度。研究子題包括重金屬存在物種含量及分佈、季節變異對重金屬存在物種之影響、測站變異對重金屬存在物種間之影響、鹽度因子與重金屬存在物種之關係及各物種中重金屬與凝絮物之關係。此研究成果，可提供水域中膠狀重金屬資訊，對未來台灣水域中膠狀重金屬之相關研究有所助益 。
實驗結果顯示二仁溪河口水域中總有機碳(TOC)及重金屬(Zn、Cu、Mn、Ni、Fe)含量皆較自然水域含量高，故該區屬污染水域。二仁溪河口水域中以鐵含量最高，其次依序鎳、錳、鋅、銅。二仁溪河口之重金屬污染主要來自三爺公溪的注入。
二仁溪各元素主要存在物種可分成兩類型，一為以顆粒態為主: 鋅、銅及鐵; 另一為以真溶解態及顆粒態為主: TOC、錳及鎳。各元素主要存在物種不隨測站及季節變異而改變。豐、枯水期中各元素總量與其主要存在物種具有顯著線性關係，其中豐水期TOC與鎳兩元素之總量與全部物種皆有顯著線性關係。重金屬之主要存在物種中顆粒態鋅主要為鋅與錳有顯著線性關係，顆粒態銅則是銅與TOC及鐵有顯著線性關係，真溶解態錳則與TOC有顯著線性關係，顆粒態鎳與鐵有顯著線性關係
鋅、銅及鐵之膠態物種(1 kD~0.45μm)佔溶解態百分比高，其均值分別為54.9 ±19.3 %, 75.6 ±12.3 % 及 72.5 ±28.0 %, 其TOC、錳及鎳溶解態部份則主要是以真溶解態型式存在，其佔溶解態百分比均值分別為63.2 ±11.5 %、 95.1 ±3.3 % 、 72.0 ±23.9 %。

二仁溪河口地區TOC、Zn、Cu、Mn、Ni、Fe等元素與鹽度之關係皆不顯著。

The aim of this research is to build up the model of trace metal phase speciation in Erh-Jen estuarine. Colloidal species were separated from the dissolved fraction by using cross-flow filtration technique. This allowed us to study the distribution of trace metal’s phase speciation and the relationships between: (1) seasonal variation and phase speciation of trace metal; (2) stational variation and phase speciation of trace metal; (3) the concentration of total and and speciations; (4) the prodution and removel of speciation in different salinity; (5) the flocculants and phase speciation of trace metal. The results will supply abundant information about colloidal metals that should be great benefit to the study of metal speciation of Taiwan waters in the future.
It is seriously polluted by trace metals in Erh-Jen estuarine. Iron has the highest concentration in river water, followed by nickel， manganese， zinc and copper. Station 3 which is located on San-Yen-Kung river is the most polluted.
Zinc, copper and iron exist in particulate phase predominately. Particle and truly dissolve phase are the major species of TOC、manganese and nickel. Contents of all the metals and TOC have significant linear correlation with their major species.
Zinc, copper and iron are found predominantly in colloidal fraction(1 kD~0.45μm), averaging 54.9 ±19.3 %, 75.6 ±12.3 % and 72.5 ±28.0 %, respectively, of the filter-passing pool. TOC, manganese and nickel, resides primarily in the truly dissolved phase , averaging 63.2 ±11.5 %, 95.1 ±3.3 % and 72.0 ±23.9 %, respectively, of the filter-passing pool.
The linear correlation between salinity and TOC, zinc, copper, manganese, nickel and iron are not significant in this study.

目錄
中文摘要 --------------------------------------------- Ⅰ
英文摘要 --------------------------------------------- Ⅲ
目 錄 --------------------------------------------- Ⅴ
表 目 錄 --------------------------------------------- Ⅶ
圖 目 錄 --------------------------------------------- Ⅸ
壹、前言 --------------------------------------------- 1
一、 重金屬物種-------------------------------------- 1
二、 研究河口之重要性-------------------------------- 2
三、 研究區域背景 ------------------------------ 4
四、 研究方向 ------------------------------------- 8
貳、材料與方法 ------------------------------------- 11一、交錯流動過濾系統------------------------------- 11
二、物種分離及濃度計算----------------------------- 16
三、水樣採集及處理 ---------------------------- 18
四、重金屬分析部份 ---------------------------- 18
五、總有機碳分析部份 ------------------------- 24
六、數據處理及統計分析-------------------- 25
參、結果 ----------------------------------- 26
一、 水質資料 ------------------------------------- 26
二、 總有機碳 ------------------------------------- 28
三、 鋅 ------------------------------------------- 39
四、 銅 -------------------------------------------- 50
五、 錳 -------------------------------------------- 61
六、 鎳 -------------------------------------------- 72
七、 鐵 -------------------------------------------- 83
八、 物種組成成份之相關性--------------------------- 94
肆、討論 -------------------------------------------- 103
伍、結論 -------------------------------------------- 117
柒、參考文獻 ----------------------------------------- 119

