本研究發展一化學序列萃取技術，有效提取海洋沉積物中的自生性鐵錳氧化物及反吸附回沉積物顆粒中的自生性鉿元素，用以追溯古氣候及古海洋循環歷史。為了解南海海盆的擴張歷史，研究樣本取自南海ODP site 1148岩心，藉由高解析感應耦合電漿質譜儀(HR-ICPMS)及四極式感應耦合電漿質譜儀(Q-ICPMS)分析稀土元素濃度，以PAAS標準化後顯示中稀土元素富集(或稱中稀土元素異常)的現象，符合前人對於深海水團中自生鐵錳氧化物稀土組成的結果。
此外，此稀土元素模型亦可驗證萃取方法並未受到沉積物殘留相的汙染。岩心釹同位素εNd值在過去三千萬年以來約座落於-7.6至-5.1之間；而自約一千萬年起，釹同位素數值從-7.2上升至-5.2，與文獻中太平洋海底錳核及印度洋深海岩心萃取後所建立之記錄反映相同趨勢，推測受印尼海峽的關閉，使得來自印度洋深層海水較低εNd的貢獻漸少所導致。
結合釹和鉿同位素系統的指示，南海深水化學組成主要受到「印度洋」及「南太平洋」深部水團的影響；而在印尼海峽關閉後，由於受到太平洋底層水水團混合比例的改變及深水團傳輸途徑的改變，使得北太平洋、印度洋和南海深部水團的釹同位素及鉿同位素訊號都有大幅升高的趨勢。

This study aims to develop a robust sequential leaching technique for extracting Nd isotopes in the Fe-Mn oxide coatings. The sediment core, ODP site 1148, was selected to study the seawater isotopic evolution of the South China Sea (SCS) since 30 Ma years ago. The distribution of the PAAS-normalized REE pattern from the extracted fraction displays a clear MREE-enriched pattern, which reveals a strong authigenic Fe-Mn oxyhydroxides in marine sediments. Tracings of the source and variability of deep-water mass shifting can be achieved by applying the Nd and Hf evidence of deep-water signal, and significantly deviates from the detrital phase.
The seawater Nd isotope composition of the Fe–Mn oxyhydroxides fraction from the SCS indicates that the flow paths of deep-water masses had changed significantly over the last 30 Ma, and showed an isotopic variation of seawater εNd in the SCS from -5.1 to -7.6. Of special interest is that a gradual increase of εNd from -7.2 to -5.2 can be found during the closure of Indonesian gateway at 10 Ma, further suggesting the potential linkage between ocean circulation and tectonic evolution. In combination of the Nd-Hf isotope system, the main pathway of the deep-water mass to the SCS might be dominated by the water masses of Indian and South Pacific Ocean at 30 Ma, followed by a shift toward the North Pacific signals during the reduction of the Indonesian-Australian Passage.

壹、中文文獻
林雅惠 (2009) 四萬年來南海深海水團之循環：沉積物中鐵錳氫氧化物的釹同位素。國立成功大學地球科學研究所碩士論文。

徐偉倫 (2009) 南海深層水流量之探討。國立台灣大學理學院海洋研究所碩士論文。

劉重強,吳佳紅,于文輝. 氫氧化鐵膠體/水介面作用與地表水中稀土元素的分異-pH控制機理的實驗研究，中國科學(D輯)，第31卷，第10期，2001年10月。

貳、英文文獻
Albarede, F., Simonetti, A., Vervoort, J.D., Blichert-Toft, J., Abouchami, W., 1998. A Hf-Nd isotopic correlation in ferromanganese nodules. Geophysical Research Letters, 25(20): 3895-3898.
Alibo, D.S., Nozaki, Y., 2000. Dissolved rare earth elements in the South China Sea: Geochemical characterization of the water masses. Journal of Geophysical Research-Oceans, 105(C12): 28771-28783.
Amakawa, H., Alibo, D.S., Nozaki, Y., 2000. Nd isotopic composition and REE pattern in the surface waters of the eastern Indian Ocean and its adjacent seas. Geochimica Et Cosmochimica Acta, 64(10): 1715-1727.
Anderson, R.F., Bacon, M.P., Brewer, P.G., 1983. Removal of230Th and231Pa from the open ocean. Earth and Planetary Science Letters, 62(1): 7-23.
Bacon, M.P., Roether, W., Elderfield, H., 1988. Tracers of Chemical Scavenging in the Ocean: Boundary Effects and Large-Scale Chemical Fractionation [and Discussion]. Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences, 325(1583): 147-160.
