臺灣博碩士論文加值系統

典寶溪為高雄縣五大河川之一，沿河兩岸金屬工業發達，再加上不肖業者偷排，造成河川水質惡劣，成為環保署列管之重點整治河川。本研究自民國95年6月起規劃了19個採樣點，使用感應耦合電漿放射光譜儀（ICP-OES），分析水體及底泥中48種金屬元素含量，以了解典寶溪中微量元素之污染狀況。
研究結果顯示：各水質分析項目多數符合法規規範。水中總Fe（1.4±0.716 mg/L）、總Mn（0.27±0.184 mg/L）的濃度最高；其中，典寶橋等4測站總B的濃度超過我國放流水排放標準；而第一科大旁測站，總Zn濃度（0.61 mg/L）超過水體水質分類管制標準。經過一年四季共68次，以長期固定採樣結果發現，寶橋測站的總As、總B和總Zn污染濃度明顯較橋子頭橋測站高，代表污染源來自典寶橋上游回溯至橋子頭橋之間，總Cr、總Cu和、Ni、總Fe、總Pb和總Mn濃度比較結果顯示，污染源是來自橋子頭橋上游。
相關性統計分析結果顯示：（1）水中總B、總Cr與總Cu，（2）總Ni與總As，及（3）總Fe與總Zn，分別呈現高度且顯著的正相關（r＞0.69，P＜0.01）。相關性高之金屬可能來自相同的污染源。水中各金屬元素污染程度以空間分佈並由集群分析得到結果可分為三類集群，分別為（一）上游河段的烏山橋至鳳山厝橋，（二）單獨為ㄧ集群的福安橋，以及（三）由其餘共11個測站所集群而成。主要污染最嚴重區域落在集群二，為流域下游感潮河段部份。
底泥中各重金屬平均濃度於福安橋河段檢出濃度為最高；其中在福安橋測站總Zn最高濃度1740 mg/kg dry wt超過國內土水法管制標準值2.9倍；另外總Ni最高濃度645 mg/kg dry wt則是在鳳山厝支線的寶溪南街測站檢出，超過土水法管制標準3.2倍之高。
福安橋底泥中總重金屬垂直濃度約在40 cm深處濃度為最高，濃度高低與樣品有機質含量有明顯相關性，底泥濃度與粒徑雖呈正相關，但其相關性較有機質含量為弱，顯示有機質含量是重金屬累積之主控因素。另外由集群分析依金屬污染程度不同可得到分為三類集群之結果。
底泥主成分分析結果顯示，在主成分一由總Cr 、Cu、Zn組成，此結果與相關性分析結果相互呼應；主成分二由總Ni組成；主成分三由總Pb組成，共可解釋掉97.36％的變異，主成分一及二可能與流域之金屬工業相關，而主成分三則看不出與金屬加工業之關連。
典寶溪底泥重金屬之富集程度分佈情形顯示，以典寶溪背景點濃度來計算富集因子校正值會優於以地殼平均濃度來計算富集因子校正值，較符合實際現況。總Cr（EF＝0.9~3.5）、總Cu（EF＝0.7~3.9）、總Ni（EF＝1.0~22.1）、總Zn（EF＝1.5~17.0）於流域內部分測站皆有富集現象，尤其是Zn明顯有遭受人為污染。
比較國內外12條河川，發現國內河川重金屬污染普遍較國外嚴重，除了總Cu和總Pb污染濃度相對較低之外，其餘重金屬污染則顯得較為嚴重，值得相關單位警惕和注意。與國內外法規相較之下，典寶溪總Ni和總Zn已超過多項法規管制標準，其中總Ni濃度更高於美國NOAA TEL管制值5.7倍之高，值得相關單位警惕、持續監測及思考污染防治策略。

Dian Bao River is one of the major five rivers in the Kaohsiung County, where there was developed metal industry along both banks of the river. However, some unworthy metal mill owners discharged industrial wastes into the river by stealth, resulting in poor water quality, and thus the department of environment protection has focused on renovating this river. This research has planned for 19 sampling points since June, 2006, and used inductively coupled plasma optical emission spectrometer (ICP-OES) to analyze the content of 48 metal elements in the water and sediment, in order to understand the situation of trace element pollution in the Dian Bao River.

The research results indicated that most of the water quality analysis items could meet the standards set by law. The average concentration of total Fe (1.4±0.716 mg/L) and total Mn (0.27±0.184 mg/L) were the highest. Wherein, the total B concentration in the 4 observation stations at the Dian Bao Bridge exceeded Effluent Standards. At the observation station near National Kaohsiung First University of Science and Technology, the total concentration of Zn (0.61 mg/L) exceeded Surface Water Classification and Water Quality Standards. It was found in the result of the long-term (68 times through four seasons in a year) fixed sampling, that the pollution concentration of total As, total B, and total Zn from the observation station at the Dian Bao Bridge was obviously higher than that at the Ciao Zih Tou Bridge, which indicated that the pollutant source was at the place between the Dian Bao Bridge’s upper reaches and the Ciao Zih Tou Bridge. The comparison of the concentration of total Cr, total Cu and Ni, total Fe, total Pb, and total Mn indicated that the potential sources came from the upper reaches of Ciao Zih Tou Bridge.
The result of correlation statistic analysis indicated: a high-level and notable positive correlation (r>0.69, P<0.01) was evident among (1) the total B, total Cr and total Cu, (2) total Ni and total As, and (3) total Fe and total Zn. The metals with high correlation between each other probably came from the same pollutant source. The significance of metallic pollution in the water could be divided into three clusters according to the result of spatial distribution and cluster analysis, that is, (1) Wu Shan Bridge to Fong Shan Cuo Bridge at the upper reaches; (2) Fu An Bridge, considered as a cluster itself; (3) a cluster consisting of 11 observation stations. The area with the most serious pollution happened at the second cluster, belonging to the tidal reaches at the lower reaches.

