本研究主要探討高屏河口與近岸海域微量金屬的分佈及其控制機制。高屏河口豐水期因受到高流量稀釋效應的影響，各金屬濃度大致皆較枯水期低；且因水體的滯留時間短也造成物理作用比生地化反應對微量元素分佈之影響顯著。由於溶解態微量元素於河口中之非守恆性習性，致Fe、Mn、Zn、Cu及Cd皆有添加的情況，但Pb於豐水期則有移除的現象。顆粒態Al、Fe主要來源為高屏溪流域地質背景之陸源輸入，TSM的分佈似為兩者傳輸的主要控制機制。枯水期河口受到大量溶解有機物質輸入與來自汕尾漁港污染注入的影響，使溶解態Mn、Zn、Cu、Cd及Pb於上河口出現高值。
高屏近岸海域主要受到高屏溪陸源輸入的影響，各溶解態微量元素在季節性分佈上明顯受制於混合層中淡海水之物理混合及混合層外峽谷底部顆粒再懸浮的影響。高屏峽谷溶解態與顆粒態微量金屬各測站濃度積分值顯示，夏季豐水期峽谷內溶解態及顆粒態微量元素之儲存量明顯高於其他季節，尤以B1出海口測站最為明顯。由溶解態Mn、Zn、Cu與Pb同一測站濃度隨深度增加而遞增的變化，顯示有側向傳輸與底部釋出的來源。溶解態Zn、Cu與Mn有顯著正相關，而顆粒態Zn、Cu與Al並無明顯的相關性，顯示在高屏海域中Zn、Cu除了受陸源的輸入影響外，生物作用也是控制其分佈的主要原因之一。而溶解態Cd與營養鹽(N+N、Phosphate)有顯著正相關及和DOC呈現的顯著負相關，顯示生物作用為峽谷中營養鹽型金屬Cd之主要控制機制。
颱風、地震等特殊事件，對高屏海域微量元素的分佈有相當程度的影響。研究期間(Aug/2004與Aug/2005)由於颱風的影響，使陸源輸入的訊號更為明顯，因此峽谷內懸浮顆粒(TSM)濃度出現異常高值，最高可達 >700 mg/L。與常態夏季航次(Jul/2003)比較，颱風效應造成峽谷內各測站TSM濃度積分值高出數倍至數十倍之多，導致顆粒態微量元素相對增高。另一方面高屏峽谷受到地震的影響，使得冬季航次(Jan/2007)各測站的底部皆顯示TSM之異常高值，與2006年1月(正常冬季)比較，地震效應造成峽谷內各測站TSM濃度之積分值約高出2~7倍，水體中主要以顆粒態型式存在的Al、Fe及Mn之積分值增加約2~10倍之多。顯示地震造成峽谷中TSM濃度的提高，同時對顆粒態微量金屬造成之影響亦較溶解態來的顯著。
由高屏河口及近岸海域中微量元素(Mn、Zn、Cu、Cd、Pb)之富集因子(EF)顯示，枯水期河口內各元素污染程度較豐水期高出數倍至數十倍。Mn在河口枯水期可以看到顯著的污染現象，但在近岸則顯示乾濕季皆無明顯的污染情況。Zn、Cu之EF值呈現河口往外海增加的趨勢，部分是由於近岸地區生物累積作用造成的結果。Zn與Pb在河川與河口乾濕季的富集因子雖有季節性的差異，但皆大於1，呈現河川至河口漸增，顯示高屏河口受到來自其他污染源(如汕尾漁港)的影響，使其Pb和Zn的污染情況更為嚴重。而Zn在近岸地區的高富集因子，顯示近岸海域也有相當程度之Zn的污染。

