The Provenance and Geochemical Alteration of Bermudan Eolianites

Large calcareous eolianites cover the remote island of Bermuda, accounting for more than 90% of the limestone bedrock. This study examines the sedimentology and geochemistry of these eolianites to better understand Pleistocene oceanography and the meteoric alteration of subtropical carbonate sediments. Cluster analyses reveal that the eolian carbonate sediments fall into two natural groups that represent lagoonal and reefal end members of marine sediment production. Coral fragments are uncharacteristically absent, possibly destroyed prior to their incorporation into eolian deposits by endolithic microboring organisms or broken up during transport. Sediment assemblages lead to the following interpretations of the Bermudan offshore environment: (1) the Ledge Flats reef system along the southwestern coast has been active since MIS 11, contributing coralline algal-rich sediment to the northern beaches of Sandy’s Parish and acting as an energy barrier in the south, allowing for low energy sedimentation in the quiet back- reef region; (2) on the northeastern coast, the low energy back-reef region landward of the Ledge Flats has thrived since MIS 11; (3) during MIS 5e, slightly warmer water temperatures led to the hindrance of coralline algal growth along the southern coast and in the North Lagoon. These are the first interpretations of Pleistocene marine assemblages on Bermuda. Meteoric fluids progressively transformed the pristine carbonate sediments into hardened limestones in a predictable solubility-dependent manner. The progressive alteration is coincident with: (1) divergence of δ18O and δ13C values from those similar to unaltered sediment towards those of calcrete, due to interaction with CO2-charged meteoric fluids; (2) depletion of elements with low partitioning coefficients and low meteoric concentrations, such as barium, boron, magnesium, potassium, sodium, strontium, and uranium; (3) enrichment of iron from Terra Rossa-hosted iron oxides; (4) enrichment of aluminum via detrital minerals sourced from protosol horizons; and (5) manganese concentrations that remain uncharacteristically low, owing to the lack of a consistent manganese source. Elemental correlations are useful for characterizing meteoric diagenesis, assuming the primary mineralogy is recognized, all components have been fully altered, and inter-particle cements are ubiquitous.

BLOCK COPOLYMERS CONTAINING A LOW-SURFACE-ENERGY BLOCK AND THEIR APPLICATIONS

This thesis reports the synthesis and/or applications of three types of block copolymers that each bear a low-surface-energy block. First, poly(dimethylsiloxane)-block-poly(2-cinnamoyloxyethyl acrylate) (PDMS-b-PCEA) was synthesized and characterized. Cotton coating using a micellar solution of this block copolymer yielded superhydrophobic cotton fabrics. X-ray photoelectron spectroscopy (XPS) and surface property analyses indicated that the PDMS block topped the polymer coating. Photocuring the cotton swatches crosslinked the underlying PCEA layer and yielded permanent coatings. More interestingly, hydrophilically patterned superhydrophobic cotton fabrics were produced using photolithography that allowed the crosslinking of the coating around irradiated fibers but the removal, by solvent extraction, of the coating on fibers that were not irradiated. Since water-based ink only permeated the uncoated regions, such patterned fabric was further used to print ink patterns onto substrates such as fabrics, cardboard, paper, wood, and aluminum foil. Then, another PDMS-based diblock copolymer poly(dimethylsiloxane)-block-poly(glycidyl methacrylate) (PDMS-b-PGMA) was prepared. Different from PCEA that photocrosslinked around cotton fibers, PGMA reacted with hydroxyl groups on cotton fiber surfaces to get covalently attached. Further, different PGMA chains crosslinked with each other. PDMS-b-PGMA-coated cotton fabrics have been used for oil-water separations. In addition, polymeric nanoparticles were grafted onto cotton fiber surface before PDMS-b-PGMA was used to cover the surfaces of the grafted spheres and the residual surfaces of the cotton fibers. These two types of fabrics, coated by the block copolymer alone or by the polymer nanospheres and then the copolymer, were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and water repellency analyses. A comprehensive comparative study was made of their performances in oil-water separation. Finally, a fluorinated ABC triblock copolymer poly(acrylic acid)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-perfluorooctylethyl methacrylate) (PAA-b-PCEMA-b-PFOEMA) was used to iii encapsulate air nanobubbles. The produced air nanobubbles were thermodynamically stable in water and were some 100 times more stable than commercially available perfluorocarbon-filled microbubbles under ultrasound. These nanobubbles, due to their small sizes and thus ability to permeate the capillary networks of organs and to reach tumors, may expand the applications of microbubbles in diagnostic ultrasonography and find new applications in ultrasound-regulated drug delivery.