Balistrieri, L., Brewer, P.G., Murray, J.W., 1981. Scavenging Residence Times of Trace-Metals and Surface-Chemistry of Sinking Particles in the Deep Ocean. Deep-Sea Research Part a-Oceanographic Research Papers, 28(2): 101-121.
Bau, M., Koschinsky, A., 2006. Hafnium and neodymium isotopes in seawater and in ferromanganese crusts: The "element perspective". Earth and Planetary Science Letters, 241(3-4): 952-961.
Bayon, G. et al., 2009. Hf and Nd isotopes in marine sediments: Constraints on global silicate weathering. Earth and Planetary Science Letters, 277(3-4): 318-326.
Bayon, G. et al., 2002. An improved method for extracting marine sediment fractions and its application to Sr and Nd isotopic analysis. Chemical Geology, 187(3-4): 179-199.
Bayon, G., German, C.R., Burton, K.W., Nesbitt, R.W., Rogers, N., 2004. Sedimentary Fe-Mn oxyhydroxides as paleoceanographic archives and the role of aeolian flux in regulating oceanic dissolved REE. Earth and Planetary Science Letters, 224(3-4): 477-492.
Ben-Avraham, Z., Uyeda, S., 1973. The evolution of the China Basin and the mesozoic paleogeography of Borneo. Earth and Planetary Science Letters, 18(2): 365-376.
Bertram, C.J., Elderfield, H., 1993. The geochemical balance of the rare earth elements and neodymium isotopes in the oceans. Geochimica Et Cosmochimica Acta, 57(9): 1957-1986.
Briais, A., Patriat, P., Tapponnier, P., 1993. Updated Interpretation of Magnetic Anomalies and Seafloor Spreading Stages in the South China Sea: Implications for the Tertiary Tectonics of Southeast Asia. J. Geophys. Res., 98(B4): 6299-6328.
Cane, M.A., Molnar, P., 2001. Closing of the Indonesian seaway as a precursor to east African aridircation around 3-4 million years ago. Nature, 411(6834): 157-162.
Chao, L., Hong, F.S., Ping, T., Wang, Z.G., 2004. Effects of rare earth elements on Vigor enhancement of aged spinach seeds. Journal of Rare Earths, 22(4): 547-551.
Chao, S.Y., Shaw, P.T., Wu, S.Y., 1996. Deep water ventilation in the South China Sea. Deep-Sea Research Part I-Oceanographic Research Papers, 43(4): 445-466.
Chester, R., Hughes, M.J., 1967. A chemical technique for the separation of ferro-manganese minerals, carbonate minerals and adsorbed trace elements from pelagic sediments. Chemical Geology, 2: 249-262.
Clift, P., Il Lee, J., Clark, M.K., Blusztajn, J., 2002. Erosional response of South China to arc rifting and monsoonal strengthening; a record from the South China Sea. Marine Geology, 184(3-4): 207-226.
David, K., Frank, M., O'Nions, R.K., Belshaw, N.S., Arden, J.W., 2001. The Hf isotope composition of global seawater and the evolution of Hf isotopes in the deep Pacific Ocean from Fe-Mn crusts. Chemical Geology, 178(1-4): 23-42.
De Baar, H.J.W., Bacon, M.P., Brewer, P.G., 1983. Rare-earth distributions with a positive Ce anomaly in the Western North Atlantic Ocean. Nature, 301(5898): 324-327.
Elderfield, H., 1982. Marine Geochemistry of the Rare-Earth Elements. Journal of the Geological Society, 139(Sep): 660-660.
Frank, M., 2002. Radiogenic isotopes: Tracers of past ocean circulation and erosional input. Reviews of Geophysics, 40(1): -.
German, C.R., Klinkhammer, G.P., Edmond, J.M., Mitra, A., Elderfield, H., 1990. HYDROTHERMAL SCAVENGING OF RARE-EARTH ELEMENTS IN THE OCEAN. Nature, 345(6275): 516-518.
Godfrey, L.V. et al., 1997. The Hf isotopic composition of ferromanganese nodules and crusts and hydrothermal manganese deposits: Implications for seawater Hf. Earth and Planetary Science Letters, 151(1-2): 91-105.
Godfrey, L.V., White, W.M., Salters, V.J.M., 1996. Dissolved zirconium and hafnium distributions across a shelf break in the northeastern Atlantic Ocean. Geochimica Et Cosmochimica Acta, 60(21): 3995-4006.
Gourlan, A.T., Meynadier, L., Allègre, C.J., 2008. Tectonically driven changes in the Indian Ocean circulation over the last 25 Ma: Neodymium isotope evidence. Earth and Planetary Science Letters, 267(1-2): 353-364.
