Thesis (M.M.P.)--University of Delaware, 2009. / Principal faculty advisor: Jeremy M. Firestone, College of Marine & Earth Studies. Includes bibliographical references.

Thesis: Ph. D., Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2019 / Cataloged from PDF version of thesis. / Includes bibliographical references. / The architecture of coral reef ecosystems is composed of coral skeletons built from the mineral aragonite (CaCO3). Coral reefs are currently being threatened by ocean acidification (OA), which may lower calcification rates, reduce skeletal density, and increase aragonite dissolution. Crystallography and chemistry are what govern the materials properties of minerals, such solubility and strength. Thus, understanding the mineralogical nature of coral aragonite and how it forms are important for predicting bulk skeletal responses under climate change. Different models based on geochemical versus biological controls over coral skeleton biomineralization propose conflicting predictions about the fate of corals under OA. Rather than investigating the mechanism directly, I use a mineralogical approach to study the aragonite end-products of coral biomineralization. / I hypothesize that coral mineralogy and crystallography will lend insights into how coral aragonite crystals form and how sensitive coral aragonite material properties may be to OA. Here I compare the crystallography, bonding environments, and compositions of coral aragonite with aragonite produced by other organisms (mollusk), synthetically (abiogenic precipitation in aragonite-supersaturated seawater and freshwater), and in natural geological settings (abiogenic). Coral aragonite crystallography does not resemble mollusk aragonite (aragonite formed with a strong biological influence), but rather is identical to abiogenic synthetic aragonite precipitated from seawater. I predict that the material properties of coral aragonite are similar to that of abiogenic synthetic seawater aragonites and that coral aragonite formation is sensitive to surrounding seawater chemistry. / To test the effect OA on coral aragonites, I studied deep-sea corals from a natural [omega][subscript sw], gradient (1.15-1.44) in the Gulf of Mexico and shallow-water corals across a natural [omega][subscript sw] (2.3-3.7) and pH (7.84-8.05) gradient in Palau. Minor shifts in crystallography are expressed by coral aragonite in these natural systems, likely governed by skeletal calcite contents, density, and [omega] of the coral calcifying fluid. My results are most consistent with a geochemical model for biomineralization, which implies that coral calcification may be sensitive to OA. However, further work is required to determine whether the modest crystallographic shifts I observe are representative on a global scale and whether they could influence bulk skeletal material properties. / by Gabriela A. Farfan. / Ph. D. / Ph.D. Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution)

Deep-sea bamboo coral (Isidella sp.) SE000901A from the southern Oregon coast (water depth 1048m) provides a high-resolution record of variability of North Pacific Intermediate Water (NPIW) and carbon rain to the sea floor, related to coastal upwelling, from 1808 to 2000AD. Counting of annual layers in magnesium to calcium (Mg/Ca) variations, measured by electron microprobe analysis, yields a detailed age model that is transferred directly to records of carbon and oxygen isotope ratios (δ¹³C and δ¹⁸O) measured by isotope ratio mass spectrometry and trace element ratios measured by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). A significant linear relationship between δ¹³C and δ¹⁸O measured on the carbonate internode of the coral specimen revealed disequilibrium kinetic isotopic variations that depend on calcification rate. The stable isotopic time series are significantly correlated to cadmium to calcium ratios (Cd/Ca) in the carbonate internode, suggesting that cadmium uptake also reflects the rate of calcification. Comparison of phosphorus to calcium ratios (P/Ca) in the carbonate internode to historical records of oxygen concentrations of NPIW suggests that coralline P/Ca is related to the phosphate content of the ambient bottom water, which covaries inversely with oxygen concentration. Stable carbon and nitrogen isotopic ratios (δ¹³C and δ¹⁵N) were measured on two organic gorgonin nodes of our bamboo coral, but incomplete understanding of the gorgonin growth patterns and the difficulty in translating ages between the proteinaceous node and calcareous internode preclude detailed comparison between organic stable isotopes and the trace element and isotopic composition of the well-dated carbonate proxies. Based on correlation of the measured properties to historical variations in coastal upwelling, and high-latitude climate variability, we demonstrate the potential and challenges in using deep-sea bamboo corals to extend records of climate variability into the pre-historical past. / Graduation date: 2012