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Pnfl7erslry of HAWAII UBRAR'l' PNfl7ERSlry OF HAWAII UBRAR'l' CLIMATE CHANGE AND ANTHROPOGENIC EFFECTS ON SHALLOW-WATER CARBONATE BIOGEOCHEMISTRY A THESIS SUBMITTED TO THE GRADUATE DIVISION OF THE UNIVERSITY OF HAWAI'I IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN OCEANOGRAPHY DECEMBER 2003 By Andreas J. Andersson Thesis Connnittee: Fred T. Mackenzie, Chairperson Edward Laws Yuan-HuiLi TABLE OF CONTENTS Acknowledgements vi Abstract viii List ofTables x List ofFigures xi CHAPTER I: Shallow-water carbonate biogeochemistry 1 1.1 Introduction 1 1.2 Background ofresearch 5 1.2.1 Atmospheric C02 and global warming 5 1.2.2 CO2 in seawater and CaC03 saturation state in the ocean 9 1.2.3 CaC03 in natural environments 15 1.2.4 Production ofCaC03 17 1.2.5 The effect ofglobal warming and increasing atmospheric CO2 on marine calcareous organisms and communities 21 1.2.6 Opposing observations and alternative predictions: The Magnesian Salvation Theory .30 1.3 Briefoverview ofthesis content .35 CHAPTER 2: Shallow-water Ocean Carbonate Model (SOCM) .37 2.1 Introduction .37 2.2 SOCM description .38 2.3 Shallow-water carbonate masses, production and accumulation .44 2.3.1 Production and accumulation .44 2.3.2 Shallow-water carbonate budget .49 2.3.3 Shallow-water carbonate sediment mass .51 2.3.4 Carbonate sediment composition .52 2.4 Biogenic calcification 53 2.4.1 Biogenic calcification and DlC 53 2.4.2 Biogenic calcification and carbonate saturation state .54 2.4.3 Biogenic calcification and temperature .56 2.4.4 Combined effect ofDIC, carbonate saturation state and temperature on biogenic calcification in SOCM .57 2.5 Carbonate dissolution and precipitation reaction kinetics 58 2.6 Terrestrial Ocean aTmosphere Ecosystem Model (TOTEM) 68 CHAPTER 3: Solution ofshallow-water carbonates: An insignificant buffer against rising atmospheric C02 (article published in Geology, June 1, 2003) 72 3.1 Abstract 72 3.2 Introduction 73 3.3 Methods 75 3.4 Results and discussion 79 III 3.5 Conclusion 84 3.6 Acknowledgement 85 3.7 References cited 85 CHAPTER 4: Sensitivity analysis and validation ofSOCM 90 4.1 Introduction 90 4.2 Validation ofSOCM 91 4.2.1 Results ofstandard run 91 4.2.2 Comparison ofmodel results to observations from the natural environment 92 4.2.2.1 Carbonate saturation state 92 a) Bermuda Atlantic Time Series (BATS) 94 b) Hawaiian Ocean Time series (HOT) 95 4.2.2.2 Biogenic calcification 97 4.2.2.3 Carbonate mineral dissolution 100 4.2.2.4 Summary 101 4.3 Sensitivity analysis 102 4.3.1 Background 102 4.3.2 Sensitivity procedure 103 4.3.3 Sensitivity analysis results 105 4.3 .3.1 Organic matter deposition and remineralization 107 4.3.3.2 Carbonate reaction kinetics 118 a) Reaction order 118 b) Reaction rate constant... 122 c) Reaction inhibition factor 122 4.3.3.3 Initial model parameters 124 a) Initial carbonate sediment mass 124 b) Initial pore water dissolved inorganic carbon composition and carbonate saturation state 124 c) Average magnesian calcite composition 126 d) Magnesian calcite solubility 130 4.3.3.4 CO2 emission scenarios 134 4.3.3.5 Shallow-water ocean - open ocean exchange 137 4.3.4 Biological implications 139 4.3.4.1 Species and community specific response to decreasing carbonate saturation state 140 4.3.4.2 CO2 emission scenarios - biogenic calcification 141 4.3.4.3 Temperature scenarios - biogenic calcification 144 4.3.4.4 Combined effect ofcarbonate saturation state and temperature on biogenic calcification 146 4.4 Summary and concluding remark 148 CHAPTER 5: Summary and conclusions 150 IV APPENDIX A 153 A.l ForcingsofSOCM 153 A.2 DIC calculations 153 A.3 Model equations 156 A3.1 Mass balance equations 159 A3.2 Flux equations 160 A3.3 Flux equations: special cases 161 A.3.3.1 Atmosphere - surface water CO2 exchange 161 A.3.3.2 Marine photosynthesis 163 A.3.3.3 Marine biogenic calcification 163 A.3.3.4 Pore water-sediment system carbonate precipitation and dissolution 164 A4 Derivation ofinitial reservoir masses in SOCM 165 A5 Derivation ofinitial carbon fluxes in SOCM 168 References 178 v ACKNOWLEDGEMENTS The completion ofthis thesis could never have been done without the support of my committee: Dr. Fred Mackenzie, Dr. Yuan-Hui (Telu) Li and Dr. Edward Laws. As a student I could never have asked for a better committee. The support, encouragement, and willingness ofthe committee members to be always available, no matter when, where or what, to answer questions or just discuss the existential questions oflife, and to share their knowledge and intellect were beyond what any student could wish for. I wish all students the same support that I received from my committee. Since the very first day when I started in the oceanography program, I have met with Fred almost on a weekly basis. Sometimes he even