Greaves, M.J., Elderfield, H., 1994. Rare-Earth Elements in the Mediterranean-Sea and Mixing in the Mediterranean Outflow - Reply. Earth and Planetary Science Letters, 121(3-4): 663-664.
Gutjahr, M., Frank, M., Stirling, C.H., Keigwin, L.D., Halliday, A.N., 2008. Tracing the Nd isotope evolution of North Atlantic deep and intermediate waters in the Western North Atlantic since the Last Glacial Maximum from Blake Ridge sediments. Earth and Planetary Science Letters, 266(1-2): 61-77.
Gutjahr, M. et al., 2007. Reliable extraction of a deepwater trace metal isotope signal from Fe-Mn oxyhydroxide coatings of marine sediments. Chemical Geology, 242(3-4): 351-370.
Haley, B.A., Klinkhammer, G.P., McManus, J., 2004. Rare earth elements in pore waters of marine sediments. Geochimica Et Cosmochimica Acta, 68(6): 1265-1279.
Hall, R., 2002. Cenozoic geological and plate tectonic evolution of SE Asia and the SW Pacific: computer-based reconstructions, model and animations. Journal of Asian Earth Sciences, 20(4): 353-431.
Hannigan, R.E., Sholkovitz, E.R., 2001. The development of middle rare earth element enrichments in freshwaters: weathering of phosphate minerals. Chemical Geology, 175(3-4): 495-508.
Jacobsen, S.B., Wasserburg, G.J., 1980. Sm-Nd isotopic evolution of chondrites. Earth and Planetary Science Letters, 50(1): 139-155.
Jeandel, C., Bishop, J.K., Zindler, A., 1995. Exchange of neodymium and its isotopes between seawater and small and large particles in the Sargasso Sea. Geochimica Et Cosmochimica Acta, 59(3): 535-547.
Johannesson, K.H., Burdige, D.J., 2007. Balancing the global oceanic neodymium budget: Evaluating the role of groundwater. Earth and Planetary Science Letters, 253(1-2): 129-142.
Koeppenkastrop, D., Decarlo, E.H., 1993. Uptake of Rare-Earth Elements from Solution by Metal-Oxides. Environmental Science & Technology, 27(9): 1796-1802.
Lacan, F., Jeandel, C., 2001. Tracing Papua New Guinea imprint on the central Equatorial Pacific Ocean using neodymium isotopic compositions and Rare Earth Element patterns. Earth and Planetary Science Letters, 186(3-4): 497-512.
Lacan, F., Jeandel, C., 2005. Acquisition of the neodymium isotopic composition of the North Atlantic Deep Water. Geochemistry Geophysics Geosystems, 6.
Li, Q.Y., Han, Z.M., Su, X., 2005a. Late Oligocene rapid transformations in the South China Sea. Marine Micropaleontology, 54(1-2): 5-25.
Li, Q.Y. et al., 2006. A 33 Ma lithostratigraphic record of tectonic and paleoceanographic evolution of the South China Sea. Marine Geology, 230(3-4): 217-235.
Li, Q.Y. et al., 2007a. Deepwater ventilation and stratification in the Neogene south China Sea. Journal of China University of Geosciences, 18(2): 95-108.
Li, T.G. et al., 2007b. Evolution and variation of the Tsushima warm current during the late Quaternary: Evidence from planktonic foraminifera, oxygen and carbon isotopes. Science in China Series D-Earth Sciences, 50(5): 725-735.
Li, T.G., Xiang, R., Sun, R.T., Cao, Q.Y., 2005b. Benthic foraminifera and bottom water evolution in the middle-southern Okinawa Trough during the last 18 ka. Science in China Series D-Earth Sciences, 48(6): 805-814.
Li, X.H. et al., 2003. Geochemical and Nd isotopic variations in sediments of the South China Sea: a response to Cenozoic tectonism in SE Asia. Earth and Planetary Science Letters, 211(3-4): 207-220.
Li, Y.H., 1991. Distribution Patterns of the Elements in the Ocean - a Synthesis. Geochimica Et Cosmochimica Acta, 55(11): 3223-3240.
Ling, H.F. et al., 1997. Evolution of Nd and Pb isotopes in Central Pacific seawater from ferromanganese crusts. Earth and Planetary Science Letters, 146(1-2): 1-12.
Liu, Q.Y., Kaneko, A., Su, J.L., 2008a. Recent progress in studies of the South China Sea circulation. Journal of Oceanography, 64(5): 753-762.
