在古環境變遷研究中，由於海洋生物性碳酸鈣的硼同位素組成可反映古海水pH值變化，因此對於瞭解大氣與海洋CO2的交換過程及與氣候變遷的關係，精確的硼同位素量測技術是極為重要的一項地化指標。本研究以多接收器感應耦合電漿質譜儀(MC-ICP-MS)的方法精確量測珊瑚骨骼中硼同位素比值。MC-ICP-MS的優點包含了所需的樣品量遠低於正離子源質譜術，且分析精度皆明顯優於傳統量測生物性碳酸鈣硼同位素的熱游離質譜術。本研究利用國際珊瑚標準品（JCp-1）和實驗室珊瑚標準品（KTP-1）系統性評估MC-ICP-MS在測量珊瑚骨骼中硼同位素比值的精確度和準確度，以標準品和樣品夾托(standard-sample bracketing)的方式修正儀器所造成的質量偏差，也進一步比較兩種質譜分析術在同位素量測上的結果。研究結果顯示珊瑚硼同位素值長期的分析精確度可優於0.25‰ (2σ, n = 35, [B] < 100ppb)，而利用MC-ICP-MS所測得的硼同位素值與正離子源質譜術之結果完全一致，但有較佳的分析精度及較低的樣品需求量，因此對於低硼自然界樣品提供絕佳的分析利器。
在自然界珊瑚骨骼硼同位素應用上，本研究利用採自台灣東南方蘭嶼的塊狀微孔珊瑚(Porites lobata)岩心作為主要研究對象，所量測得到的硼同位素值在西元1991至1996年間有約2 ‰的年際變化(23.6  25.1 ‰)，此硼同位素變化與澳洲珊瑚海的Flinders Reef 相似。與珊瑚骨骼的碳、氧同位素及Mg/Ca比計算所得到的海水表面溫度相互比較，可發現蘭嶼珊瑚硼同位素比值具有明顯的季節性變化，在溫暖的時期有較低pH值，而在較冷的時期則有高的pH值，此與Takahashi et al. (2002)在西太平洋所觀測到的現代表水pCO2變化相符。此結果進一步證實蘭嶼珊瑚所記錄的硼同位素值可以忠實反映西太平洋海水pH值變化，未來將有助於我們了解全球氣候變遷和表層海水變化的關係及可能的反應。

Boron isotopic compositions in biogenic carbonates are useful proxy for evaluation of oceanic pH in the past. This information is essential for a better understanding of possible mechanisms that controlled global environmental and climatic changes. In this study, a high-precision analytical technique was developed for isotopic determination of boron in coral skeletons using high-resolution multi-collector ICP-MS (MC-ICP-MS, Neptune, Thermo-Fisher). The mass discrimination was corrected by the standard-sample-standard bracketing procedure. The main advantage of the MC-ICP-MS technique is that both of sample throughput and analytical precision are significantly higher than P-TIMS. The accuracy of this technique is further examined by replicated analyses of several international standards and an in-house coral standard, KTP-1, using both MC-ICP-MS and P-TIMS. The long-lived massive coral skeletons (Porites lobata) collected from an offshore Lan-Yu Island, the southeastern Taiwan show annual δ11B variation of around 2 ‰, 23.6 to 25.1 ‰ (n=80) during 1991 to 1996 A.D., which is similar to recent results from Flinders Reef in the Coral Sea. In combination with Mg/Ca-based thermometry, the intra-annual pH record derived from δ11B shows clear seasonal cycles with high pH at cold period, which is in agreement with the modern observation of seawater pCO2 in the western Pacific (TAKAHASHI et al., 2002), indicating that coral δ11B in the Lan-Yu Island record faithfully of seawater pH changes in the west Pacific Ocean, and would assist us to understand relationships between the global climatic change and the potential responses preser in the surface ocean.

Aggarwal, J. K. and Palmer, M. R., 1995. Boron Isotope Analysis - a Review. Analyst 120, 1301-1307.
Aggarwal, J. K., Sheppard, D., Mezger, K., and Pernicka, E., 2003. Precise and accurate determination of boron isotope ratios by multiple collector ICP-MS: origin of boron in the Ngawha geothermal system, New Zealand. Chem Geol 199, 331-342.
