(Table 4) Chemistry of iron-rich basalts from ODP Hole 106-648B

Analysis numbers 344-370, SAMF 12.5-12.7; 442-369, SAMF 12.7-12.9; 422-77, SAMF 12.9-13.1; 95-156, SAMF 13.1-13.3; 272-82, SAMF 13.3-13.5; 285-33, SAMF 13.5-13.7. Analyses are listed in depth order within each SAMF division.

(Table 1, page 168) Iron, manganese, and phosphorus concentrations in Fe-Mn-concretions from the Gulf of Bothnia, northern Baltic Sea

Fe-Mn-concretions of a spheroidal type were found according to electron probe determinations to consist of alternating iron- and manganese-rich layers. This pattern was ascribed to seasonal variations in the physico-chemical conditions governing the precipitation of the hydrous oxides of iron and manganese. Calculations based on the rhythmic growth of the concretions investigated gave a mean accumulation rate of 0.15-0.20 mm/yr. The rather high phosphorus content (average 3.5 % P2O5) of the concretions was found to be concentrated in the iron-rich layers, probably as a result of the scavenging effect of ferric hydroxide.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Inorganic nanoparticles as carriers for efficient cellular delivery

Cellular delivery involving the transfer of various drugs and bio-active molecules (peptides, proteins and DNAs, etc.) through the cell membrane into cells has attracted increasing attention because of its importance in medicine and drug delivery. This topic has been extensively reviewed. The direct delivery of drugs and biomolecules, however, is generally inefficient and suffering from problems such as enzymic degradation of DNAs. Therefore, searching for efficient and safe transport vehicles (carriers) to delivery genes or drugs into cells has been challenging yet exciting area of research. In past decades, many carriers have been developed and investigated extensively which can be generally classified into four major groups: viral carriers, organic cationic compounds, recombinant protiens and inorganic nanoparticles. Many inorganic materials, such as calcium phosphate, gold, carbon materials, silicon oxide, iron oxide and layered double hydroxide (LDH), have been studied. Inorganic nanoparticles show low toxicity and promise for controlled delivery properties, thus presenting a new alternative to viral carriers and cationic carriers. Inorganic nanoparticles generally possess versatile properties suitable for cellular delivery, including wide availability, rich functionality, good biocompatibility, potential capability of targeted delivery (e.g. selectively destroying cancer cells but sparing normal tissues) and controlled release of carried drugs. This paper reviews the latest advances in inorganic nanoparticle applications as cellular delivery carriers and highlights some key issues in efficient cellular delivery using inorganic nanoparticles. Critical proper-ties of inorganic nanoparticles, surface functionalisation (modification), uptake of biomolecules, the driving forces for delivery, and release of biomolecules will be reviewed systematically. Selected examples of promising inorganic nanoparticle delivery systems, including gold, fullerences and carbon nanotubes, LDH and various oxide nanoparticles in particular their applications for gene delivery will be discussed. The fundamental understanding of properties of inorganic nanoparticles in relation to cellular delivery efficiency as the most paramount issue will be highlighted. (c) 2005 Elsevier Ltd. All rights reserved.

Three-dimensional calibration targets for optical coherence tomography

The recent expansion of clinical applications for optical coherence tomography (OCT) is driving the development of approaches for consistent image acquisition. There is a simultaneous need for time-stable, easy-to-use imaging targets for calibration and standardization of OCT devices. We present calibration targets consisting of three-dimensional structures etched into nanoparticle-embedded resin. Spherical iron oxide nanoparticles with a predominant particle diameter of 400 nm were homogeneously dispersed in a two part polyurethane resin and allowed to harden overnight. These samples were then etched using a precision micromachining femtosecond laser with a center wavelength of 1026 nm, 100kHz repetition rate and 450 fs pulse duration. A series of lines in depth were etched, varying the percentage of inscription energy and speed of the translation stage moving the target with respect to the laser. Samples were imaged with a dual wavelength spectral-domain OCT system and point-spread function of nanoparticles within the target was measured.

