臺灣博碩士論文加值系統

礦業發展過程中所產生之廢礦經風化作用可進一步衍生出酸性礦山排水（acid mine drainage; AMD），其所含高濃度有毒元素及後續形成之大量含水氧化鐵沉澱皆可能對環境生態及人體健康造成影響。瞭解AMD及其沉澱物之特性、危害性及再利用性有助於對其之預防與整治外，也有利於環境之永續發展。本研究以Ｘ光繞射、傅利葉轉換紅外線光譜、電子顯微鏡和感應藕合電漿放射光譜等方法分析金瓜石酸性礦山排水（pH = 2.8）及其與溪水（pH = 6.0）和海水（pH = 8.0）混染過程中之水化學特性以及所沉澱物質之礦物學特徵，以探討其中之元素遷移行為與微奈米硫酸氫氧氧化鐵物質沉澱作用之關係，並考量瀑布地形與季節變化之影響。
金瓜石黃金瀑布、濂洞溪下游河床和本山七坑坑口及其溝渠流徑之表層沉澱物以具刺蝟狀形貌之四方硫酸纖鐵礦（schwertmannite）球粒集合體為主要組成。酸性礦山排水中鐵和砷濃度由上游往下游相對其他金屬離子濃度大幅減少，顯示四方硫酸纖鐵礦為現地沉澱，並且具有顯著之砷吸收能力。酸性礦山排水受瀑布曝氣效應影響可加速其二價鐵氧化速率，使得瀑布段之二價鐵氧化速率及模式速率常數（0.5-2.0×10-7 mol L-1 sec-1和1.1-5.7×10-3 sec-1）及鐵（四方硫酸纖鐵礦）沉澱作用之速率及模式速率常數（1.5-7.3×10-7 mol L-1 sec-1和1.9-2.4×10-7 mol L-1 sec-1）較下游溪流段快或高出1至2個量級，並具有高砷吸收率（4.7-6.3×10-9 mol L-1 sec-1）。溪流段夏季之速率受溫度影響比冬季高出4至5倍，但瀑布段冬季之速率與夏季差異不大，可歸因於冬季水流量大時瀑布曝氣效應可增強鐵沉澱速率。
草酸銨溶樣分析結果顯示黃金瀑布表層四方硫酸纖鐵礦之平均化學式為Fe16O16(OH)11(SO4)2.5•16H2O，並含有2794 ppm砷、439 ppm鋁、115 ppm銅及23 ppm鉻。隨著沉澱深度增加，四方硫酸纖鐵礦先逐漸轉變成低結晶度針鐵礦，再轉變成較高結晶度針鐵礦。同時沉澱物整體之Al/Fe、Cr/Fe與S/Fe莫耳比值減少，As/Fe無顯著變化，Cu/Fe增加，顯示四方硫酸纖鐵礦轉變過程中，鋁、鉻與硫酸根被釋放至溶液中，砷可被保留，銅則被富集。低結晶度針鐵礦之形成對相轉變過程中元素之遷移及滯留行為有顯著影響。
四方硫酸纖鐵礦之沉澱可使金瓜石酸性礦山排水中砷及金屬濃度往下游衰減，但仍約有每年3235公噸鐵、737公噸鋁、191公噸銅及2.4公噸砷排放至濂洞灣中，並且在海水表層沉澱大量懸浮粒。入海口海水（酸鹼值小於4）所形成短柱狀懸浮奈米微粒，乃是四方硫酸纖鐵礦及少量針鐵礦所組成；而濂洞灣近岸海水（酸鹼值大於5.5）所形成球狀懸浮奈米微粒，屬非晶質水合氧化鐵、鋁，並含有微量四方硫酸纖鐵礦。隨著水體酸鹼值升高，海水懸浮粒之組成從相對富含砷、鉻、鉛、鐵及硫轉而相對富含鋁、矽、銅、鋅、錳、鎳、鈷及鎘。金瓜石酸性礦山排水之水體化學及沉澱物組成變化主要受控於（硫酸）氫氧氧化鐵、鋁物質沉澱與水體酸鹼值之改變，以及中和過程中金屬元素逐步於不同階段共沉澱或被吸附作用。這些過程可延緩或降低金瓜石地區酸性礦山排水對環境污染之影響，然而富含重金屬之海水懸浮粒的後續脫附、轉變或溶解作用值得追蹤和關注。

Acid mine drainage (AMD) often occurs as a result of weathering of mine wastes in mining areas. Migration of high concentrations of toxic elements and subsequent precipitation of hydrous iron oxides in AMD areas could pose great threats on environmental quality, ecosystem, and human health. Analyzing the characteristics and reactions of AMDs and their precipitates is fundamentally important for understanding geochemical reactions in such an environment. It can also provide parameters essential for contamination assessment and remediation crucial to environmental sustainability.
