臺灣博碩士論文加值系統

造山帶榴輝岩為基性火成岩於板塊聚合帶受高溫–高壓變質作用所形成，其成份受控於原岩性質及變質作用。許多研究致力於探討海洋型榴輝岩成份變化，以瞭解隱沒帶元素之遷移能力及分化特性。相對而言，在大陸板塊隱沒環境，其含水量較低且可達較高之變質溫度–壓力，故元素化學行為應異於海洋板塊隱沒環境，然而迄今對於大陸板塊於隱沒及折返過程中元素變化之研究相對較少。中國大陸東部大別–蘇魯縫合帶為典型大陸板塊隱沒形成之超高壓變質岩帶，此區榴輝岩成份變化大且部份岩體具異常之化學特徵，顯示超高壓榴輝岩原岩性質迥異且局部受後期地質作用影響。本研究將探討蘇魯超高壓變質岩帶中，三群榴輝岩之原岩性質及大陸隱沒過程中變質作用對榴輝岩岩象與化學特性之影響。
本研究三群地表樣本包括毛北地區中國大陸科學深鑽探（CCSD）場址西北方之高鈦鐵榴輝岩、東南方之高鋁榴輝岩及青龍山高鋁榴輝岩。毛北地區兩群榴輝岩共同特徵為重稀土元素含量低（[HREE]ch = 1–6）、Sr-Nd同位素落於地函演化陣列、�徛d(220 Ma)為-5.1–0.86及�庴f(220 Ma)為0.2–11.5，顯示此兩群榴輝岩之原岩均為堆晶岩且受大陸地殼混染程度低。蘇魯榴輝岩之原岩年代為新元古代（650–800 Ma），文獻報導同時代揚子板塊內之火成岩部份具島弧岩漿岩特性，但亦有部份岩體為地函柱熔融之產物。通常相對不易變遷之重稀土元素及高場強元素可反映原岩性質，雖然高鈦榴輝岩中高場強元素間分化現象於島弧及大陸裂谷堆晶岩中均有報導，但高鋁榴輝岩之重稀土元素含量即使考慮變質作用影響仍遠低於大陸裂谷堆晶岩範圍。毛北榴輝岩之�徛d(220 Ma)–�庴f(220 Ma)變化與島弧火成岩相似，可進一步證實其原岩為島弧環境。再者，�庴f(750 Ma)–�徛d(750 Ma)變化顯示高鈦鐵榴輝岩之Sm/Nd比值已受變質作用影響，但Lu/Hf比值仍反映原岩性質；而高鋁榴輝岩之高場強元素及稀土元素含量則均受變質作用影響。
毛北地表高鈦鐵榴輝岩特徵為FeOtot（16.7–20.9%）、TiO2（3–4%）含量高、SiO2（38.2–42.8%）含量低，且具高場強元素間分化現象（Ti正異常而Nb-Ta-Zr-Hf負異常），此類特性與CCSD於530–600公尺所採之岩芯樣本相似。本研究之地表高鈦–鐵榴輝岩局部有角閃岩脈發育，而影響榴輝岩全岩之SiO2、Al2O3及輕稀土元素含量。部份樣本SiO2含量偏低為流體作用及變質分異作用富集石榴子石之結果；但樣本中無明顯變質分異作用富集金紅石之現象，且大部分主要元素含量與富鐵輝長岩相似，故其全岩成份主要仍反映原岩性質。此結果可利用質量平衡及結晶模擬方式驗證，CCSD淺層之高鈦及正常型榴輝岩岩芯樣本（318–380及420–470公尺）具玄武岩化學特性，其MgO含量低為岩漿演化晚期之岩漿特性，且Ti/Eu比值與球粒隕石相近並具Nb-Ta-Zr-Hf虧損，此特徵與島弧玄武岩相似。假設此類榴輝岩為初始岩漿並計算與其平衡之堆晶岩化學組成，結果顯示模擬堆晶岩含有∼41%斜長石、∼39%斜輝石、∼8%橄欖石及∼12%鈦鐵氧化物，此礦物比例指示堆晶岩形成於2–8 kb且為岩漿演化晚期之產物。模擬堆晶岩微量元素變化與實際量測之高鈦–鐵榴輝岩相似，證實高場強元素間分化現象及高鈦含量均反映其原岩特性，即島弧環境岩漿演化晚期大量結晶鈦鐵氧化物之富鐵輝長岩。故富鐵輝長岩經變質作用即可使金紅石富集成礦；然而具玄武岩原岩性質之高鈦榴輝岩中，部份樣本TiO2含量超過玄武岩範圍（> 4%），故此類樣本金紅石富集之機制可能與變質分異作用有關。
毛北地表高鋁榴輝岩之Al2O3（18.4–29.2%）及MgO（8.59–11.3%）含量高且具Sr正異常，其原岩應為富斜長石堆晶岩；與石榴子石及綠輝石平衡共存之他形藍晶石即為斜長石於榴輝岩化過程中瓦解所形成。高鋁榴輝岩之Al2O3-SiO2及Al2O3-CaO呈反比趨勢，此特性非富斜長石堆晶岩所有，且部分樣本Al2O3含量已超過堆晶岩範圍（> 26%）代表其全岩成份受變質作用影響。低Al2O3含量樣品之質量平衡計算結果顯示，其原岩為橄欖石蘇長輝長岩。高鋁榴輝岩中藍晶石及黝簾石變質斑晶含石榴子石及綠輝石包裹體，其形成機制與包裹體礦物瓦解有關。此區變質溫壓條件及礦物組合與榴輝岩部分熔融實驗結果不符，但熱力學計算結果顯示黝簾石變質斑晶可於高壓環境下透過流體作用形成，故水岩反應為促使前期礦物瓦解並形成變質斑晶之主因。高鋁榴輝岩依微量元素變化可分作兩群La/Yb、Zr/Sm比值迥異之樣本群，推測兩群榴輝岩微量元素變化亦與形成變質斑晶之流體作用有關。兩群樣本之MgO及Ni含量變化小且Sr-Nd同位素比值相近，故其原岩性質相似且流體來源相同，推測兩群樣本微量元素變化應反映流體成份隨流動距離改變之結果。高壓環境下流體可溶解Al、Si、高場強元素、輕稀土元素及大離子親石元素，當流體近距離遷移時，水岩反應將形成次生含鈣金紅石、鋯石及藍晶石變質斑晶，使此群樣本呈高Zr/Sm及Ti/Gd比值。而流體移動至較遠距離，則使榴輝岩增生藍晶石及黝簾石變質斑晶，並富集輕稀土元素及大離子親石元素。由此可知大陸地殼隱沒過程，榴輝岩受流體作用可造成元素強烈分化，但元素之遷移距離有限，故隱沒帶釋放之元素主要應源自於隱沒沈積物。
青龍山榴輝岩依組構可分作等粒狀、葉理狀及變斑晶狀，各類樣本含不等量角閃石、多矽白雲母及綠簾石/黝簾石含水變質斑晶。其中變斑晶狀榴輝岩之含水變質斑晶含量最高；此類樣本石榴子石呈顆粒狀、環礁狀及變斑晶狀，且均具複雜之化學環帶，成份由高鈣–低鐵漸變為低鈣–高鐵。通常變斑晶狀石榴子石核心成分為高鈣–低鐵，與含水變質斑晶含量較少之等粒狀及葉理狀榴輝岩相似；而低鈣–高鐵石榴子石則常與含水變質斑晶緊鄰，故推測高鈣–低鐵石榴子石形成於峰期變質階段，而低鈣–高鐵成份則與變質斑晶生長有關。變斑晶狀榴輝岩中，環礁狀石榴子石中綠輝石、多矽白雲母及角閃石包裹體與基質中相同礦物相成份相似，有時石榴子石沿基質顆粒邊緣發育，顯示環礁狀石榴子石形成於峰期變質礦物之後。相同樣本中，顆粒狀石榴子石具多個高鈣–低鐵之核，且外圍由低鈣–高鐵成份組成。由以上特徵推測環礁狀石榴子石於後期地質作用階段透過增生及顆粒間接合而形成。熱力學計算結果顯示，不同類型榴輝岩之峰期變質條件均為749–782 oC、31.5–36.0 kb，而變質斑晶生長階段為岩體折返初期之角閃石–榴輝岩相（755–791 oC、18.3–19.8 kb）。通常大陸隱沒板塊折返初期，因快速降壓而釋放大量流體。青龍山地區高壓石英岩脈應形成於此階段，由於其礦物組合與變質斑晶相似，故推斷榴輝岩中變質斑晶為折返初期水岩反應之結果，此推論仍需透過同位素方法驗證。