Three-dimensional calibration targets for optical coherence tomography

The recent expansion of clinical applications for optical coherence tomography (OCT) is driving the development of approaches for consistent image acquisition. There is a simultaneous need for time-stable, easy-to-use imaging targets for calibration and standardization of OCT devices. We present calibration targets consisting of three-dimensional structures etched into nanoparticle-embedded resin. Spherical iron oxide nanoparticles with a predominant particle diameter of 400 nm were homogeneously dispersed in a two part polyurethane resin and allowed to harden overnight. These samples were then etched using a precision micromachining femtosecond laser with a center wavelength of 1026 nm, 100kHz repetition rate and 450 fs pulse duration. A series of lines in depth were etched, varying the percentage of inscription energy and speed of the translation stage moving the target with respect to the laser. Samples were imaged with a dual wavelength spectral-domain OCT system and point-spread function of nanoparticles within the target was measured.

Biogeochemical effects of iron availability on primary producers in a shallow marine carbonate environment

We completed a synoptic survey of iron, phosphorus, and sulfur concentrations in shallow marine carbonate sediments from south Florida. Total extracted iron concentrations typically were 50 μmol g-1 dry weight (DW) and tended to decrease away from the Florida mainland, whereas total extracted phosphorus concentrations mostly were 10 μmol g-1 DW and tended to decrease from west to east across Florida Bay. Concentrations of reduced sulfur compounds, up to 40 μmol g-1 DW, tended to covary with sediment iron concentrations, suggesting that sulfide mineral formation was iron-limited. An index of iron availability derived from sediment data was negatively correlated with chlorophyll a concentrations in surface waters, demonstrating the close coupling of sediment-water column processes. Eight months after applying a surface layer of iron oxide granules to experimental plots, sediment iron, phosphorus, and sulfur were elevated to a depth of 10 cm relative to control plots. Biomass of the seagrass Thalassia testudinum was not different between control and iron addition plots, but individual shoot growth rates were significantly higher in experimental plots after 8 months. Although the iron content of leaf tissues was significantly higher from iron addition plots, no difference in phosphorus content of T. testudinum leaves was observed. Iron addition altered plant exposure to free sulfide, documented by a significantly higher δ34S of leaf tissue from experimental plots relative to controls. Iron as a buffer to toxic sulfides may promote individual shoot growth, but phosphorus availability to plants still appears to limit production in carbonate sediments.

Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Element abundances, loss on ignition, total analyzed abundances, CIA values, and Al-oxide/Ti-oxide ratios of sediment core CRP-2A (Table1)

The CRP-2/2A core, drilled in western McMurdo Sound in October and November 1998, penetrated 624 m of Quaternary. Pliocene, lower Miocene, and Oligocene glacigenic sediments. The palaeoclimatic record of CRP-2/2A is examined using major element analyses of bulk core samples of fine grained sediments (mudstones and siltstones) and the Chemical Index of Alteration (CIA) of Nesbitt & Young (1982). The CIA is calculated from the relative abundances of AI, K, Ca, and Na oxides, and its magnitude increases as the effects of chemical weathering increase. However, changes in sediment provenance can also affect the CIA, and provenance changes are recorded by shifts in the Al2O3/TiO2 ratios and the Nb contents of these CRP-2/2A mudstones. Relatively low CIA values (40-50) occur throughout the CRP-2/2A sequence, whereas the Al2O3/TiO2 ratio decreases upsection. The major provenance change is an abrupt onset of McMurdo Volcanic Group detritus at ~300 mbsf and is best characterized by a rapid increase in Nb content in the sediments. This provenance shift is not evident in the CIA record, suggesting that a contribution from the Ferrar Dolerite to the older sediments was replaced by an input of McMurdo Volcanic Group material in the younger sediments. If this is true, then the relatively uniform CIA values indicate relatively consistent palaeoweathering intensities throughout the Oligocene and early Miocene in the areas that supplied sediment to CRP-2/2A.