Al-Ammar, A., Gupta, R. K., and Barnes, R. M., 1999. Elimination of boron memory effect in inductively coupled plasma-mass spectrometry by addition of ammonia. Spectrochimica Acta Part B-Atomic Spectroscopy 54, 1077-1084.
Al-Ammar, A., Reitznerova, E., and Barnes, R. M., 2000. Improving boron isotope ratio measurement precision with quadrupole inductively coupled plasma-mass spectrometry. Spectrochimica Acta Part B-Atomic Spectroscopy 55, 1861-1867.
Al-Horani, F. A., Al-Moghrabi, S. M., and de Beer, D., 2003. The mechanism of calcification and its relation to photosynthesis and respiration in the scleractinian coral Galaxea fascicularis. Marine Biology 142, 419-426.
Allison, N., Finch, A. A., Webster, J. M., and Clague, D. A., 2007. Palaeoenvironmental records from fossil corals: The effects of submarine diagenesis on temperature and climate estimates. Geochim Cosmochim Ac 71, 4693-4703.
Barth, S., 1997. Boron isotopic analysis of natural fresh and saline waters by negative thermal ionization mass spectrometry. Chem Geol 143, 255-261.
Birck, R., Knoll, T., Braun, C., VanderWoude, F. J., and Rohmeiss, P., 1997. Effects of the selective cyclooxygenase-2 inhibitor meloxicam on renal hemodynamics compared to indomethacin. J Am Soc Nephrol 8, A1584-A1584.
Caldeira, K. and Wickett, M. E., 2003. Anthropogenic carbon and ocean pH. Nature 425, 365-365.
Chaussidon, M., Robert, F., Mangin, D., Hanon, P., and Rose, E. F., 1997. Analytical procedures for the measurement of boron isotope compositions by ion microprobe in meteorites and mantle rocks. Geostandard Newslett 21, 7-17.
Chen, C. T. A., Wang, S. L., Chou, W. C., and Sheu, D. D., 2006. Carbonate chemistry and projected future changes in pH and CaCO3 saturation state of the South China Sea. Mar Chem 101, 277-305.
Chen, Y. L. L., Chen, H. Y., Lin, I. I., Lee, M. A., and Chang, J., 2007. Effects of cold eddy on Phytoplankton production and assemblages in Luzon Strait bordering the South China Sea. J Oceanogr 63, 671-683.
Chou, W. C., Sheu, D. D., Chen, C. T. A., Wen, L. S., Yang, Y., and Wei, C. L., 2007. Transport of the South China Sea subsurface water outflow and its influence on carbon chemistry of Kuroshio waters off southeastern Taiwan. J Geophys Res-Oceans 112, -.
Correge, T., 2006. Sea surface temperature and salinity reconstruction from coral geochemical tracers. Palaeogeogr Palaeocl 232, 408-428.
Erez, J. and Braun, A., 2007. Calcification in hermatypic corals is based on direct seawater supply to the biomineralization site. Geochim Cosmochim Ac 71, A260-A260.
Fallon, S. J., McCulloch, M. T., and Alibert, C., 2003. Examining water temperature proxies in Porites corals from the Great Barrier Reef: a cross-shelf comparison. Coral Reefs 22, 389-404.
Foster, G. L., 2008. Seawater pH, pCO2 and [CO32-] variations in the Caribbean Sea over the last 130 kyr: A boron isotope and B/Ca study of planktic forminifera. Earth Planet Sc Lett 271, 254-266.
Foster, G. L., Ni, Y. Y., Haley, B., and Elliott, T., 2006. Accurate and precise isotopic measurement of sub-nanogram sized samples of foraminiferal hosted boron by total evaporation NTIMS. Chem Geol 230, 161-174.
Gabler, H. E. and Bahr, A., 1999. Boron isotope ratio measurements with a double-focusing magnetic sector ICP mass spectrometer for tracing anthropogenic input into surface and ground water. Chem Geol 156, 323-330.
Gagan, M. K., Chivas, A. R., and Isdale, P. J., 1994. High-Resolution Isotopic Records from Corals Using Ocean Temperature and Mass-Spawning Chronometers. Earth Planet Sc Lett 121, 549-558.