had to deal with me on many more occasions. In addition to my appreciation ofthe magnificent scientific guidance that Fred has given me, I'm extremely appreciative ofthe support and advice he has provided me in times when science has been out offocus for various reasons. Similarly, Telu and Ed have always made themselves available to me and I am tremendously grateful for their willingness to always put the student in focus and for offering their guidance and help. Furthermore I would like to thank the Mackenzie group: Mike Guidry, Dan Hoover, Stephanie Ringuet, May Ver, as well as Jane Schoonmaker, for their unconditional support and encouragement; Ricky Grigg for keeping me updated on the ongoing discussion about the Magnesian Salvation Theory; Jim Cowen and Eric Hochberg for giving me valuable ship and field time; Bob Buddemeier, Jean-Pierre Gattuso and Dave Barnes for providing me with reprints and insightful information about coral reefs and calcification; Rudolf Kloosterziel for mathematical assistance; Kathy Kozuma and her student helpers Kellie VI Gushiken and Kellie Shek whom always have a smile to spare; and Varis Grundmanis and Christopher Winn for introducing me to the field ofoceanography. Finally, I would like to acknowledge my mother Ann-Birgitt Andersson, who has always been of tremendous support although I have always gone my own way and moved as far away from Sweden as I possibly could. Since I was born she has always taught me that "the more you know, the more you realize you do not know" and although I have always acknowledged these words ofwisdom, they have never been more clear to me as they are now after completing my master's thesis. Financial support ofmy thesis research was provided by National Science Foundation grants ATMOO-80878 and EAR02-235090 and partial assistance was also provided by Sigma Xi. VB ABSTRACT As a consequence ofanthropogenic activities, future projections suggest that the saturation state ofsurface ocean waters with respect to carbonate minerals will decline during the twenty-first century owing to increasing atmospheric C02. As a result calcareous organisms could have difficulty calcifying, leading to production ofweaker skeletons and their greater vulnerability to erosion, and ultimately leading to dissolution ofcalcareous sediments. At the same time, sea surface temperature could be significantly higher and the amount oforganic matter deposited within the coastal zone could also increase owing to human activities. Increased deposition oforganic matter and subsequent remineralization within the sediments ofthe coastal region could have implications with respect to the carbonate geochemistry ofthe pore water-sediment system, affecting rates ofcarbonate dissolution and precipitation. Increasing dissolution ofmetastable carbonate minerals, such as high magnesian calcite has been suggested as a mechanism to restore changes in saturation state and pH owing to increasing atmospheric C02, acting as a buffer, and could counteract any negative effects on calcareous organisms and communities. In order to investigate the effects ofclimate change and anthropogenic activities on the carbonate biogeochemistry ofthe shallow water ocean enviromnent, a global physical-biogeochemical box model referred to as SOCM (Shallow-water Ocean Carbonate Model) was developed. Numerical simulations demonstrated that biogenic calcification could decrease by 7-44% throughout the 21 5t century owing to a decrease in carbonate saturation state. Dissolution ofmetastable carbonate minerals could increase owing to increased deposition and remineralization of Vlll organic matter, but will not result in the production ofsufficient alkalinity to buffer the carbon chemistry ofthe surface ocean water. However, a buffer effect was observed within the pore water system. Sensitivity analysis indicated that the extent ofdissolution was mainly controlled by remineralization oforganic matter rather than reaction kinetics. In the current standard simulation, the metastable equilibrium ofthe pore water changed from 21 mol% magnesian calcite to 14 mol% magnesian calcite. Future changes in pore water carbonate saturation state could affect the average composition and rates of precipitation ofcarbonate cements in contemporary shallow-water sediments. IX LIST OF TABLES 1.1 Carbonate mineralogy ofmajor carbonate organism groups 18 2.1 Calcium carbonate production and accumulation in the shallow- water ocean environment in the late Holocene ocean 46 2.2 Relative rate ofcalcification as a function ofaragonite saturation state .........55 2.3 Relative rate ofcalcification as a function oftemperature change 57 2.4 Kinetic rate constants and reaction order from selected carbonate precipitation and dissolution experiments 61
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