Re-evaluation of pulmonary titanium dioxide nanoparticle distribution using the "relative deposition index": Evidence for clearance through microvasculature

ABSTRACT: BACKGROUND: Translocation of nanoparticles (NP) from the pulmonary airways into other pulmonary compartments or the systemic circulation is controversially discussed in the literature. In a previous study it was shown that titanium dioxide (TiO2) NP were "distributed in four lung compartments (air-filled spaces, epithelium/endothelium, connective tissue, capillary lumen) in correlation with compartment size". It was concluded that particles can move freely between these tissue compartments. To analyze whether the distribution of TiO2 NP in the lungs is really random or shows a preferential targeting we applied a newly developed method for comparing NP distributions. METHODS: Rat lungs exposed to an aerosol containing TiO2 NP were prepared for light and electron microscopy at 1 h and at 24 h after exposure. Numbers of TiO2 NP associated with each compartment were counted using energy filtering transmission electron microscopy. Compartment size was estimated by unbiased stereology from systematically sampled light micrographs. Numbers of particles were related to compartment size using a relative deposition index and chi-squared analysis. RESULTS: Nanoparticle distribution within the four compartments was not random at 1 h or at 24 h after exposure. At 1 h the connective tissue was the preferential target of the particles. At 24 h the NP were preferentially located in the capillary lumen. CONCLUSION: We conclude that TiO2 NP do not move freely between pulmonary tissue compartments, although they can pass from one compartment to another with relative ease. The residence time of NP in each tissue compartment of the respiratory system depends on the compartment and the time after exposure. It is suggested that a small fraction of TiO2 NP are rapidly transported from the airway lumen to the connective tissue and subsequently released into the systemic circulation.

The role of macrophages in the clearance of inhaled ultrafine titanium dioxide particles

The role of macrophages in the clearance of particles with diameters less than 100 nm (ultrafine or nanoparticles) is not well established, although these particles deposit highly efficiently in peripheral lungs, where particle phagocytosis by macrophages is the primary clearance mechanism. To investigate the uptake of nanoparticles by lung phagocytes, we analyzed the distribution of titanium dioxide particles of 20 nm count median diameter in macrophages obtained by bronchoalveolar lavage at 1 hour and 24 hours after a 1-hour aerosol inhalation. Differential cell counts revealing greater than 96% macrophages and less than 1% neutrophils and lymphocytes excluded inflammatory cell responses. Employing energy-filtering transmission electron microscopy (EFTEM) for elemental microanalysis, we examined 1,594 macrophage profiles in the 1-hour group (n = 6) and 1,609 in the 24-hour group (n = 6). We found 4 particles in 3 macrophage profiles at 1 hour and 47 particles in 27 macrophage profiles at 24 hours. Model-based data analysis revealed an uptake of 0.06 to 0.12% ultrafine titanium-dioxide particles by lung-surface macrophages within 24 hours. Mean (SD) particle diameters were 31 (8) nm at 1 hour and 34 (10) nm at 24 hours. Particles were localized adjacent (within 13-83 nm) to the membrane in vesicles with mean (SD) diameters of 592 (375) nm at 1 hour and 414 (309) nm at 24 hours, containing other material like surfactant. Additional screening of macrophage profiles by conventional TEM revealed no evidence for agglomerated nanoparticles. These results give evidence for a sporadic and rather unspecific uptake of TiO(2)-nanoparticles by lung-surface macrophages within 24 hours after their deposition, and hence for an insufficient role of the key clearance mechanism in peripheral lungs.

