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UNIVERSITY of CALIFORNIA Los Angeles Li/Ca, B UNIVERSITY OF CALIFORNIA Los Angeles Li/Ca, B/Ca, and Mg/Ca Composition of Cultured Sea Urchin Spines and Paleo-Echinoderms Measured Using a Secondary Ion Mass Spectrometer A thesis submitted in partial satisfaction of the requirements for the degree Master of Science in Atmospheric and Oceanic Science by Trung Timothy Do Nguyen 2013 ABSTRACT OF THE THESIS Li/Ca, B/Ca, and Mg/Ca Composition of Cultured Sea Urchin Spines and Paleo-Echinoderms Measured Using a Secondary Ion Mass Spectrometer By Trung Timothy Do Nguyen Master of Science in Atmospheric and Oceanic Science University of California, Los Angeles, 2013 Professor Aradhna K. Tripati, Chair Element-to-calcium (X/Ca) ratios within biogenic calcium carbonate minerals are used as proxies to reconstruct past seawater temperature and composition. This study focuses on examining Li/Ca, B/Ca, and Mg/Ca ratios in sea urchins cultured at different temperatures and pCO2 levels. In situ secondary ion mass spectrometry (SIMS) analyses were conducted on two species of sea urchins cultured under controlled conditions and several species of paleo- echinoderms. A temperate species, Arbacia punctulata, was cultured at various pCO2 levels (400, 600, 900, 2850 ppmv) with temperature held constant at 25°C. A tropical species, Echinometra viridis, was cultured in variable pCO2 (400 and 1000 ppmv) and temperature (20°C and 30°C) conditions. In the tropical species, a positive correlation was found between temperature and the analyzed (Li, B, Mg) element-to-calcium ratios of the spines, while variable responses to pCO2 were observed. In the temperate species, a variable response to increasing pCO2 was observed, with B/Ca having a similar trend to the calcification rate found in a previous study by Ries et al. (2009). Paleo-echinoderm samples varied in age from 518 to 53 Ma, and have a global distribution. The X/Ca ratios from paleo-echinoderms were used, along with the full range c of observed partition coefficients (D X/Ca=X/Cacarbonate/X/Cafluid, with X=Li, B, or Mg in this study) from the cultured sea urchins, to model element-to-calcium ratios of paleo-seawater. ii The thesis of Trung Timothy Do Nguyen is approved. Ulrike Seibt Axel K. Schmitt Aradhna K. Tripati, Committee Chair University of California, Los Angeles 2013 iii Dedication I would like to dedicate this thesis to my family for their support and encouragement throughout my program. I would also like to dedicate this to Christy. iv Table of Contents Introduction ................................................................................................................................... 1 Acidification of the Oceans ........................................................................................................ 1 Evolution and Biology of Sea Urchins ....................................................................................... 2 Sea Urchin Calcification ............................................................................................................ 4 Cultured Sea Urchins ................................................................................................................ 5 Fossilized Echinoderms ............................................................................................................ 7 Paleo-Climate Proxies ............................................................................................................... 8 Lithium/Calcium ..................................................................................................................... 8 Boron/Calcium ..................................................................................................................... 10 Magnesium/Calcium ............................................................................................................ 11 Secondary Ion Mass Spectrometery (SIMS) ........................................................................... 13 Methodology ............................................................................................................................... 14 Preparation of Cultured Sea Urchin Spines ............................................................................ 14 Polishing .............................................................................................................................. 17 Determination of Calcite within Urchin Spine .......................................................................... 21 Preparation of Paleo-Echinoderms ......................................................................................... 23 Analytical Conditions ............................................................................................................... 26 Standards ................................................................................................................................ 27 Normalizing Intensity Ratios .................................................................................................... 28 Analysis of Sea Urchin Spines ................................................................................................ 29 Images After SIMS Analysis .................................................................................................... 30 Analysis of Paleo-Echinoderms ............................................................................................... 31 Results ........................................................................................................................................ 33 Individual Spines of A. punctulata ........................................................................................... 33 Averaged Culturing Conditions of A. punctulata ...................................................................... 35 Individual Spines of E. viridis ................................................................................................... 36 Averaged Culturing Conditions of E. viridis ............................................................................. 40 Paleo-Echinoderms ................................................................................................................. 41 Discussion ................................................................................................................................... 42 Is X/Ca in Sea Urchin Calcite Sensitive to Carbonate Chemistry, Temperature, or Both? ..... 42 v Lithium/Calcium ................................................................................................................... 42 Boron/Calcium ..................................................................................................................... 45 Magnesium/Calcium ............................................................................................................ 49 Summary of Cultured Sea Urchin Element-to-Calcium SIMS Analysis ............................... 52 Fossilized Paleo-Echinoderms ................................................................................................ 53 Variations in X/Ca Over the Past 400 Million Years ............................................................ 54 Using Cultured Sea Urchins to Calculate Partition Coefficient ............................................ 56 Partition Coefficient Based on Corrected Temperature ................................................... 57 SIMS and Electron Ion Microprobe Analysis on Mg/Ca in Paleo-Echinoderm Samples...... 65 Implications from Paleo-Echinoderm Analysis ........................................................................ 67 Conclusion .................................................................................................................................. 70 Appendix A: A. punctulata SIMS Data ........................................................................................ 72 A.1: Intensity Ratios ................................................................................................................ 72 A.2: Normalized Ratios ............................................................................................................ 76 Appendix B: E. viridis SIMS Data ................................................................................................ 79 B.1: Intensity Ratios ................................................................................................................ 79 B.2: Normalized Ratios ............................................................................................................ 87 Appendix C: Paleo-Echinoderm SIMS Data ............................................................................... 93 C.1: Intensity Ratios ................................................................................................................ 93 C.2 : Normalized Ratios .......................................................................................................... 97 Appendix D: Reference Material SIMS Data ............................................................................. 100 D.2: Intensity Ratios .............................................................................................................. 100 References ................................................................................................................................ 102 vi Acknowledgements I would like to thank Dr. Kevin McKeegan and Dr. Axel Schmitt in the department of Earth and Space Sciences, UCLA, for allowing us to perform the SIMS analysis on their equipment. I would also like to thank
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