陸、參考文獻

英文參考資料
APHA. “Standard method for the examination of water and wastewater”, 18th
edition, APHA, Washington, D. C., 1992.
Benoit, G., “Evidence of the particle concentration effect for lead and other metals in
fresh waters based on ultraclean technique analyes”. Geochim. Cosmochm. Acta,
1995, 59, 2677-2687
Fletcher, W. K., Holmes, G. S., “Geochemistry and biological availability of iron and
trace elements in the upper fraser river estuary”. Mar. Chem., 1983, 12, 195-217
Benoit, G., Oktay-Marshall, S. D., Cantu, A., Hood, E. M., Coleman, C.
H.,Corapcioglu, M. O., Santschi, P. H., “Partitioning of Cu, Pb, Ag, Zn, Fe, Al, and
Mn between filter retained particles, colloid, and solution in six Texas estuaries”.
Mar. Chem., 1994, 45, 307~336.
Bertine, K. K., Vernon, C. R., “Elemental composition of the colloidal phase isolated
by cross-flow filtration from coastal seawater samples”. Mar.Chem., 1996, 55,
189~204.
Buesseler, K., “Introduction to Use of cross-flow filtration（CFF）for the isolation of
marine colloids”. Mar. Chem., 1994, 45, 105~119.
Coale, K. H., Bruland, K. W., “Copper complexation in the Northeast Pacific”.
Limnol Oceanogr., 1988, 33, 1084~1101.
Dai, M., Martin, J. –M., Cauwet, G., “The significant role of colloids in the transport
and transformation of organic carbon and associated trace metals（Cd, Cu and
Ni）in the Rhone delta（France）”. Mar. Chem., 1995, 51, 159-175.
Dai, M., Buesseler, K. O., Ripple, P., Andrews, J., “ Evaluation of two cross-flow
ultrafiltration membranes for isolating marine organic colloids”. Mar. Chem.,
1998, 62, 117-136.
Dijk, H. V., “Cation binding of humic acids”. Geoderma, 1971, 5, 53.
Florence, T. M., “Trace elements speciation and aquatic toxicology”. Trends Anal.
Chem., 1983, 2, 162~166.
Forbes, E. A., Posner, A. M., Quirk, J. P., ”The specific adsorption of divalent Cd,
Co, Cu, Pb, and Zn on goethite”. J. Soil Sci., 1976, 27, 154.
Hasle, J. R. Abdullah, M. I., “Analytical fractionation of dissolved copper, lead
and cadmium in coastal seawater”. Mar. Chem., 1981, 10, 487~503.
Holliday, L. M., Liss, P. S., “The behavior of dissolved iron, manganese and
zinc in the Beaulieu Estuary”. Estaurine Coastal Mar. Sci., 1976, 4, 349~353.
Honeyman, B. D., Balistrieri, L. S., Murray, J. W., “Oceanic trace metal scavenging:
the importance of particle concentration”. Deep-Sea Research, 1988, 35, 227~246.