The orogenic eclogites are metamorphosed from the mafic rocks under high P-T conditions in the collision zone, and their compositions are mainly controlled by the protolith characteristics and metamorphic modifications. Many researches have focused on the chemical variations of oceanic eclogites to investigate the element mobility and fractionation in subduction zone. Contrasting to the oceanic subduction zone, the subducted continental slab is characterized by relatively dry and higher metamorphic grade; therefore, the elemental behaviors should be different between these two settings. However, the chemical variations during subduction and exhumation of continental slab have not been intensively investigated. The Dabie-Sulu ultrahigh-pressure metamorphic belt, located at Eastern China, is a typical continental subduction zone. Eclogites in this region show large compositional variation and anomalies in chemical signatures, reflecting their distinct protolith features and regional metamorphic modification. In this study, three groups of eclogites were investigated to further discuss the impact of protolith features and subducted processes on the chemical and petrographic characteristics of the continental eclogites.
Three groups of surface samples include high Fe-Ti eclogites and high-Al eclogites from northwest and southeast of CCSD (Chinese Continental Scientific Drilling) site near Maobei, and hydrous mineral-rich eclogites were collected from Qinglongshan. The Maobei eclogites have low HREE contents ([HREE]ch = 1–6), Sr-Nd isotopic ratios within the mantle array, εNd(220 Ma) of -5.1–0.86, and εHf(220 Ma) of 0.2–11.5, indicating their protoliths were cumulate rocks with limited extent of crustal contamination. The protoliths of Sulu eclogites are contemporary with the Neoproterozoic magmatisms in the Yangtze Block, which were proposed as “superplume” event related to the rifting of the Rodinia supercontinent or arc-related magmatism. The so-called immobile elements, such as high field strength elements (HFSE) and heavy rare earth elements (HREE), of eclogites usually reflect their protolith origins. The HFSE-decoupling in the high Fe-Ti eclogites can be observed in both arc and rift cumulates; whereas, the low HREE contents of the high-Al eclogites are different