Gagan, M. K., Chivas, A. R., and Isdale, P. J., 1996. Timing coral-based climatic histories using 13C enrichments driven by synchronized spawning. Geology 24, 1009-1012.
Gaillardet, J. and Allegre, C. J., 1995. Boron isotopic compositions of corals: Seawater or diagenesis record? Earth Planet Sc Lett 136, 665-676.
Gaillardet, J., Lemarchand, D., Gopel, C., and Manhes, G., 2001. Evaporation and sublimation of boric acid: Application for boron purification from organic rich solutions. Geostandard Newslett 25, 67-75.
Gattuso, J. P., Allemand, D., and Frankignoulle, M., 1999. Photosynthesis and calcification at cellular, organismal and community levels in coral reefs: A review on interactions and control by carbonate chemistry. American Zoologist 39, 160-183.
Grottoli, A. G., 2002. Effect of light and brine shrimp on skeletal delta C-13 in the Hawaiian coral Porites compressa: A tank experiment. Geochim Cosmochim Ac 66, 1955-1967.
Grottoli, A. G. and Wellington, G. M., 1999. Effect of light and zooplankton on skeletal delta C-13 values in the eastern Pacific corals Pavona clavus and Pavona gigantea. Coral Reefs 18, 29-41.
Hönisch, B. and Hemming, N. G., 2005. Surface ocean pH response to variations in pCO2 through two full glacial cycles. Earth Planet Sc Lett 236, 305-314.
Hönisch, B., Hemming, N. G., Grottoli, A. G., Amat, A., Hanson, G. N., and Buma, J., 2004. Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects. Geochim Cosmochim Ac 68, 3675-3685.
Hemming, N. G., Guilderson, T. P., and Fairbanks, R. G., 1998. Seasonal variations in the boron isotopic composition of coral: A productivity signal? Global Biogeochem Cy 12, 581-586.
Hemming, N. G. and Hanson, G. N., 1992. Boron Isotopic Composition and Concentration in Modern Marine Carbonates. Geochim Cosmochim Ac 56, 537-543.
Hemming, N. G. and Hanson, G. N., 1994. A Procedure for the Isotopic Analysis of Boron by Negative Thermal Ionization Mass-Spectrometry. Chem Geol 114, 147-156.
Hemming, N. G., Reeder, R. J., and Hanson, G. N., 1995. Mineral-Fluid Partitioning and Isotopic Fractionation of Boron in Synthetic Calcium-Carbonate. Geochim Cosmochim Ac 59, 371-379.
Hogan, J. F. and Blum, J. D., 2003. Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill, Staten Island, New York, USA. Applied Geochemistry 18, 615-627.
Hsin, Y. C., Wu, C. R., and Shaw, P. T., 2008. Spatial and temporal variations of the Kuroshio east of Taiwan, 1982-2005: A numerical study. J Geophys Res-Oceans 113, C04002.
Huang, K.-F., 2007. Trace element ratio and isotopic composition of planktonic foraminiferal shell collected from the south china sea: geochemical calibration and paleoceanographic implication, National Cheng Kung University.
IPCC, 2007. Climate Change 2007: Synthesis Report. Contribution of Working Groups I, II and III to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change In: Team, T. C. W., Pachauri, R. K., and Reisinger, A. Eds.). Intergovernmental Panel on Climate Changes, Geneva, Switzerland.
Kakihana, H., Kotaka, M., Satoh, S., Nomura, M., and Okamoto, M., 1977. Fundamental Studies on Ion-Exchange Separation of Boron Isotopes. Bulletin of the Chemical Society of Japan 50, 158-163.
Klochko, K., Kaufman, A. J., Yao, W. S., Byrne, R. H., and Tossell, J. A., 2006. Experimental measurement of boron isotope fractionation in seawater. Earth Planet Sc Lett 248, 276-285.
Lemarchand, D., Gaillardet, J., Gopel, C., and Manhes, G., 2002a. An optimized procedure for boron separation and mass spectrometry analysis for river samples. Chem Geol 182, 323-334.