Jerry, L. H., Peter, F. L., Harold, L. B., William, H. B., Bioavailability : Physical,
Chemical, Biological interactions , CRC, Boca Raton, FL, 1992.
Khan, S. U., “Interaction Between humic acid fraction of soils and certain metallic
cations”. Proc. Soil Sci. Soc. Am., 1969, 33, 851.
Kinniburgh, D. G., “Cation absorption by hydrous metal oxides”. Ph. D. Thesis,
University of Wisconsin, 1973, 100.
Kramer, C. J. M., Duinker, J. C., “Complexation capacity and conditional
stability constants for copper of sea and estuarine waters”. Sediments extracts and
colloids. In : C. J. M. Kramer and Duinker, J. C.,(Editors), Complexation of Trace
Metals in Natural Waters. Junk. Dordrecht, 217~228. Mar. Chem., 1983, 12,
195~217.
Krauskopf, K. B., “Factors controlling the concentration of thirteen rare metals in
sea-water” . Geochim. Cosmochm. Acta, 1956, 10, 1~26.
Koike, I. H., Shigemitsu, K. T., Kazuhiro, K., “Role of sub-micrometer particles in
the ocean”. Nature, 1990, 345, 242~244.
Li, Y. –H., Burkhardt, L., Teraoka, H., “Desorption and coagulation of trace
elements during estuarine mixing”. Geochim. Cosmochm. Acta,1984, 48, 1879-
1884.
Gaddle, R. R., Laitiner, H. A., “Stuaies of heavy metal absorption by hydrous iron
and manganese oxides”. Anal. Chem., 1974, 46, 2022.
Guo, L., Coleman Jr., Charlie, H., Santschi, P. H., “The distribution of colloidal and
dissolved organic carbon in the Gulf of Mexico”. Mar. Chem., 1994, 45, 105-119.
Guo, L., Santschi, P. H., “A critical evaluation of the cross-flow ultrafiltration
technique for sampling colloidal organic in seawater”. Mar. Chem., 1996, 55, 113~
127.
Goldberg, E. D., “Marine Geochemistry, 1. Chemical Scavengers of the Sea”. J.
Geol., 1954, 62, 249~265.
Goldberg, E. D., Baker, M. and Fox, D. L., “Microfilitration in Oceanographic
Research, 1.Marine Sampling with the Molecular Filter”. J. Mar. Res., 1952,
11, 194~203.
Greenamoyer, J. M., Moran, S. B., “Evaluation of an Osmonics sprial-wound cross-
flow filtration system for sub-µm Sampling of Cd, Cu, and Ni in Seawater”. Mar.
Chem., 1996, 55, 153~163.
Martin, J. –M., and Dai, M. -H., “Significance of colloids in the biogeochemical
cycling of organic carbon and trace metals in the Venice Lagoon（Italy）”. Limnol.
Oceanogr., 1995, 40, 119~131.
Miller, L. A., Bruland, K. W., “Determination of copper speciation in marine waters
by competitive ligand equilibration/ liquid-liquid extraction: an evaluation of the
technique”. Geo. Chim. Acta, 1994, 284, 573~586.
Millipore, “Selecting a membrane for clarification or cell harvest “. 1998.
Moran, S. B., Buesseler, K. O., “Size-fractionated 234 Th in continental shelf waters
off New England：Implications for the role of colloids in oceanic trace metal
scavenging”. J. Mar. Res., 1993, 51, 983~922.
Moffett, J. W., Zika, R. G., Brand, L. E., “Distribution and potential sources and
sinks of copper chelators in the Sargasso Sea”. Deep- Sea Res., 1990, 37, 27~36.
Murray, J. W., Brewer, P. G., ”The mechanism of remova of manganese, iron and
other trace metals from seawater in: Marine manganese Deposits”. G. P. Glasby,
ed., 1977, 10, 291.
Powell, R. T., Landing, W. M., Bauer, J. E., “Colloidal trace metals, organic carbon
and nitrogen in a southeastern U. S. estuary”. Mar. Chem., 1996, 55, 165~176.
Rashid, M. A., “Absorption of metals on sedimentary and peat humic acids”. Chem.
Geol. 1974,13, 115.
Reitmeyer, R., Powell, R. T., Landing, W. M., Measures, C. I., “Colloidal aluminum
and iron in seawater：An intercomparison between various cross-flow
ultrafiltration systems”. Mar. Chem., 1996, 55, 75~91.
Sergio, S. –W., Ignacio, R. –D., Flegal, R., “Distribution of colloidal trace
metals in the San Francisco Bay estuary”. Geochim. Cosmochm. Acta, 1996,
24, 4933~4944.
Stevenson, F. J., “Nature of divalent transition metal complexes of humic acids as
revealed by a modified potentiometric titration method”. Soil Sci., 1977, 123, 10.
Stordal, M. C., Gill, G. A., Wen, L. -S., Santschi, P. H., “Mercury phase
speciation in the surface waters of three Texas estuaries：Importance of
colloidal forms”. Limnol. Oceanogr.,1996, 41, 52~61.
Sholkovitz, E. R., “The flocculation of dissolved Fe, Mn, Al, Cu, Ni, Co, and Cd
during estuarine mixing”. Ear. Plan. Sci. Lett., 1978, 41, 77-86
Well, M. L., and Goldberg , E. D., “Marine Submicro Particles”. Mar. Chem., 1992,
40, 5~18.
Whitehouse, B. G., Yeats, P. A., Strain, P. M., “Cross-flow filtration of colloids
from aquatic environments.” Limnol. Oceanogr., 1990, 35, 1368~1375.
Windom, H. S., Rawlinson, R. Jr., “Trace Metal Transport in a Tropical Estuary”.
Mar. Chem., 1988, 24, 293-305.
Wen, L. –S., Stordal, M. C., Tang, D., Gill, G. A., Santschi, P. H., “An ultraclean
cross-flow ultrafiltration technique for the study of trace metal phase speciation in
seawater”. Mar. Chem., 1996, 55, 129~152.
Wen, L. –S., Santschi, P., Gill, G., Paternostro, C., “Estaurine trace metal distribution
in Galveston Bay : importance of colloidal forms in the speciation of the dissolved
phase”. Mar. Chem., 1999, 63, 185~212.

中文參考資料
二仁溪流域污染整治計畫（1987），賽蒙斯李顧問公司。
臺灣水文年報（1988~1998）。台灣省水利局。
王銀波；王敏昭（1990），引響二仁溪流域污染直重金屬與底泥及土壤相互
反應之水體環境因子之探討，科資中心編號 PB7911-2002。
洪佳章，河口重金屬之凝絮與吸脫附及脫附作用（1990），中山大學海洋
地質及化學研究所。
何先聰（1992），二仁溪各河段底泥污染質與底棲生物之相關研究，科資中
心編號 PA8104-2129。
洪楚璋（1993），改善二仁溪附近海域生態環境之研究，科資中心編號
PA8209-1038。
洪楚璋（1993），海水與沉積物中銅物種與生物累積銅間之交互作用，科資
中心編號PA8012-1049。
水質檢測方法(1995), 行政院環保署環境檢驗所。
劉士萍(1998)， 朴子溪河口地區重金屬之分佈與物種之研究， 國立中山大學
海洋資源學系。