from the rift cumulates, even when intensive chemical modification is considered for the samples. The �徛d(220 Ma) and �庴f(220 Ma) values of the Maobei eclogites are similar to those of arc magmatic rocks, further confirming their arc origin. The �徛d(750 Ma)-�庴f(750 Ma) variations show that Lu/Hf ratio in the high Fe-Ti eclogites still reflect their protolith features; however, the Sm/Nd ratio in the high Fe-Ti eclogites and HFSE and HREE contents in the high-Al eclogites are altered during metamorphism.
The surface high Fe-Ti eclogites from Maobei show low SiO2 (38.2�{42.8 %), high iron (16.7�{20.9 %) and TiO2 (3�{4 %) contents, and HFSE decoupling (Ti-enrichment with Nb-Ta-Zr-Hf depletion). These geochemical features are correspondent with the high Fe-Ti eclogites cored by the CCSD project at the depth range of 530�{600 m. The surface high Fe-Ti eclogites were locally developed amphibolitic veins to affect the SiO2, Al2O3, and LREE abundances. Some samples with low SiO2 reflect the combined effect of fluid infiltration and garnet enrichment by metamorphic segregation. Besides, there is no evidence for rutile segregation, and most of major oxide contents of the Maobei high Fe-Ti eclogites are similar to those of ferrogabbros. These results indicate that their compositions mainly reflect the protolith characteristics, which can be proved by the mass balance calculation and crystallization modeling. The normal and high-Ti eclogites cored at the depth of 318�{380 m and 420�{470 m in the CCSD site represent basaltic compositions with low MgO content and Nb-Ta-Zr-Hf depletions, which are typical features of evolved lava in arc setting. Assuming these eclogites as initial melts, the gabbro compositions equilibrated with these basaltic melts can be calculated. The modeled gabbros contain ~41% plagioclase, ~39% clinopyroxene, ~8% olivine, and ~12% Fe-Ti oxides, consistent with crystallization at 2–8 kb and the late stage of magmatic evolution. The modeled results of trace element patterns in gabbros are similar to the high Fe-Ti eclogites studied in this study. This inferred that the HFSE-decoupling is mainly the protolith control, which is related to ferrogabbros with large amounts of Fe-Ti oxides crystallized from evolved basalts in arc setting. The rutile enrichments in eclogites with ferrogabbroic protoliths are resulted from metamorphism. However, some high-Ti eclogites derived from basalts have high TiO2 content (> 4%) exceeding the range of basalt, indicating the role of metamorphic segregation to concentrate rutile.