Graphite exfoliation by supercritical carbon dioxide extraction

Supercritical carbon dioxide is used to exfoliate graphite, producing a small, several-layer graphitic flake. The supercritical conditions of 2000, 2500, and 3000 psi and temperatures of 40°, 50°, and 60°C, have been used to study the effect of critical density on the sizes and zeta potentials of the treated flakes. Photon Correlation Spectroscopy (PCS), Brunauer-Emmett-Teller (BET) surface area measurement, field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) are used to observe the features of the flakes. N-methyl-2-pyrrolidinone (NMP), dimethylformamide (DMF), and isopropanol are used as co-solvents to enhance the supercritical carbon dioxide treatment. As a result, the PCS results show that the flakes obtained from high critical density treatment (low temperature and high pressure) are more stable due to more negative charges of zeta potential, but have smaller sizes than those from low critical density (high temperature and low pressure). However, when an additional 1-hour sonication is applied, the size of the flakes from low critical density treatment becomes smaller than those from high critical density treatment. This is probably due to more CO2 molecules stacked between the layers of the graphitic flakes. The zeta potentials of the sonicated samples were slightly more negative than nonsonicated samples. NMP and DMF co-solvents maintain stability and prevented reaggregation of the flakes better than isopropanol. The flakes tend to be larger and more stable as the treatment time increases since larger flat area of graphite is exfoliated. In these experiments, the temperature has more impact on the flakes than pressure. The BET surface area resultsshow that CO2 penetrates the graphite layers more than N2. Moreover, the negative surface area of the treated graphite indicates that the CO2 molecules may be adsorbed between the graphite layers during supercritical treatment. The FE-SEM and AFM images show that the flakes have various shapes and sizes. The effects of surfactants can be observed on the FE-SEM images of the samples in one percent by weight solution of SDBS in water since the sodium dodecylbenzene sulfonate (SDBS) residue covers all of the remaining flakes. The AFM images show that the vertical thickness of the graphitic flakes can ranges from several nanometers (less than ten layers thick), to more than a hundred nanometers. In conclusion, supercritical carbon dioxide treatment is a promising step compared to mechanical and chemical exfoliation techniques in the large scale production of thin graphitic flake, breaking down the graphite flakes into flakes only a fewer graphene layers thick.

Carbon dioxide sequestration in cement kiln dust through miner carbonation

The feasibility of carbon sequestration in cement kiln dust (CKD) was investigated in a series of batch and column experiments conducted under ambient temperature and pressure conditions. The significance of this work is the demonstration that alkaline wastes, such as CKD, are highly reactive with carbon dioxide (CO2). In the presence of water, CKD can sequester greater than 80% of its theoretical capacity for carbon without any amendments or modifications to the waste. Other mineral carbonation technologies for carbon sequestration rely on the use of mined mineral feedstocks as the source of oxides. The mining, pre-processing and reaction conditions needed to create favorable carbonation kinetics all require significant additions of energy to the system. Therefore, their actual net reduction in CO2 is uncertain. Many suitable alkaline wastes are produced at sites that also generate significant quantities of CO2. While independently, the reduction in CO2 emissions from mineral carbonation in CKD is small (~13% of process related emissions), when this technology is applied to similar wastes of other industries, the collective net reduction in emissions may be significant. The technical investigations presented in this dissertation progress from proof of feasibility through examination of the extent of sequestration in core samples taken from an aged CKD waste pile, to more fundamental batch and microscopy studies which analyze the rates and mechanisms controlling mineral carbonation reactions in a variety of fresh CKD types. Finally, the scale of the system was increased to assess the sequestration efficiency under more pilot or field-scale conditions and to clarify the importance of particle-scale processes under more dynamic (flowing gas) conditions. A comprehensive set of material characterization methods, including thermal analysis, Xray diffraction, and X-ray fluorescence, were used to confirm extents of carbonation and to better elucidate those compositional factors controlling the reactions. The results of these studies show that the rate of carbonation in CKD is controlled by the extent of carbonation. With increased degrees of conversion, particle-scale processes such as intraparticle diffusion and CaCO3 micropore precipitation patterns begin to limit the rate and possibly the extent of the reactions. Rates may also be influenced by the nature of the oxides participating in the reaction, slowing when the free or unbound oxides are consumed and reaction conditions shift towards the consumption of less reactive Ca species. While microscale processes and composition affects appear to be important at later times, the overall degrees of carbonation observed in the wastes were significant (> 80%), a majority of which occurs within the first 2 days of reaction. Under the operational conditions applied in this study, the degree of carbonation in CKD achieved in column-scale systems was comparable to those observed under ideal batch conditions. In addition, the similarity in sequestration performance among several different CKD waste types indicates that, aside from available oxide content, no compositional factors significantly hinder the ability of the waste to sequester CO2.