Lemarchand, D., Gaillardet, J., Lewin, E., and Allegre, C. J., 2000. The influence of rivers on marine boron isotopes and implications for reconstructing past ocean pH. Nature 408, 951-954.
Lemarchand, D., Gaillardet, J., Lewin, E., and Allegre, C. J., 2002b. Boron isotope systematics in large rivers: implications for the marine boron budget and paleo-pH reconstruction over the Cenozoic. Chem Geol 190, 123-140.
Lin, H. L., Wang, L. W., Wang, C. H., and Gong, G. C., 1999. Vertical distribution of delta C-13 of dissolved inorganic carbon in the northeastern South China Sea. Deep-Sea Res Pt I 46, 757-775.
Liu, Y., Liu, W. G., Peng, Z. C., Mao, Y. K., Wei, G. J., Sun, W. D., He, J. F., Liu, G. J., and Chou, C. L., 2009. Instability of seawater pH in the South China Sea during the mid-late Holocene: Evidence from boron isotopic composition of corals. Geochim Cosmochim Ac 73, 1264-1272.
McConnaughey, T. A. and Whelan, J. F., 1997. Calcification generates protons for nutrient and bicarbonate uptake. Earth-Science Reviews 42, 95-117.
NOAA, NOAA's Coral Reef Information System (CoRIS).
Omata, T., Suzuki, A., Kawahat, H., and Okamoto, M., 2005. Annual fluctuation in the stable carbon isotope ratio of coral skeletons: The relative intensities of kinetic and metabolic isotope effects. Geochim Cosmochim Ac 69, 3007-3016.
Orr, J. C., Fabry, V. J., Aumont, O., Bopp, L., Doney, S. C., Feely, R. A., Gnanadesikan, A., Gruber, N., Ishida, A., Joos, F., Key, R. M., Lindsay, K., Maier-Reimer, E., Matear, R., Monfray, P., Mouchet, A., Najjar, R. G., Plattner, G. K., Rodgers, K. B., Sabine, C. L., Sarmiento, J. L., Schlitzer, R., Slater, R. D., Totterdell, I. J., Weirig, M. F., Yamanaka, Y., and Yool, A., 2005. Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms. Nature 437, 681-686.
Ourbak, T., Correge, T., Malaize, B., Le Cornec, F., Charlier, K., and Peypouquet, J. P., 2006. A high-resolution investigation of temperature, salinity, and upwelling activity proxies in corals. Geochemistry Geophysics Geosystems 7, Q03013.
Pagani, M., Lemarchand, D., Spivack, A., and Gaillardet, J., 2005. A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates. Geochim Cosmochim Ac 69, 953-961.
Pagani, M. and Spivack, A., 2007. Response to the Comment by B. Honisch, N.G. Hemming, B. Loose on "A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates". Geochim Cosmochim Ac 71, 1642-1642.
Palmer, M. R. and Pearson, P. N., 2003. A 23,000-year record of surface water pH and PCO2 in the western equatorial Pacific Ocean. Science 300, 480-482.
Palmer, M. R., Spivack, A. J., and Edmond, J. M., 1987. Temperature and Ph Controls over Isotopic Fractionation during Adsorption of Boron on Marine Clay. Geochim Cosmochim Ac 51, 2319-2323.
Palmer, M. R. and Swihart, G. H., 1996. Boron isoyope geochemistry: an overview. In: Crew, E. S. and Anovitz, L. M. Eds.), Boron: Mineralogy, Petrology and Geochemistry Mineral. Soc. Am.
Park, H. and Schlesinger, W. H., 2002. Global biogeochemical cycle of boron. Global Biogeochem Cy 16, 1072.
Pearson, P. N. and Palmer, M. R., 2000. Atmospheric carbon dioxide concentrations over the past 60 million years. Nature 406, 695-699.
Pelejero, C., Calvo, E., McCulloch, M. T., Marshall, J. F., Gagan, M. K., Lough, J. M., and Opdyke, B. N., 2005. Preindustrial to modern interdecadal variability in coral reef pH. Science 309, 2204-2207.
Pelletier, G., Lewis, E., and Wallace, D., 2005. A calculator for the CO2 system in seawater for Microsoft Excel/VBA. Washington State Department of Ecology, Olympia, WA, Brookhaven National Laboratory, Upton, NY.