The highest average concentration of each heavy metal in the sediment was observed at the Fu An Bridge river section; wherein the highest concentration of total Zn at the Fu An Bridge observation station was 1740 mg/kg dry wt, 2.9 times higher than the standard value regulated by the Soil and Groundwater Pollution Remediation Act; in addition, the highest concentration of total Ni, 645 mg/kg dry wt, was tested at the Bao Si South Street observation station at the Fong Shan Cuo branch, which was 3.2 times higher than the standard value regulated by the Soil and Groundwater Pollution Remediation Act.

The vertical distribution of total heavy metal concentration in the sediment at the Fu An Bridge reached its maximum value at about the 40 cm depth, and there was an obvious correlation between the concentration and the content of organic matter in the sample. Although the sediment concentration had a positive correlation with the particle diameter, it was not as obvious as that with the content of organic matter, which indicated that the content of organic matter was the main controlling factor of heavy metal accumulation. In addition, the cluster analysis based on metallic concentration could result in three kinds of clusters.

The sediment principle component analysis showed that, the component one consisted of Cr, Cu, and Zu, corresponding with the result of correlation analysis; the component two consisted of Ni, and the principle component three consisted of Pb, both of the components could explain 97.36% of the variations. The component one and two were probably related to the different types of metal industry at this drainage basin, whereas no correlation was found between the principle component three and the metal processing industry.

The sediment heavy metal enrichment factor analysis at the Dian Bao Stream indicated that it was better to calculate the enrichment factor based on the Dian Bao Stream background concentration than that by the crustal average concentration, in order to better match the actual situation. The enrichment factors of total Cr（0.9~3.5）, total Cu（0.7~3.9）, total Ni（1.0~22.1）, and total Zn（1.5~17.0）all supported that enrichment effect in part of the observation stations within that drainage basin, especially for Zn.

By comparing with 12 domestic and foreign rivers, it was found that the heavy metal pollution in domestic rivers was more serious than that in foreign rivers. There was severe pollution by all heavy metals except the total Cu and total Pb, which should draw attention from relevant entities. Compared with domestic and overseas laws in this regard, the total Ni and total Zn at Dian Bao River has exceeded several standards regulated by law, and the total Ni concentration was 5.7 times higher than the value regulated by the US NOAA TEL, and therefore relevant entities shall keep their eyes on and keep monitoring this problem, and try to develop a sound pollution prevention strategy.

摘要 I
Abstrace III
誌謝 VII
目錄 VIII
表目錄 XI
圖目錄 XIII
第一章、前言 1
1.1 研究動機 1
1.2 研究目的 2
1.3 研究架構 3
第二章、文獻回顧 4
2.1 典寶溪流域背景簡介 4
2.1.1 典寶溪流域水文與人文資訊 4
2.1.2 重金屬廢水來源 5
2.2 微量元素與重金屬種類及毒性危害 12
2.3 重金屬污染之環境宿命與傳輸 19
2.4 我國金屬元素管制標準 19
2.4.1 我國水質管制標準 19
2.4.2 我國底泥管制標準 22
2.5 重金屬污染分佈之富集因子校正 22
2.6 國內外河川金屬元素調查研究 24
2.7 統計分析 27
第三章、材料與方法 29
3.1 採樣規劃 29
3.1.1 採樣地點 29
3.1.2 採樣時間 30
3.1.3 採樣方法 30
3.2 材料與研究設備 32
3.3 水質及底泥分析方法 32
3.3.1 水質分析方法 32
3.3.2 底泥分析方法 34
3.3.3 品保品管 37
第四章、結果與討論 38
4.1 ㄧ般水質特性 38
4.1.1 水溫之季節變化 38
4.1.2 pH之季節變化 38
4.1.3 導電度之季節變化 39
4.1.4 鹽度之季節變化 39
4.1.5 溶氧之季節變化 40
4.1.6 濁度之季節變化 40
4.2 水中各金屬元素分析結果與討論 48
4.2.1 空間污染分佈特性探討 48
4.2.2 時間污染分佈特性探討 51
4.2.3 水中各金屬元素相關性探討 70
4.2.4 水中各金屬元素集群相關分析 71
4.3 雨季之水中金屬濃度變化探討 73
4.4 底泥各金屬元素分析結果與討論 79
4.4.1 底泥空間污染分佈特性探討 79
4.4.2 福安橋測站底泥垂直深度重金屬分佈探討 86
4.4.3 底泥基本特性與各金屬元素之相關性探討 91
4.4.4 底泥各金屬元素集群相關分析 94
4.4.5 底泥污染物之主成分分析 96
4.4.6 底泥各重金屬濃度與富集因子校正比較 98
4.4.7 底泥中重金屬濃度與國內外各河川及法規值之比較 105
第五章、結論與建議 109
5.1 結論 109
5.2 建議 112
參考文獻 113
附錄 120

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