Structural and surface property characterization of titanium dioxide nanotubes for orthopedic implants

This research focused on the to modification of the surface structure of titanium implants with nanostructured morphology of TiO2 nanotubes and studied the interaction of nanotubes with osteoblast cells to understand the parameters that affect the cell growth. The electrical, mechanical, and structural properties of TiO2 nanotubes were characterized to establish a better understanding on the properties of such nanoscale morphological structures. To achieve the objectives of this research work I transformed the titanium and its alloys, either in bulk sheet form, bulk machined form, or thin film deposited on another substrate into a surface of titania nanotubes using a low cost and environmentally friendly process. The process requires only a simple electrolyte, low cost electrode, and a DC power supply. With this simple approach of scalable nanofabrication, a typical result is nanotubes that are each approximately 100nm in diameter and have a wall thickness of about 20nm. By changing the fabrication parameters, independent nanotubes can be fabricated with open volume between them. Titanium in this form is termed onedimensional since electron transport is narrowly confined along the length of the nanotube. My Ph.D. accomplishments have successfully shown that osteoblast cells, the cells that are the precursors to bone, have a strong tendency to attach to the inside and outside of the titanium nanotubes onto which they are grown using their filopodia – cell’s foot used for locomotion – anchored to titanium nanotubes. In fact it was shown that the cell prefers to find many anchoring sites. These sites are critical for cell locomotion during the first several weeks of maturity and upon calcification as a strongly anchored bone cell. In addition I have shown that such a surface has a greater cell density than a smooth titanium surface. My work also developed a process that uses a focused and controllably rastered ion beam as a nano-scalpel to cut away sections of the osteoblast cells to probe the attachment beneath the main cell body. Ultimately the more rapid growth of osteoblasts, coupled with a stronger cell-surface interface, could provide cost reduction, shorter rehabilitation, and fewer follow-on surgeries due to implant loosening.

Synthesis of novel solid materials from carbon dioxide and carbon monoxide

The increase of atmospheric CO2 has been identified as the primary cause for the observed global warming over the past century. The geological and oceanic sequestration of CO2 has issues, such as cost and leakage as well as effects on sea biota. The ideal solution should be the conversion of CO2 into useful materials. However, most processes require high energy input. Therefore, it is necessary to explore novel processes with low energy demands to convert CO2 to useful solid materials. Amorphous carbon nitride and graphone received much attention due to their unusual structures and properties as well as their potential applications. However, to date there has been no attempt to synthesize those solid materials from CO2. Lithium nitride (Li3N) and lithium imide (Li2NH) are important hydrogen storage materials. However, their optical properties and reactivity has not yet studied. This dissertation research is aimed at the synthesis of carbon nitrides and graphone from CO2 and CO via their reaction with Li3N and Li2NH. The research was focused on (1) the evaluation of Li3N and Li2NH properties, (2) thermodynamic analysis of conversion of carbon dioxide and carbon monoxide into carbon nitride and other solid materials, (3) synthesis of carbon nitride from carbon dioxide, and (4) synthesis of graphone from carbon monoxide. First, the properties of Li3N, Li2NH, and LiNH2 were investigated. The X-ray diffraction measurements revealed that heat-treatment at 500°C introduce a phase transformation of β-Li3N to α-Li3N. Furthermore, the UV-visible absorption evaluation showed that the energy gaps of α-Li3N and β-Li3N are 1.81 and 2.14 eV, respectively. The UV-visible absorption measurements also revealed that energy gaps are 3.92 eV for Li2NH and 3.93 eV for LiNH2. This thermodynamic analysis was performed to predict the reactions. It was demonstrated that the reaction between carbon dioxide and lithium nitride is thermodynamically favorable and exothermic, which can generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

Approach to carbon dioxide capture and storage at ambient conditions

Carbon dioxide (CO2) capture and storage experiments were conducted at ambient conditions in varying weight % sodium carbonate (Na2CO3) solutions. Experiments were conducted to determine the optimal amount of Na2CO3 in solution for CO2 absorption. It was concluded that a 2% Na2CO3 solution, by weight, was the most efficient solution. The 2% Na2CO3 solution is able to absorb 0.5 g CO2/g Na2CO3. These results led to studies to determine how the gas bubble size affected carbon dioxide absorption in the solution. Studies were conducted using ASTM porosity gas diffusers to vary the bubble size. Gas diffusers with porosities of fine, medium, and extra coarse were used. Results found that the medium porosity gas diffuser was the most efficient at absorbing CO2 at 50%. Variation in the bubble size concluded that absorption of carbon dioxide into the sodium carbonate solution does depend on the bubble size, thus is mass transfer limited. Once the capture stage was optimized (amount of Na2CO3 in solution and bubble size), the next step was to determine if carbon dioxide could be stored as a calcium carbonate mineral using calcium rich industrial waste and if the sodium carbonate solution could be simultaneously regenerated. Studies of CO2 sequestration at ambient conditions have shown that it is possible to permanently sequester CO2 in the form of calcium carbonate using a calcium rich industrial waste. Studies have also shown that it is possible to regenerate a fraction of the sodium carbonate solution.

