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研究生： 王博賢
Wang, Bo-Shian
論文名稱： 珊瑚骨骼硼同位素記錄與其環境意義
Environmental Significance of the Boron Isotopic Composition in Coral Skeletons
指導教授： 游鎮烽
You, Chen-Feng
學位類別： 碩士
Master
系所名稱： 理學院 - 地球科學系
Department of Earth Sciences
論文出版年： 2005
畢業學年度： 93
語文別： 中文
論文頁數： 87
中文關鍵詞： 珊瑚 、黑潮 、硼同位素
外文關鍵詞： coral, Kuroshio Current, Boron isotope
相關次數： 點閱：89  下載：3 
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    • 　　溫室氣體中的二氧化碳與全球氣候變遷環環相扣，而海洋是地表二氧化碳主要的儲庫。海水硼同位素可作為pH值或pCO2的指標，因此藉由海洋生物性碳酸鈣中的硼同位素記錄，有機會了解過去海洋二氧化碳濃度的變化。本研究改良硼微昇華純化技術，取代繁雜的樹脂管柱程序，並有效去除有機質及大部分的鹽類。同位素分析則發展Cs2BO2+正離子質譜術，目前樣品硼需要量達250ng水準。以國際標準樣品NIST951測試，硼同位素比值11B/10B = 4.0519 (2σm = ± 0.09‰，n = 33)，符合世界主要實驗室測值，且樣品經純化及濃縮步驟後，硼同位素比值不變。實驗室內標準珊瑚樣品經微昇華與濃縮步驟後， 11B/10B = 4.1517 (2σm = ± 0.19‰, n = 7)，以NIST951為標準樣品換算，其δ11B = 24.66‰。實際應用於自然界樣品，分析綠島Porites sp.珊瑚骨骼的硼、氧及碳同位素，配合水文資料及Sr/Ca溫度，探討影響骨骼硼同位素變化的可能因素。研究結果顯示1988年至1990年δ11B分佈從21.3‰至29.1‰，平均，換算成相對應pH值，範圍從pH = 7.6到pH = 8.3；δ18O平均為-4.81‰，δ13C平均為-2.94‰，與世界其他地區珊瑚骨骼的氧、碳同位素比值相近。硼同位素與溫度及碳同位素呈現夏高冬低的週期起伏，而氧同位素則無明顯的季節性變化。研究結果推論珊瑚骨骼硼同位素變化可能主要與季節性黑潮的擺盪、菲律賓海與南海水團的分佈以及湧升流強度的變化有關，重以溫度驅動，使得夏季海水pCO2高於冬季，造成微環境海水在夏季有較高的pH值；此外短期的氣候事件（如聖嬰、反聖嬰事件）亦可能加劇季節性pH值的變化。至於生機效應的貢獻需要更進一步研究釐清。另外，骨骼碳同位素經修正動力學效應後顯示共生藻在夏季光合作用的時間或效率較高；而氧同位素則主要受溫度及動力學效應影響。

    　Carbon dioxide is one of the most important greenhouse gases tightly linking to the global climatic variation. Geochemical investigations have demonstrated that boron isotope in marine carbonates is the only validated record to understand pH or pCO2 of seawater in the past. In this study, coral skeleton collected from an offshore islet, Lutao, southeastern Taiwan, was used for high precision trace element and stable isotope (C, O and B) analyses. We modified the micro-sublimation technique for boron separation and purification, which was manifested not only to avoid the complicated resin procedures but also to eliminate most of the organic matter and salt interferences. A modified Cs2BO2+ TIMS technique was developed for boron isotopic analyses with precision of 0.09‰ and 0.19‰ for NBS951 (11B/10B = 4.0519, 2σm = ± 0.09‰，n = 33) and a coral standard (11B/10B = 4.1517, 2σm = ± 0.19‰, n = 7) respectively and applied successfully for 30 coral determination. The δ11B in Lutao coral skeleton varies largely from 21.3 to 29.1‰ during 1988 to 1990 (from pH = 7.6 to 8.3) with a mean value of 24.0‰. These results display strong seasonal variability, which is similar to the variation of carbon isotope and monthly average temperature. Interestingly, the variation of oxygen isotope is much smaller and shows no effect of seasonality. The boron isotopic composition of Lutao coral skeletons are affected mainly by: (1) variation of seawater pCO2 as a result of seasonal influence by intrusion of the Kuroshio Current or local upwelling; (2) short-term climatic event such as El Niño or La Niña; and (3) biological vital effect. The carbon isotopes reflect possible effects of symbiotic photosynthetic activity and the oxygen is mainly influenced both by temperature or kinetic. Future study will focus on laboratory culture experiments to evaluate possible vital artifact in coral skeleton.