Variations of water chemistry and precipitate mineralogy during mixing of acid mine drainage (AMD) (pH = 2.8) with a creek (pH = 6.0) and seawater (pH = 8.0) were investigated by XRD, SEM, TEM, IR, ICP analysis to discuss the relationships between metal mobility and precipitation of micro-nanometric iron oxyhydroxysulfate minerals in the Chinkuashih AMD area in consideration of reaction kinetics, waterfall effects, and seasonal variations. In terms of Fe(II) oxidation and Fe(III) precipitation in the creek section, the summer rates were 4-5 times higher than the winter rates, largely attributed to a temperature effect. In contrast, the seasonal differences in rate and rate constant were small in the waterfall section due to waterfall aeration which enhanced the Fe precipitation rate when the flow rate was large in the winter.
Radiating aggregates of schwertmannite with an overall hedgehog morphology occurred as a principal constituent of the surface precipitates on the bedrocks of Golden Falls and downstream Lian-Dong Creek and a channel at the Penshan 7th adit. Remarkable downstream reduction of Fe and As concentrations with respect to other metals in the water suggested in-situ precipitation of schwertmannite associated with an arsenate sorption process. Under the influence of water aeration, the waterfall section showed up to 1-2 orders of magnitude faster rates and higher model rate constants of Fe(II) oxidation (6.1-6.7×10-6 mol L-1 sec-1and 2.7-2.9×10-2 sec-1) and Fe (schwertmannite) precipitation (1.7-2.1×10-6 mol L-1 sec-1and 3.5-4.1×10-7 mol L-1 sec-1) than the creek section, and had a high As sorption rate (4.7-6.3×10-9 mol L-1 sec-1).
The schwertmannite in the surface precipitate at Golden Falls had an chemical formula of Fe16O16(OH)11(SO4)2.5•16H2O, and contained 2794 ppm As, 439 ppm Al, 115 ppm Cu, and 23 ppm Cr on average. With increasing depth, a transformation from schwertmannite, poorly crystalline goethite, to better crystallized goethite was characterized. In addition, bulk analyses indicated decreases of Al/Fe, Cr/Fe and S/Fe molar ratios and an increase of Cu/Fe and with rather small variations in As/Fe as the sample depth increased. The data suggested that Al, Cr and sulfate were released, As was retained, and Cu was accumulated, and that the formation of poorly crystalline goethite had a strong effect on the mobility and attenuation of elements during the transformation.
Schwertmannite precipitation was the main cause for downstream attenuation of As and metal concentrations in the Chinkuashih AMD and creek waters. However, there were still about 3235 metric tons per year (t yr-1) of Fe, 737 t yr-1 Al, 191 t yr-1 Cu, and 2.4 t yr-1 As discharged into Lian-Dong Bay, which produced abundant suspended particulates in the surface seawater near the estuary. The estuarine suspended particulates formed at pH 〈 4 were short nanorods consisting of schwertmannite and subordinate goethite, and the inshore suspended particulates formed at pH 〉 5.5 were composed of non-crystalline hydrous iron and aluminum oxides (HFO and HAO) with a trace of schwertmannite, in a form of nanoballs. As the pH increased in the water, the suspended particulates were enriched in Al, Si, Cu, Zn, Mn, Ni, Co, and Cd relative to As, Cr, Pb, Fe, and S.