This study investigates the distributions of trace metals and their controlling mechanisms in the Kaoping coastal zone. Concentrations of most dissolved metals were generally lower in the wet season than in the dry season in the Kaoping Estuary, showing clearly the effects of river discharge rate and water residence time on metal distributions. Dissolved trace metals (Fe, Mn, Zn, Cu, Cd and Pb) behaved non-conservatively with addition in the estuary. Nevertheless, dissolved Pb was apparently removed from the estuary in the wet season. Particulate Al and Fe were derived mainly from continental weathering and their transports through the estuary depend highly on the distribution of total suspended matter (TSM). During the dry season, the occurrence oxygen-deficit condition in the low salinity region and possible pollution from the San-Wei fishery harbor likely determined the distributions and solid-solution partitions of Mn, Zn, Cu, Cd and Pb in the estuary.
Distributions of dissolved trace metals in the Kaoping coastal zone were significantly influenced by terrestrial inputs from the Kaoping River. Seasonal variations were attributed largely from the mixing between river water and sea water in the mixing layer and sediment resuspension from canyon bed. The column integrated dissolved and particulate metals were generally higher in the summer season than in other seasons. The difference was especially pronounced in nearshore stations. Concentrations of dissolved Mn, Zn, Cu and Pb increased generally with depth, reflecting the effects of resuspension and lateral transport of bottom sediment. Dissolved Zn and Cu concentrations correlated well with dissolved Mn concentration, but particulate Zn and Cu correlated poorly with particulate Al, implying that distributions of Zn and Cu were controlled by terrestrial inputs and biogeochemical processes in the Kaoping Canyon. Positive and negative correlations are found between dissolved Cd and nutrients (N+N，orthophosphate) and between dissolved Cd and dissolved organic carbon (DOC), respectively, indicating that Cd is a nutrient-type metal and controlled biogeochemically in the Kaoping Canyon.
Specific events such as typhoon and earthquake influenced significantly the distributions of trace metals in the Kaoping coastal zone. The integrated suspended-matter and suspended-metal concentrations showed an order magnitude higher during the typhoon season than in the normal summer season. Under the influence of earthquake, the TSM values of the bottom waters were much higher (2-7 folds) during the post- earthquake cruise (Jan/2007) than in the normal season (Jan/2006). Meanwhile, particulate Al, Fe, and Mn can increase up to 2- to 10-folds after earthquake in the bottom layer of canyon.
Metal enrichment factor (EF) is an indicator of metal pollution. The EFs show an order magnitude higher in the dry season than in the wet season both in the estuary and canyon. Such seasonal patterns clearly indicate the impacts of local and river inputs on metal distributions in the estuary and canyon.

致謝……………………………………………………………………I
中文摘要………………………………………………………...…....II
英文摘要………………………………………………..……………III
目錄………………………………………...……………..………….IV
圖目錄……………………………………………………...….……. .V
表目錄…………………………………………………..……………VI

第一章 前言……………………………………..………….………….1
第二章 研究區域…………………………………..……………….….4
2.1高屏溪河口….………………………..…………….….….4
2.2高屏峽谷…………………………………………………..7
第三章 研究材料及方法………………………....……………….…...9
3.1 採樣時期及位置……………..………………..……..…...9
3.2 採樣方法…………………………...……..……………..10
3.3實驗方法…………………………………………………15
第四章 結果與討論…………………………..…………...……….....25
4.1高屏溪河口水文化學與季節變化.……………...………30
4.2高屏溪河口營養鹽之分佈及其季節性變化...………….35
4.3高屏溪河口微量金屬之分佈與季節性變化……..……..38

4.4高屏河口微量金屬之地化特徵與污染現況…………......64
4.5高屏峽谷水文化學與季節變化…….…………...……......69
4.6高屏海域營養鹽之分佈及河川輸出的影響..……………78
4.7高屏峽谷微量金屬之分佈與季節性變化………………..82
4.7-1溶解態微量金屬…………………………………….82
4.7-2總懸浮顆粒物質(TSM)之分佈……………………101
4.7-3顆粒態微量金屬…………………………………...104
4.8颱風及地震的效應………………………………………115
4.9高屏海域微量金屬之污染現況………............................120
第五章 結論…..………………….…………………………...……....123
參考文獻……………………………...………….…..….…….………126
中文部分…………………………………..…......….……….126
英文部分……………………………………..…...………….127

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