Liu, Z.F. et al., 2007. Climatic and tectonic controls on weathering in south China and Indochina Peninsula: Clay mineralogical and geochemical investigations from the Pearl, Red, and Mekong drainage basins. Geochemistry Geophysics Geosystems, 8: -.
Liu, Z.F. et al., 2008b. Detrital fine-grained sediment contribution from Taiwan to the northern South China Sea and its relation to regional ocean circulation. Marine Geology, 255(3-4): 149-155.
Lu, Y., Makishima, A., Nakamura, E., 2007. Purification of Hf in silicate materials using extraction chromatographic resin, and its application to precise determination of Hf-176/Hf-177 by MC-ICP-MS with Hf-179 spike. Journal of Analytical Atomic Spectrometry, 22(1): 69-76.
Ludmann, T., Wong, H.K., 1999. Neotectonic regime on the passive continental margin of the northern South China Sea. Tectonophysics, 311(1-4): 113-138.
Ludmann, T., Wong, H.K., Berglar, K., 2005. Upward flow of North Pacific Deep Water in the northern South China Sea as deduced from the occurrence of drift sediments. Geophysical Research Letters, 32(5): -.
Ludmann, T., Wong, H.K., Wang, P.X., 2001. Plio-Quaternary sedimentation processes and neotectonics of the northern continental margin of the South China Sea. Marine Geology, 172(3-4): 331-358.
Martin, E.E. et al., 2010. Extraction of Nd isotopes from bulk deep sea sediments for paleoceanographic studies on Cenozoic time scales. Chemical Geology, 269(3-4): 414-431.
McKelvey, B.A., Orians, K.J., 1998. The determination of dissolved zirconium and hafnium from seawater using isotope dilution inductively coupled plasma mass spectrometry. Marine Chemistry, 60(3-4): 245-255.
Morton, B., Blackmore, G., 2001. South China sea. Marine Pollution Bulletin, 42(12): 1236-1263.
Nowell, G.M. et al., 1998. High precision Hf isotope measurements of MORB and OIB by thermal ionisation mass spectrometry: insights into the depleted mantle. Chemical Geology, 149(3-4): 211-233.
Nozaki, Y., 2000. RARE EARTH ELEMENTS AND THEIR ISOTOPES, Encyclopedia of Ocean Science.
Nozaki, Y., 2001. Rare Earth Elements and their Isotopes in the Ocean. In: John, H.S. (Ed.), Encyclopedia of Ocean Sciences. Academic Press, Oxford, pp. 2354-2366.
Nozaki, Y., Alibo, D.S., Amakawa, H., Gamo, T., Hasumoto, H., 1999. Dissolved rare earth elements and hydrography in the Sulu Sea. Geochimica Et Cosmochimica Acta, 63(15): 2171-2181.
Nozaki, Y., Lerche, Alibo, Tsutsumi, 2002. Dissolved indium and rare earth elements in three Japanese rivers and Tokyo Bay: Evidence for anthropogenic Gd and In (vol 64, pg 3975, 2000). Geochimica Et Cosmochimica Acta, 66(20): 3673-3673.
Ohr, M., Halliday, A.N., Peacor, D.R., 1994. Mobility and fractionation of rare earth elements in argillaceous sediments: Implications for dating diagenesis and low-grade metamorphism. Geochimica Et Cosmochimica Acta, 58(1): 289-312.
Piepgras, D.J., Jacobsen, S.B., 1992. THE BEHAVIOR OF RARE-EARTH ELEMENTS IN SEAWATER - PRECISE DETERMINATION OF VARIATIONS IN THE NORTH PACIFIC WATER COLUMN. Geochimica Et Cosmochimica Acta, 56(5): 1851-1862.
Piotrowski, A.M., Goldstein, S.L., Hemming, S.R., Fairbanks, R.G., 2005. Temporal Relationships of Carbon Cycling and Ocean Circulation at Glacial Boundaries. Science, 307(5717): 1933-1938.
Qu, T., Mitsudera, H., Yamagata, T., 2000. Intrusion of the North Pacific waters into the South China Sea. Journal of Geophysical Research-Oceans, 105(C3): 6415-6424.
Rickli, J., 2009. THE HAFNIUM AND NEODYMIUM ISOTOPIC COMPOSITION OF SEAWATER AND RIVERS, ETH Zürich
Rickli, J., Frank, M., Halliday, A.N., 2009. The hafnium-neodymium isotopic composition of Atlantic seawater. Earth and Planetary Science Letters, 280(1-4): 118-127.
Shao, L. et al., 2007a. Deep water bottom current deposition in the northern South China Sea. Science in China Series D: Earth Sciences, 50(7): 1060-1066.