Quinn, T. M. and Sampson, D. E., 2002. A multiproxy approach to reconstructing sea surface conditions using coral skeleton geochemistry. Paleoceanography 17, 1062.
Reuer, M. K., Boyle, E. A., and Cole, J. E., 2003. A mid-twentieth century reduction in tropical upwelling inferred from coralline trace element proxies. Earth Planet Sc Lett 210, 437-452.
Reynaud-Vaganay, S., Juillet-Leclerc, A., Jaubert, J., and Gattuso, J. P., 2001. Effect of light on skeletal d13C and d18O, and interaction with photosynthesis, respiration and calcification in two zooxanthellate scleractinian corals. Palaeogeogr Palaeocl 175, 393-404.
Reynaud, S., Hemming, N. G., Juillet-Leclerc, A., and Gattuso, J. P., 2004. Effect Of pCO2 and temperature on the boron isotopic composition of the zooxanthellate coral Acropora sp. Coral Reefs 23, 539-546.
Rollion-Bard, C., Chaussidon, M., and France-Lanord, C., 2003. pH control on oxygen isotopic composition of symbiotic corals. Earth Planet Sc Lett 215, 275-288.
Rose, E. F., Chaussidon, M., and France-Lanord, C., 2000. Fractionation of Boron isotopes during erosion processes: The example of Himalayan rivers. Geochim Cosmochim Ac 64, 397-408.
Sanchez-Valle, C., Reynard, B., Daniel, I., Lecuyer, C., Martinez, I., and Chervin, J. C., 2005. Boron isotopic fractionation between minerals and fluids: New insights from in situ high pressure-high temperature vibrational spectroscopic data. Geochim Cosmochim Ac 69, 4301-4313.
Sanyal, A., Bijma, J., Spero, H., and Lea, D. W., 2001. Empirical relationship between pH and the boron isotopic composition of Globigerinoides sacculifer: Implications for the boron isotope paleo-pH proxy. Paleoceanography 16, 515-519.
Sanyal, A., Hemming, N. G., Broecker, W. S., Lea, D. W., Spero, H. J., and Hanson, G. N., 1996. Oceanic pH control on the boron isotopic composition of foraminifera: Evidence from culture experiments. Paleoceanography 11, 513-517.
Sanyal, A., Nugent, M., Reeder, R. J., and Buma, J., 2000. Seawater pH control on the boron isotopic composition of calcite: Evidence from inorganic calcite precipitation experiments. Geochim Cosmochim Ac 64, 1551-1555.
Schwarcz, H. P., Agyei, E. K., and Mccmulle.Cc, 1969. Boron Isotopic Fractionation during Clay Adsorption from Sea-Water. Earth Planet Sc Lett 6.
Shimamura, M., Irino, T., Oba, T., Xu, G. Q., Lu, B. Q., Wang, L. J., and Toyoda, K., 2008. Main controlling factors of coral skeletal carbon isotopic composition and skeletal extension rate: High-resolution study at Hainan Island, South China Sea. Geochemistry Geophysics Geosystems 9, Q04024.
Sinclair, D. J., 1999. High spatial-resolution analysis of trace elements in corals using laser ablation ICP-MS, Australian National University.
Sinclair, D. J., 2005. Correlated trace element "vital effects" in tropical corals: A new geochemical tool for probing biomineralization. Geochim Cosmochim Ac 69, 3265-3284.
Smith, H. J., Spivack, A. J., Staudigel, H., and Hart, S. R., 1995. The boron isotopic composition of altered oceanic crust. Chem Geol 126, 119-135.
Spivack, A. J. and Edmond, J. M., 1986. Determination of Boron Isotope Ratios by Thermal Ionization Mass-Spectrometry of the Dicesium Metaborate Cation. Anal Chem 58, 31-35.
Spivack, A. J. and Edmond, J. M., 1987. Boron Isotope Exchange between Seawater and the Oceanic-Crust. Geochim Cosmochim Ac 51, 1033-1043.
Spivack, A. J., Palmer, M. R., and Edmond, J. M., 1987. The Sedimentary Cycle of the Boron Isotopes. Geochim Cosmochim Ac 51, 1939-1949.