    摘要 I Abstract II 誌謝 III 章節目錄 IV 表目錄 VII 圖目錄 VIII ＝ 章節目錄 ＝ 第一章 序論 1.1 研究背景……………………………………………………………………1 1.2 前人研究……………………………………………………………………4 1.2.1 珊瑚骨骼的生長與鈣化……………………………………………4 1.2.2 珊瑚骨骼的螢光…………………………………………………….6 1.2.3 珊瑚骨骼中的微量元素…………………………………………….6 1.2.3.1 Sr/Ca溫度計………………………………………………8 1.2.3.2 Mg/Ca及U/Ca溫度計……………………………………10 1.2.4 珊瑚骨骼中的氧、碳同位素………………………………………10 1.2.5 珊瑚骨骼中的硼同位素…………………………………………11 1.3 研究目的…………………………………………………………………16 第二章 原理 2.1 珊瑚的構造、生理與生長環境……………………………………………17 2.2 珊瑚鈣化與骨骼化學組成的機制………………………………………19 2.3 珊瑚骨骼中的同位素……………………………………………………23 2.3.1 硼同位素…………………………………………………………23 2.3.1.1 硼的同位素分化係數………………………………………24 2.3.1.2 海水硼同位素組成與pH值的關係………………………25 2.3.2 氧同位素…………………………………………………………28 2.3.3 碳同位素…………………………………………………………29 第三章 研究方法 3.1 綠島環境、氣候與水文背景………………………………………………30 3.1.1 地理與地質…………….…………………………………………30 3.1.2 氣候與水文………………………………………………………30 3.2 珊瑚標本的採集與前處理………………………………………………34 3.2.1 標本採集……………………………………………………………34 3.2.2 標本細部取樣………………………………………………………34 3.2.3 標本前處理…………………………………………………………34 3.3 硼同位素分析方法………………………………………………………35 3.3.1 硼同位素質譜分析術的演進………………………………………35 3.3.2 實驗環境……………………………………………………………37 3.3.3 樣品前處理…………………………………………………………39 3.3.4 樣品裝載……………………………………………………………41 3.3.5 Cs2BO2+正離子硼同位素分析……………………………………41 3.3.6 重複（duplicate）檢驗……………………………………………42 3.4 氧、碳同位素分析方法…………………………………………………43 第四章 實驗結果與討論 4.1 技術評估…………………………………………………………………45 4.1.1 樹脂回收率測試…………………………………………………45 4.1.2 微昇華及濃縮回收率測試………………………………………...45 4.1.3 硼正離子質譜分析術之評估……………………………………...47 4.1.4 珊瑚骨骼清洗程序評估（氧、碳同位素前處理）…………………47 4.1.5 綠島珊瑚骨骼硼同位素重複分析………………………………50 4.2 珊瑚標本的生長速率、螢光與同位素分析………………………………50 4.2.1 骨骼x-ray與螢光分析…………………………………………50 4.2.2骨骼硼、氧及碳同位素……………….……………………………51 4.3 硼、氧及碳同位素主控制因子解析……………………………………56 4.3.1 溫度對硼同位素的效應.….………………………………………56 4.3.2 鹽度對氧同位素的貢獻……………………………………………57 4.3.3 基礎生產力變化對海水碳同位素的影響…………………………60 4.3.4 碳同位素動力學效應的修正………………………………………60 4.4 影響珊瑚骨骼硼同位素變化的因素……………………………………62 4.4.1 季節性洋流及水團的變化…………………………………………64 4.4.1.1 黑潮的特性…………………………………………………64 4.4.1.2 季節性黑潮變化對海水pH值的影響……………………65 4.4.2 海水的二氧化碳分壓（pCO2）……………………………………67 4.4.2.1 海洋pCO2的變化機制……………………………………67 4.4.2.2 西菲律賓海與南海季節性pCO2的變化…………………67 4.4.3 湧升流的作用………………………………………………………71 4.4.4 短期氣候事件………………………………………………………71 4.4.4.1 聖嬰與反聖嬰現象…………………………………………71 4.4.4.2 反聖嬰現象對海洋pH值/ pCO2的影響…………………74 4.5 綠島柴口珊瑚骨骼硼同位素對於環境的意義…………………………75 第五章 結論………………………………………………………………………76 參考文獻…………………………………………………………………………78 ＝ 表目錄 ＝ 表1-1、常見珊瑚骨骼環境記錄指標…………………………………………………5 表2-1、文獻中以實驗或計算得到硼的同位素分化係數………………………24 表3-1、硼同位素主要分析技術比較……………………………………………38 