The water chemistry and precipitate constituents in areas affected by AMDs at Chinkuashih were mainly influenced by the formation of iron oxyhydroxysulfate minerals and HFO/HAO and sequential co-precipitation or adsorption of trace elements interrelated to changes in solution pH at various stages of water mixing and neutralization. These processes may have reduced and/or deferred environmental impacts made by the Chinkuashih AMDs. However, further investigations and continuous monitoring of the potential influences of desorption, transformation, and/or dissolution of the suspended particulates in Lian-Dong Bay are apparently important.

目錄
摘要 Ⅰ
Abstract Ⅲ
誌謝 Ⅵ
目錄 Ⅶ
表目錄 ⅩⅠ
圖目錄 ⅩⅡ
第一章、緒論 1
第二章、研究方法 6
2.1野外工作 6
2.1.1採樣 6
2.1.2二價鐵與硫酸根濃度之現地量測 7
2.1.3流速與流量 8
2.2水樣之化學組成 8
2.2.1感應耦合電漿光譜元素分析 8
2.2.2離子層析儀分析 9
2.3固樣之礦物學特徵 9
2.3.1Ｘ光繞射分析 9
2.3.2傅利葉轉換紅外線光譜分析 9
2.3.3掃瞄式電子顯微鏡分析 10
2.3.4穿透式電子顯微鏡分析 10
2.4 固樣溶樣成份分析 10
2.5 地化模擬計算 11
第三章、瀑布曝氣及季節性溫度變化對酸性礦山排水系統鐵和砷的衰減率之影響 13
3.1前言 13
3.2研究區域 14
3.3研究方法 17
3.3.1採樣及實地量測 17
3.3.2實驗室分析 17
3.3.3污染物量和反應率計算 17
3.4研究結果與討論 19
3.4.1酸性礦山排水源化學組成 19
3.4.2水化學成份隨下游之變化 22
3.4.3四方硫酸纖鐵礦之礦物學與形成 25
3.4.4反應速率 33
3.4.5速率常數計算 33
3.4.5.1二價鐵氧化速率 33
3.4.5.2四方硫酸纖鐵礦沉澱速率 34
3.4.5.3砷吸收 34
3.4.6二價鐵氧化動力學 34
3.4.7季節溫度和瀑布效果對四方硫酸纖鐵礦沉澱的影響 37
3.4.8四方硫酸纖鐵礦之砷移除作用 38
3.4.9沉澱/吸附量和溶解量 39
3.5結論 42
第四章、金瓜石酸性礦山排水地區四方硫酸纖鐵礦之沉澱及其轉變針鐵礦過程中
元素之分化作用 43
4.1前言 43
4.2研究方法 44
4.2.1採樣 44
4.2.2固樣分析 44
4.3結果 46
4.3.1水合氧化鐵沉澱之礦物學特徵 46
4.3.2沉澱物之化學組成 53
4.4討論 58
4.4.1四方硫酸纖鐵礦之形成及轉變 58
4.4.2四方硫酸纖鐵礦之砷與微量金屬吸附 61
4.4.3四方硫酸纖鐵礦轉變至針鐵礦過程中砷與金屬之遷移 68
4.5結論 71
第五章、海水與酸性礦山排水反應沉澱懸浮粒與海水成份之關係 72