Understanding volcanic processes using UV camera measurements of sulfur dioxide and coincident infrasound and seismicity

The exsolution of volatiles from magma maintains an important control on volcanic eruption styles. The nucleation, growth, and connectivity of bubbles during magma ascent provide the driving force behind eruptions, and the rate, volume, and ease of gas exsolution can affect eruptive activity. Volcanic plumes are the observable consequence of this magmatic degassing, and remote sensing techniques allow us to quantify changes in gas exsolution. However, until recently the methods used to measure volcanic plumes did not have the capability of detecting rapid changes in degassing on the scale of standard geophysical observations. The advent of the UV camera now makes high sample rate gas measurements possible. This type of dataset can then be compared to other volcanic observations to provide an in depth picture of degassing mechanisms in the shallow conduit. The goals of this research are to develop a robust methodology for UV camera field measurements of volcanic plumes, and utilize this data in conjunction with seismoacoustic records to illuminate degassing processes. Field and laboratory experiments were conducted to determine the effects of imaging conditions, vignetting, exposure time, calibration technique, and filter usage on the UV camera sulfur dioxide measurements. Using the best practices determined from these studies, a field campaign was undertaken at Volcán de Pacaya, Guatemala. Coincident plume sulfur dioxide measurements, acoustic recordings, and seismic observations were collected and analyzed jointly. The results provide insight into the small explosive features, variations in degassing rate, and plumbing system of this complex volcanic system. This research provides useful information for determining volcanic hazard at Pacaya, and demonstrates the potential of the UV camera in multiparameter studies.

NICKEL-COBALT SOLID SOLUTION AND ITS APPLICATIONS AS CATALYSTS FOR CARBON DIOXIDE REFORMING OF METHANE

Global warming issue becomes more significant to human beings and other organisms on the earth. Among many greenhouse gases, carbon dioxide (CO2) has the largest contribution to global warming. To find an effective way to utilize the greenhouse gas is urgent. It is the best way to convert CO2 to useful compounds. CO2 reforming of methane is an attractive process to convert CO2 and methane into synthesis gas (CO/H2), which can be used as a feedstock for gasoline, methanol, and other hydrocarbons. Nickel and cobalt were found to have good activity for CO2 reforming. However, they have a poor stability due to carbon deposition. This research developed efficient Ni-Co solid solution catalysts with excellent activities and high stability for CO2 reforming of methane. First, the structure of binary oxide solid solution of nickel and cobalt was investigated. It was found that while the calcination of Ni(NO3)2 and Co(NO3)2 mixture with 1:1 molar ratio at a high temperature above 800 oC generated NiO-CoO solid solution, only Ni3O4-Co3O4 solid solution was observed after the calcination at a low temperature of 500 oC. Furthermore, if the calcination was carried out at a medium temperature arranged from 600 to 700 oC, both NiO-CoO and Ni3O4-Co3O4 solid solutions can be formed. This occurred because Co3O4 can induce the formation of Ni3O4, whereas NiO can stabilize CoO. In addition, the lattice parameter of Ni3O4, which was predicted by using Vegard’s Law, is 8.2054 Å. As a very important part of this dissertation, Ni-Co solid solution was evaluated as catalysts for CO2 reforming of methane. It was revealed that nickel-cobalt solid solution showed excellent catalytic performance and high stability for CO2 reforming of methane. However, the stability of Ni-Co solid solution catalysts is strongly dependent on their composition and preparation condition. The optimum composition is 50%Ni-50%Co. Furthermore, the structure of Ni-Co catalysts was characterized by XRD, Vvis, TPR, TPD, BET, AES, TEM, XANES and EXAFS. The relationship between the structure and the catalytic performance was established: (1) The reduced NiO-CoO solid solution possesses better catalytic performance and stability than the reduced Ni3O4-Co3O4 solid solution. (2) Ni is richer on surface in Ni-Co catalysts. And (3) the reduction of Ni-Co-O solid solution generated two types of particles, small and large particles. The small ones are dispersed on large ones as catalytic component.