表3-2、陰離子交換樹脂Amberlite IRA-743純化試劑的程序……………………38 表4-1、微昇華純化技術回收評估…………………………………………………46 表4-2、世界主要實驗室Cs2BO2+分析技術比較…………………………………48 表4-3、兩種清洗方式的氧、碳同位素比值無明顯差異…………………………47 表4-4、柴口珊瑚岩芯標本的年生長速率………………………………………52 表4-5、現生珊瑚的硼濃度與同位素文獻資料……………………………………53 表4-6、硼在不同溫度下的分化係數……………………………………………56 ＝ 圖目錄 ＝ 圖1-1、冰芯二氧化碳濃度變化記錄與硼同位素氣候重建應用……………………3 圖1-2、水箱養殖實驗：水溫與骨骼生長速率之關係………………………………7 圖1-3、澳洲大堡礁珊瑚螢光強度與河水逕流量的關係…………………………7 圖1-4、以SIMS分析珊瑚骨骼Sr/Ca比值探討微環境的生機效應……………9 圖1-5、氧、碳同位素的動力學效應修正原理…………………………………12 圖1-6、早全新世有孔蟲硼同位素記錄…………………………………………12 圖1-7、實驗室養殖珊瑚骨骼硼、碳同位素隨光度、餵食量及深度的變化………14 圖1-8、高解析珊瑚骨骼硼氧同位素記錄………………………………………15 圖2-1、珊瑚蟲主要結構特徵……………………………………………………18 圖2-2、”Trans Calcification Mechanism”模型…………………………………18 圖2-3、全球珊瑚礁分佈…………………………………………………………21 圖2-4、珊瑚得到骨骼中微量元素對海水的分配係數……………………………21 圖2-5、骨骼微環境中可能的離子傳輸或交換途徑………………………………22 圖2-6、水體中兩種型態硼濃度及其同位素比值隨pH值的變化………………27 圖3-1、綠島地質圖…………………………………………………………………31 圖3-2、綠島海域溫度、鹽度及密度隨深度的變化…………………………………32 圖3-3、綠島北面的海水溫鹽圖……………………………………………………32 圖3-4、衛星拍攝台灣附近海域冬季季節性平均海水表面溫……………………33 圖3-5、衛星拍攝台灣附近海域季節性海洋基礎生產力的變化…………………33 圖3-6、鋸片機使用實體圖…………………………………………………………36 圖3-7、微採樣用三維立體鋸台……………………………………………………36 圖3-8、Class 10工作箱……………………………………………………………40 圖3-9、微昇華純化技術…………………………………………………………40 圖3-10、成功大學TIMS實機圖………………………………………………44 圖3-11、成功大學IRMS實機圖………………………………………………44 圖4-1、Amberlite IRA-743陰離子交換樹脂對硼回收率測試………………….46 圖4-2、以Cs2BO2+ TIMS質譜術分析國際標準樣品NIST 951………………49 圖4-3、以Cs2BO2+ TIMS質譜術分析實驗室內標準珊瑚樣品…………………49 圖4-4、珊瑚骨骼硼同位素重複分析的結果………………………………………50 圖4-5、骨骼螢光與x-ray攝影……………………………………………………52 圖4-6、各文獻珊瑚骨骼硼同位素比值分佈之比較……………………………53 圖4-7、骨骼硼、氧、碳同位素與海表溫異常隨時間的變化………………………54 圖4-8、移動平均後硼、氧、碳同位素與海表溫異常隨時間的變化………………55 圖4-9、溫度對硼同位素的分化效應………………………………………………58 圖4-10、氧同位素換算為鹽度後隨時間的變化…………………………………58 圖4-11、綠島周圍海域實測鹽度資料……………………………………………59 圖4-12、台東成功自1971至2000年的平均逐月雨量變化……………………59 圖4-13、碳同位素動力學效應的修正……………………………………………61 圖4-14、硼同位素與動力學效應修正之碳同位素隨時間的變化…………………63 圖4-15、硼同位素對動力學效應修正後碳同位素相關性比較…………………63 圖4-16、綠島柴口珊瑚骨骼所記錄微環境pH值隨時間的變化………………64 圖4-17、台灣附近海域水深30公尺平均流矢圖…………………………………66 圖4-18、OR 266、 287及 316航次海水垂直剖面pH值隨深度的變化……66 圖4-19、1995年全球表層海水季節性二氧化碳分壓的變化……………………68 圖4-20、北太平洋二氧化碳通量的季節性變化…………………………………69 圖4-21、全球二氧化碳通量季節性分佈……………………………………………69 圖4-22、南海SEATS站混合層時間序列之TCO2/NTCO2及fCO2………………70 圖4-23、南海ΔfCO2的時間序列變化……………………………………………70 圖4-24、西北太平洋自赤道至中緯海域的海水與大氣pCO2……………………72 圖4-25、台灣東南海域2002年七月，pH值隨深度的變化………………………72 圖4-26、El Niño及La Niña的發生時，全球各地氣候異常的現象………………73 圖4-27、正常年、聖嬰與反聖嬰年大氣及海洋環流變化…………………………74 圖4-28、海洋-大氣季節性的碳循環變化與控制因子……………………………75

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