For the Maobei high-Al eclogites, characterized by high Al2O3 (18.4–29.2 %), MgO (8.6–11.3%) contents, positive Sr anomalies, and the occurrence of kyanite neoblasts in equilibrium with garnet and omphacite, require > 30% cumulate feldspar in their protoliths. However, the inverse Al2O3-SiO2 and Al2O3-CaO correlations and extremely high Al2O3 abundances (> 26 %) of three high-Al samples cannot be explained by the magmatic processes, but most likely reflecting the metamorphic modifications. The results of mass balance calculation from the low-Al samples indicate that their protoliths were olivine gabbronorites. The kyanite and zoisite porphyroblasts with garnet and omphacite inclusions were formed at expense of these inclusion minerals. The P-T conditions and mineral assemblages of the studied eclogites are different from the experiments of eclogite partial melting; whereas, the thermodynamic calculation shows that the zoisite porphyroblasts can be formed by fluid interactions under high pressure conditions. Furthermore, trace element variations between group I eclogites with low La/Yb but high Zr/Sm ratios and group II eclogites with contrasting element ratios are probably related to the fluid interactions. All samples with similar MgO, Ni contents and Sr-Nd isotopic ratios reflect their comparable protolith compositions and the similar sources for interacting fluids. Therefore, the trace element variations in the studied eclogites can be explained by the compositional evolution during fluid migration. Under high-pressure conditions, fluids were enriched in Al, Si, HFSE, REE, and LILE. Upon migration, the fluids first precipitated HFSE into the group I samples, then, LILE and LREE into the group II samples. This model is supported by the occurrence of zoisite porphyroblasts in the group II samples, and interstitial zircon and clusters of small rutile grains along annealed fractures in the group I samples. Our interpretation for the observed compositional variations implies limited element mobility during subduction and exhumation of continental lithosphere, consistent with existing models, which proposed that the chemical flux to metasomatized mantle wedge are mainly from subducted sediments.
The hydrous mineral-rich eclogites from Qinglongshan can be divided into three subgroups with equigranular, foliated, and porphyroblastic textures, respectively. Three groups of samples contain various amounts of hydrous porphyroblasts, i.e., amphibole, phengite, and epidote/zoisite. The porphyroblastic eclogites with highest abundances of hydrous porphyroblasts are composed of granular, atoll, and porphyroblastic garnets, which show complex chemical zoning ranging from high-Ca–low-Fe to low-Ca–high-Fe. Generally, the high-Ca–low-Fe core of garnet porphyroblasts in porphyroblastic eclogites are compositionally similar to garnets in the equigranular and foliated eclogites, which have less abundance of hydrous porphyroblasts. The low-Ca–high-Fe garnets are closely associated with the hydrous minerals, suggesting that the former composition represented the peak metamorphism, but the forming mechanism for the later one was possibly related to the hydrous porphyroblasts. In the porphyroblastic eclogites, the matrix grains of omphacite, phengite, and amphibole and inclusions of those minerals in atoll garnets have similar compositions. Sometimes, garnets are developed along the matrix grain boundaries. These indicate that the atoll garnets were formed after peak metamorphic assemblage. In the same samples, granular garnets contain many cores with high-Ca–low-Fe compositions, and their outer portions are composed of low-Ca–high-Fe compositions. It is supposed that the atoll garnets were formed by overgrowth and coalescence of grains. The peak metamorphic conditions for three subgroups of eclogites are 49–782 oC and 31.5–36.0 kb; subsequently, the porphyroblasts are crystallized under amphibole-eclogite facies (755–791 oC and 18.3–19.8 kb) during early exhumation stage. Generally, fluids were released from the subducted continental slab during early exhumation stage because of the rapid decompression. In Qinglongshan area, the high-pressure quartz veins formed at this stage contain similar minerals to the porphyroblastic assemblage in eclogites; therefore, the porphyroblast formation is probably related to the fluid-rock interaction during early exhumation stage. This explanation should be further verified by using the isotopic signatures.