ASTAXANTHIN PRODUCTION FROM HAEMATOCOCCUS PLUVIALIS UNDER VARIOUS LIGHT INTENSITIES AND CARBON DIOXIDE CONCENTRATIONS

The microalga Haematococcus pluvialis was cultivated in MES-volvox medium at various light intensities and CO2 concentrations. It was found that CO2 concentrations of 10 and 15%, in combination with high irradiance at initial pH =6.7, accelerate astaxanthin accumulation in H. pluvialis cells but obstruct cell growth. The purpose of this research study was to devise a one-stage process consisting of the simultaneous cultivation of H. pluvialis and astaxanthin production using high light intensity and high CO2 concentration. This could be achieved at 200 µE/m2s and 15% CO2 in growth medium at initial pH = 4.3. Compared to the traditional two-stage H. pluvialis cultivation system, this one-step process can save up to 8-9 days of astaxanthin production time. The astaxanthin content in H. pluvialis cells induced with high light intensity only or with a combination of high light intensity and high CO2 concentration had comparable astaxanthin content; 94 and 97 mg/g dry biomass, respectively. However, it was extremely low in nitrate-free medium at high irradiance alone or combined with high CO2 concentration, with an average value of 4 mg/g dry biomass. Cell density was 40% less in cultures under discontinuous illumination compared to continuous illumination. This process could serve as a microalgal CO2 mitigation system after further understanding of the CO2 fixation ability of H. pluvialis has been gained.

A Novel Approach to Carbon Dioxide Capture and Storage

The novel approach to carbon capture and storage (CCS) described in this dissertation is a significant departure from the conventional approach to CCS. The novel approach uses a sodium carbonate solution to first capture CO2 from post combustion flue gas streams. The captured CO2 is then reacted with an alkaline industrial waste material, at ambient conditions, to regenerate the carbonate solution and permanently store the CO2 in the form of an added value carbonate mineral. Conventional CCS makes use of a hazardous amine solution for CO2 capture, a costly thermal regeneration stage, and the underground storage of supercritical CO2. The objective of the present dissertation was to examine each individual stage (capture and storage) of the proposed approach to CCS. Study of the capture stage found that a 2% w/w sodium carbonate solution was optimal for CO2 absorption in the present system. The 2% solution yielded the best tradeoff between the CO2 absorption rate and the CO2 absorption capacity of the solutions tested. Examination of CO2 absorption in the presence of flue gas impurities (NOx and SOx) found that carbonate solutions possess a significant advantage over amine solutions, that they could be used for multi-pollutant capture. All the NOx and SOx fed to the carbonate solution was able to be captured. Optimization studies found that it was possible to increase the absorption rate of CO2 into the carbonate solution by adding a surfactant to the solution to chemically alter the gas bubble size. The absorption rate of CO2 was increased by as much as 14%. Three coal combustion fly ash materials were chosen as the alkaline industrial waste materials to study the storage CO2 and regeneration the absorbent. X-ray diffraction analysis on reacted fly ash samples confirmed that the captured CO2 reacts with the fly ash materials to form a carbonate mineral, specifically calcite. Studies found that after a five day reaction time, 75% utilization of the waste material for CO2 storage could be achieved, while regenerating the absorbent. The regenerated absorbent exhibited a nearly identical CO2 absorption capacity and CO2 absorption rate as a fresh Na2CO3 solution.

The Control of the Grain Size of Tin.

The tin alloys of tellurium are extremely hard and have very great tensile strength. It was thought that the reduction of the rate of grain growth of tin with the addition of tellurium accompanied this hardening and strengthening and such way found to be true.

Porosity and Oil Absorption Properties of Metal Compacts of Copper - Tin - Graphite

Powder metallurgy, the most recent innovation in met­allurgical process, is not a new art; although not until recently did it become a matter of general interest, this being due not only to the products formed but also to the possibilities of future developments. The manufacture and application of metal powders is now beginning to take a position as a recognized part of the science of metallurgy.

Production of Iron-Tin Compacts by Powder Metallurgy and a Synopsis of their Principle Properties

This thesis is concerned primarily with the production of metal powder compacts of iron and tin. In producing these compacts, the effects of process­ing variables on some of the essential properties of the pellets made were investigated.