5.1前言 72
5.2研究區域 75
5.3研究方法 75
5.3.1採樣與現場量測 75
5.3.2水樣與固樣分析 76
5.3.3實驗室礦山排水與海水混染實驗 76
5.3.4混染實驗模擬計算 76
5.4結果 77
5.4.1懸浮粒之礦物學特徵 77
5.4.1.1入海口海水懸浮粒 77
5.4.1.2濂洞灣近岸海水懸浮粒 88
5.4.2酸性礦山排水、濂洞溪及陰陽海之水化學特性 89
5.4.3實驗室酸性礦山排水與海水混染產物之礦物學特徵 91
5.4.4實驗室酸性礦山排水與海水混染過程之水化學變化 96
5.5討論 99
5.5.1海水懸浮粒之形成及變化 99
5.5.2懸浮粒之微量元素吸收與共沉澱作用 111
5.5.3懸浮粒之轉變對金屬遷移之影響 113
5.6結論 114
第六章、總結 115
附錄一、利用EXAFS及FTIR光譜探討砷酸根及硫酸根與四方硫酸纖鐵礦結構
之關係 117
1前言 117
2研究方法 119
2.1四方硫酸纖鐵礦之合成 119
2.2砷吸附實驗 119
2.3砷共沉澱實驗 119
2.4固樣與水樣分析 120
2.5同步輻射吸收光譜之延伸性X光吸收精細結構分析 120
3結果 123
3.1四方硫酸纖鐵礦之砷吸附 123
3.2含砷四方硫酸纖鐵礦與非晶質砷酸鐵 129
4討論 135
4.1四方硫酸纖鐵礦之砷吸收能力 135
4.2四方硫酸纖鐵礦之砷吸收機制 137
4.3砷酸根及硫酸根於四方硫酸纖鐵礦結構中之配置 141
5結論 143
參考文獻 144

表目錄
表3-1金瓜石礦區酸性礦山排水及其污染水體之化學特性 20
表3-2金瓜石酸性礦山排水及其污染水體之四方硫酸纖鐵礦及針鐵礦飽和指數 29
表3-3黃金瀑布及濂洞溪總鐵沉澱量及速率、二價鐵氧化速率以及砷與微量金屬移除速率 30
表3-4黃金瀑布段與濂洞溪段二價鐵氧化與四方硫酸纖鐵沉澱之模式速率常數及砷吸收之分配係數 31
表3-5文獻資料計算所得二價鐵氧化與四方硫酸纖鐵沉澱之模式速率常數及砷吸收之分配係數 32
表3-6金瓜石地區流入濂洞灣之污染物傳輸量與流入西班牙Huelva海灣之傳輸量及全球傳輸總量之比較 41
表4-1金瓜石水合氧化鐵沉澱物之化學組成及礦物比例 55
表4-2表層四方硫酸纖鐵礦之化學組成及化學式 56
表4-3金瓜石水合氧化鐵沉澱及其四方硫酸纖鐵礦組成所含元素對鐵之莫耳比值 57
表4-4金瓜石酸性礦山排水沉澱物中砷與微量金屬之濃度係數 65
表4-5金瓜石酸性礦山排水中元素之莫耳濃度及其主要物種之比例 66
表5-1海水懸浮粒之化學組成 87
表5-2金瓜石酸性礦山排水與濂洞灣海水之化學成份 90
表5-3實驗室酸性礦山排水與海水混染水體之水化學成份 97
表5-4濂洞灣海水化學成分對可能沉澱相之飽和指數 104
表5-5酸性礦山排水與海水混染之模擬水體對可能沉澱相之飽和指數 105
表5-6海水懸浮粒所含元素之濃度相對鐵濃度之莫耳比 108
表5-7懸浮粒子成分相對於其採樣點水化學成份計算所得之濃度係數 108
附表1-1砷吸附實驗中四方硫酸纖鐵礦之砷吸收邊緣EXAFS光譜擬合參數值 127
附表1-2砷共沉澱產物之鐵吸收邊緣EXAFS光譜擬合參數值 132
附表1-3砷共沉澱產物之砷吸收邊緣 EXAFS 光譜擬合參數值 134

圖目錄
圖3-1台灣北部金瓜石酸性礦山排水地區之位置圖及水樣採集位置 15
圖3-2台灣北部金瓜石酸性礦山排水地區之野外照片 16
圖3-3金瓜石黃金瀑布至濂洞灣入海口沿線水體化學之變化 24
圖3-4黃金瀑布和濂洞溪基岩表面富鐵沉澱物Ｘ光粉末繞射圖 25