Spivack, A. J., You, C. F., and Smith, H. J., 1993. Foraminiferal Boron Isotope Ratios as a Proxy for Surface Ocean Ph over the Past 21-Myr. Nature 363, 149-151.
Suzuki, A., Hibino, K., Iwase, A., and Kawahata, H., 2005. Intercolony variability of skeletal oxygen and carbon isotope signatures of cultured Porites corals: Temperature-controlled experiments. Geochim Cosmochim Ac 69, 4453-4462.
Sverdrup, K. A., Duxbury, A. C., and Duxbury, A. B., 2005. The benthos: dwellers of the sea floor, An Introduction to the World’s Oceans. Margaret J. Kemp.
Swart, P. K., Leder, J. J., Szmant, A. M., and Dodge, R. E., 1996. The origin of variations in the isotopic record of scleractinian corals .2. Carbon. Geochim Cosmochim Ac 60, 2871-2885.
Swart, P. K., Szmant, A., Porter, J. W., Dodge, R. E., Tougas, J. I., and Southam, J. R., 2005. The isotopic composition of respired carbon dioxide in scleractinian corals: Implications for cycling of organic carbon in corals. Geochim Cosmochim Ac 69, 1495-1509.
Takahashi, T., Sutherland, S. C., Sweeney, C., Poisson, A., Metzl, N., Tilbrook, B., Bates, N., Wanninkhof, R., Feely, R. A., Sabine, C., Olafsson, J., and Nojiri, Y., 2002. Global sea-air CO2 flux based on climatological surface ocean pCO2, and seasonal biological and temperature effects. Deep-Sea Res Pt Ii 49, 1601-1622.
Tseng, C. M., Wong, G. T. F., Chou, W. C., Lee, B. S., Sheu, D. D., and Liu, K. K., 2007. Temporal variations in the carbonate system in the upper layer at the SEATS station. Deep-Sea Res Pt Ii 54, 1448-1468.
Vengosh, A., Kolodny, Y., Starinsky, A., Chivas, A. R., and Mcculloch, M. T., 1991. Coprecipitation and Isotopic Fractionation of Boron in Modern Biogenic Carbonates. Geochim Cosmochim Ac 55, 2901-2910.
Wang, B.-S., 2005. Environmental significance of the boron isotopic composition in coral skeletons, National Cheng Kung University.
Wang, W.-H., 2008. Temperature Effect on Stable Isotope Fractionation and Trace Element Partition in Aragonite：Inorganic Precipitation Experiments, National Cheng Kung University.
Wei, G. J., McCulloch, M. T., Mortimer, G., Deng, W. F., and Xie, L. H., 2009. Evidence for ocean acidification in the Great Barrier Reef of Australia. Geochim Cosmochim Ac 73, 2332-2346.
Wei, G. J., Sun, M., Li, X. H., and Nie, B. F., 2000. Mg/Ca, Sr/Ca and U/Ca ratios of a porites coral from Sanya Bay, Hainan Island, South China Sea and their relationships to sea surface temperature. Palaeogeogr Palaeocl 162, 59-74.
Xiao, Y. K., Shirodkar, P. V., Zhang, C. G., Wei, H. Z., Liu, W. G., and Zhou, W. J., 2006. Isotopic fractionation of boron in growing corals and its palaeoenvironmental implication. Curr Sci India 90, 414-420.
You, C. F., Spivack, A. J., Smith, J. H., and Gieskes, J. M., 1993. Mobilization of Boron in Convergent Margins - Implications for the Boron Geochemical Cycle. Geology 21, 207-210.
Yu, T.-L., 2007. Geochemical and Environmental Significance of Ba/Ca Ratio in Coral Skeletons, National Cheng Kung University.
Zeebe, R. E., 2005. Stable boron isotope fractionation between dissolved B(OH)3 and B(OH)4-. Geochim Cosmochim Ac 69, 2753-2766.
Zeebe, R. E., Sanyal, A., Ortiz, J. D., and Wolf-Gladrow, D. A., 2001. A theoretical study of the kinetics of the boric acid-borate equilibrium in seawater. Mar Chem 73, 113-124.