Table of Contents
Chapter 1 Introduction…………………………………………………………1
1.1 Ultra-high pressure metamorphism and continental subduction………………1
1.2 Reconstruction of protolith environment for eclogites…………………………4
1.3 Implications of eclogite compositions on the element behaviors in the subduction zone………………………………………………………………5
1.4 Geological setting and samples…………………………………………………7
1.5 Aims of the study………………………………………………………………11
Chapter 2 Analytical Method…………………………………………………13
2.1 Mineral compositions…………………………………………………………13
2.2 Bulk major element compositions……………………………………………14
2.3 Bulk trace element compositions………………………………………………15
2.4 Sr and Nd isotopes……………………………………………………………16
2.5 Hf isotope………………………………………………………………………16
Chapter 3 Compositions of high Fe-Ti eclogites from the Sulu UHP metamorphic terrane, China: HFSE decoupling and protolith characteristics………………………………………………………20
3.1 Petrographic descriptions………………………………………………………20
3.2 Results…………………………………………………………………………23
3.2.1 Mineral compositions……………………………………………………23
3.2.2 Bulk major and trace element compositions………………………………29
3.3 Discussion……………………………………………………………………31
3.3.1 Factors controlling bulk compositions of the analyzed high Fe-Ti eclogites: protolith or process control? ………………………………………………31
3.3.2 Compositions and proportions of minerals in gabbroic protoliths: major element constraints………………………………………………………33
3.3.3 Trace element compositions of the protoliths: constraints from crystallization modeling…………………………………………………36
3.3.4 Causes of decoupling between Ti and other HFSEs……………………….40
3.3.5 Is the high TiO2 (> 5%) in CCSD eclogites magmatic or metamorphic origin? …………………………………………………………………41
3.4 Summary…………………………………………………………………42
Chapter 4 Kyanite formation and element fractionation in the high-Al eclogites from the Sulu UHP metamorphic terrane…45
4.1 Petrographic descriptions……………………………………………………45
4.2 Results………………………………………………………………………49
4.2.1 Mineral compositions, equilibrium P-T, and zoisite formation reaction…49
4.2.2 Bulk compositions…………………………………………………………55
4.2.3 Sr-Nd-Hf isotopic ratios…………………………………………………59
4.3 Discussion……………………………………………………………………62
4.3.1 Mechanisms and timing for kyanite and zoisite formation………………62
4.3.2 Protolith characteristics…………………………………………………65
4.3.3 Metamorphic modifications on bulk compositions………………………69
4.3.4 Implications on element fractionations in eclogites………………………75
4.3.5 Hf-Nd isotope systematics: evidence for precursor signatures and element fractionation caused by metamorphism……………………………77
4.4 Summary……………………………………………………………………81
Chapter 5 The chemical zoning and metamorphic conditions for garnet porphyroblasts in the Qinglongshan eclogites…………………83
5.1 Sample descriptions…………………………………………………………83
5.2 Results and discussion……………………………………………………87
5.2.1 Mineral compositions…………………………………………………87
5.2.2 Garnet zoning and the forming mechanisms for atoll and porphyroblastic garnets…………………………………………………………………91
5.2.3 Estimation of P-T conditions…………………………………………95
5.3 Summary…………………………………………………………………100
Chapter 6 Conclusions…………………………………………………………101
References………………………………………………………………………103

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