圖3-5金瓜石酸性礦山排水沉澱物之二次電子影像及Ｘ光能量分散光譜 26
圖3-6四方纖鐵礦與四方硫酸纖鐵礦之結構 27
圖4-1台灣北部金瓜石酸性礦山排水地區之沉澱物及鄰近水體採樣位置圖 45
圖4-2金瓜石黃金瀑布景觀及採集之厚層富鐵沉澱殼 45
圖4-3黃金瀑布與濂洞溪富鐵沉澱物之Ｘ光粉末繞射圖 48
圖4-4採樣點G-1P沉澱物中針鐵礦（110）晶面繞射峰之半高寬隨深度之變化 49
圖4-5黃金瀑布與濂洞溪富鐵沉澱物之傅利葉紅外線吸收光譜 50
圖4-6採樣點G-1P不同深度富鐵沉澱物之二次電子影像 51
圖4-7四方硫酸纖鐵礦、針鐵礦及赤鐵礦之穿透式電子顯微鏡影像 51
圖4-8置於黃金瀑布頂層階地之陶瓷板上之四方硫酸纖鐵礦沉澱 52
圖4-9標本G-1P沉澱物之元素/鐵莫耳比及四方硫酸纖鐵礦比例隨深度之變化 67
圖5-1濂洞灣海水與酸性礦山排水混合反應形成大量黃色懸浮粒。 73
圖5-2金瓜石酸性礦山排水、濂洞灣海水及懸浮粒採樣位置圖 74
圖5-3濂洞灣海水懸浮物之Ｘ光粉末繞射圖 79
圖5-4入海口和濂洞灣近岸海水懸浮粒之傅利葉紅外線吸收光譜 80
圖5-5濂洞溪與海水混合所形成懸浮粒之二次電子影像 81
圖5-6本山七坑酸性礦山排水與海水混合所形成懸浮粒之二次電子影像 82
圖5-7濂洞溪與海水混合所形成懸浮粒之穿透式電子顯微影像、電子繞射圖及
Ｘ光能量分散光譜 83
圖5-8本山七坑酸性礦山排水與海水混合所形成懸浮粒穿透式電子顯微影像、
電子繞射圖及Ｘ光能量分散光譜 84
圖5-9本山七坑AMD入海口SR-1海水懸浮粒之穿透式電子顯微影像、STEM影像及其Ｘ光能量分散光譜所得之元素分佈圖 85
圖5-10濂洞灣近岸SR-3海水懸浮粒之穿透式電子顯微影像、STEM影像及其Ｘ光能量分散光譜所得之元素分佈圖 86
圖5-11實驗室AMD與海水混染產物之Ｘ光粉末繞射圖 92
圖5-12實驗室AMD與海水混染產物之傅利葉紅外線吸收光譜 93
圖5-13實驗室AMD與海水混染產物（pH 〈 5.5）之穿透式電子顯微影像、電子繞射圖及Ｘ光能量分散光譜 94
圖5-14實驗室AMD與海水混染產物（pH 〉 5.5）之穿透式電子顯微影像、電子繞射圖及Ｘ光能量分散光譜 95
圖5-15實驗室AMD與海水混染溶液元素移除率隨pH之變化 98
圖5-16酸性礦山排水環境鐵沉澱相之Eh-pH投圖 100
圖5-17 AMD與海水混染區域鐵沉澱相之Eh-pH投圖 101
圖5-18近岸海水環境鐵沉澱相之Eh-pH投圖 102
圖5-19濂洞灣海水環境鋁沉澱相之Eh-pH投圖 103
圖5-20表層沉澱物及海水懸浮粒對AMD中元素富集之能力 104
圖5-21 AMD所含元素之濃度係數隨pH之變化 110
附圖1-1砷氧四面體與（氫氧）氧化鐵礦物鐵氧八面體可能之鍵結型態 118
附圖1-2四方硫酸纖鐵礦之砷吸附量與硫酸根釋放量隨砷濃度之變化 124
附圖1-3合成四方硫酸纖鐵礦吸砷前後X光粉末繞射圖譜之比較 125
附圖1-4砷吸附實驗中四方硫酸纖鐵礦之砷吸收邊緣EXAFS光譜 126
附圖1-5砷吸附實驗中四方硫酸纖鐵礦及砷共沉澱實驗產物之傅利葉紅外線
吸收光譜隨砷含量之變化 128
附圖1-6砷共沉澱實驗產物之X光繞射圖譜 130
附圖1-7砷共沉澱實驗產物之鐵吸收邊緣EXAFS光譜 131
附圖1-8砷共沉澱實驗產物之砷吸收邊緣EXAFS光譜 133
附圖1-9四方硫酸纖鐵礦之結構及其砷吸附機制 136
附圖1-10硫酸根四面體鍵結型態及對稱性差異對傅利葉紅外線吸收光譜振動膜分離程度之影響 141

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