Shao, L. et al., 2004. SEDIMENTARY RECORD OF THE TECTONIC EVOLUTION OF THE SOUTH CHINA SEA SINCE THE OLIGOCENE--Evidence from deep sea sediments of ODP Site 1148. ADVANCES IN EARTH SCIENCE, 19(4).
Shao, L. et al., 2007b. Deep water bottom current deposition in the northern South China Sea. Science in China Series D-Earth Sciences, 50(7): 1060-1066.
Sholkovitz, E.R., Landing, W.M., Lewis, B.L., 1994. Ocean Particle Chemistry - the Fractionation of Rare-Earth Elements between Suspended Particles and Seawater. Geochimica Et Cosmochimica Acta, 58(6): 1567-1579.
Siddall, M., Rohling, E.J., Thompson, W.G., Waelbroeck, C., 2008. Marine isotope stage 3 sea level fluctuations: Data synthesis and new outlook. Rev. Geophys., 46(4): RG4003.
Tachikawa, K., Jeandel, C., Roy-Barman, M., 1999. A new approach to the Nd residence time in the ocean: the role of atmospheric inputs. Earth and Planetary Science Letters, 170(4): 433-446.
Turner, D.R., Whitfield, M., Dickson, A.G., 1981. The equilibrium speciation of dissolved components in freshwater and sea water at 25°C and 1 atm pressure. Geochimica Et Cosmochimica Acta, 45(6): 855-881.
Uematsu, M., Wang, Z.F., Uno, I., 2003. Atmospheric input of mineral dust to the western North Pacific region based on direct measurements and a regional chemical transport model. Geophysical Research Letters, 30(6): -.
van de Flierdt, T., Frank, M., Lee, D.C., Halliday, A.N., 2002. Glacial weathering and the hafnium isotope composition of seawater (vol 198, pg 167, 2002). Earth and Planetary Science Letters, 201(3-4): 639-647.
Van De Flierdt, T. et al., 2004. New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts. Geochimica Et Cosmochimica Acta, 68(19): 3827-3843.
van de Flierdt, T. et al., 2007. Global neodymium-hafnium isotope systematics - revisited. Earth and Planetary Science Letters, 259(3-4): 432-441.
van de Flierdt, T., Hemming, S.R., Goldstein, S.L., Abouchami, W., 2006a. The radiogenic isotope fingerprint of Wilkes Land-Adelie Coast Bottom Water in the Circum-Antarctic Ocean. Geochimica Et Cosmochimica Acta, 70(18): A665-A665.
van de Flierdt, T., Hemming, S.R., Goldstein, S.L., Abouchami, W., 2006b. Radiogenic isotope fingerprint of Wilkes Land - Adelie Coast Bottom Water in the circum-Antarctic Ocean. Geophysical Research Letters, 33(12).
Vervoort, J.D., Patchett, P.J., Blichert-Toft, J., Albarede, F., 1999. Relationships between Lu-Hf and Sm-Nd isotopic systems in the global sedimentary system. Earth and Planetary Science Letters, 168(1-2): 79-99.
Wang, P. et al., 2003a. Evolution of the South China Sea and monsoon history revealed in deep-sea records. Chinese Science Bulletin, 48(23): 2549-2561.
Wang, P.X. et al., 2003b. Evolution of the South China Sea and monsoon history revealed in deep-sea records. Chinese Science Bulletin, 48(23): 2549-2561.
Wang, Z.L., Liu, C.Q., Han, G.L., Zhu, J.M., 2000. ADVANCES IN RESEARCH ON GEOCHEMISTRY OF RARE EARTH ELEMENTS IN RIVERS. Advences in Earth Sciences 15(5): 553-558.
Wei, G., Li, X.H., Liu, Y., Shao, L., Liang, X.R., 2006. Geochemical record of chemical weathering and monsoon climate change since the early Miocene in the South China Sea. Paleoceanography, 21(4): -.
Wyrtki, K., 1961. Physical Oceanography of the Southeast Asian waters . UC San Diego: Scripps Institution of Oceanography.
Xue, H.J. et al., 2004. Kuroshio intrusion and the circulation in the South China Sea. Journal of Geophysical Research-Oceans, 109(C2): -.
Zhang, Y., Lacan, F., Jeandel, C., 2008. Dissolved rare earth elements tracing lithogenic inputs over the Kerguelen Plateau (Southern Ocean). Deep-Sea Research Part Ii-Topical Studies in Oceanography, 55(5-7): 638-652.
Zimmermann, B. et al., 2009. The hafnium isotope composition of Pacific Ocean water. Geochimica Et Cosmochimica Acta, 73(1): 91-101.