Approximately 378 million metric tons of soil in the Upper Coastal Plain of Virginia and North Carolina may be processed during proposed titanium mining.. This area is prime agricultural land, and with proper management productivity can be maintained with treated mine tailings. Since P is usually a limiting plant nutrient, proper P fertilization is essential for continued agricultural productivity. Seven different soil systems including unamended tailings (UT), a series of 5 treatments with fertilizers, wood ash, and increasing rates of compost (treatments 1, 3, 6, 8, and 9), and natural soil (NS) were evaluated and compared with regards to P status. Comparisons were based on standard Langmuir adsorption isotherms, Mehlich III extractable-P, and selected chemical and physical properties including pH, cation exchange capacity, compost rate, and specific surface area. Phosphorus adsorption decreased in the order UT, 1, 3, 6, 8, 9, and NS. Decrease in P adsorption was due primarily to increasing organic matter which both physically blocks P adsorption sites, and competes for these sites. Previous addition of large amounts of P fertilizer caused a decrease in P adsorption by occupying some adsorption sites. Wood ash increased pH, which decreased anion exchange capacity and thereby decreased P adsorption. Treatment 9 (12% compost) most closely resembled the natural soil in terms of P status. Agriculturally, economically, and environmentally, the tailings may be suitably managed with high compost rates, an initial heavy application of P fertilizer, and lighter yearly supplements of P fertilizer. / Master of Science

Discharge of colored effluents without decoloration originated from textile industries may cause serious problems in the receiving environments. In this study, natural materials that are basaltic tephra and clinoptilolite were used to remove various dyestuffs used in the textile industry. Those materials are cheap and available in large quantities in Turkey. The investigation of adsorption of basic, acidic and reactive dyes on these materials is the objective of this study. During preliminary experiments it was seen that adsorption equilibrium was reached in about 2 days. In adsorption experiments, in order to obtain adsorption isotherms, a fixed amount of adsorbent and 100 mL dye solutions of different concentrations were placed in glass bottles which were shaken at 200 rpm and 25&plusmn / 2oC for 2 days. Then, samples were filtered and the equilibrium concentrations of dyestuffs in the solutions were determined by using spectrophotometer at appropriate wavelength corresponding to the maximum absorbency. After equilibrium concentrations of the solutions were obtained, Langmuir and Freundlich adsorption isotherm constants were calculated for the adsorbents used in this study. The removal efficiencies for cationic basic dyes are higher than those for anionic acidic and reactive dyes with the natural materials. Therefore, modification of surface properties of natural materials with a cationic surfactant was considered to increase the removal efficiencies of those for anionic dyes. After modification of the surface properties, adsorption capacities of adsorbents for anionic dyes were higher than those of natural materials. Finally, the adsorption capacity of activated carbon for the same dyes was determined to compare with that of natural and modified materials. The results showed that the adsorption of dyes on adsorbents used in this study fitted nicely the Langmuir Isotherm Equations.

This thesis is an experimental investigation on the binding of self-assembling peptides to oligodeoxynucleotides (ODNs) and the characterization of the resulting peptide-ODN complexes/aggregates, the first key step in the development of a peptide-based gene delivery system. Effects of pH, charge distribution along the peptide backbone, and oligonucleotide sequences on the peptide-ODN binding were investigated by a series of physicochemical methods. UV-Vis absorption and fluorescence anisotropy experiments demonstrate that aggregates are formed after mixing the peptide and ODN in aqueous solution. The aggregates in solution can be centrifuged out. Based on this property, the fraction of ODNs incorporated in the peptide-ODN aggregates can be obtained by comparing the UV-Vis absorption of the solution before and after centrifugation. Binding isotherms are generated by a binding density function analysis of the UV absorbance results. The binding parameters are extracted from the analysis of the binding isotherms based on the McGhee and von Hippel model. Equilibrium binding parameter studies show that the binding of two self-assembling peptides, EAK16-II and EAK 16-IV, to model single and double-stranded ODNs at pH 4 is stronger than at pH 7, and that no binding occurs at pH 11. These results demonstrate that electrostatic interactions play an important role in the EAK-ODN binding because EAKs are more positively charged at low pH. EAKs bind more strongly to dG16 than to the other ODN sequences dC16 and dGC16. This demonstrates that the hydrogen bond might be involved because they promote the binding of the lysine residues of the peptide to dG16 to a greater extent than to dC16. The charge distribution along the peptides is found to have an effect on the binding. EAK16-IV, whose positively charged residues are clustered at one end of the peptide, binds to the ODNs more strongly than EAK16-II, whose positively charged residues are distributed throughout the peptide chain, at the same pH. The binding process of EAKs to the ODNs was investigated by fluorescence anisotropy and static light scattering experiments. The results show that individual EAK and ODN molecules complex first, followed by the aggregation of these complexes into large aggregates. The nature of the resulting peptide-ODN complexes/aggregates is examined by UV-Vis absorption, fluorescence anisotropy, and PAGE experiments. The results demonstrate that free EAK, free ODNs, and small EAK-ODN complexes, which can not be centrifuged out, exist in the supernatant, and that large aggregates are collected in the pellets after centrifugation of the solution. The size of the resulting EAK-ODN complexes/aggregates measured by AFM and DLS is around a few hundreds of nanometers at low EAK concentrations. The accessibility of the ODNs to the quencher in the solution is reduced by 40 % and 60 % after binding to EAK16-II and EAK16-IV, respectively, as determined by fluorescence quenching experiments on EAK-ODN mixture solutions. An ODN protection from Exonuclease 1 degradation is provided by the EAK16-II or EAK16-IV matrix when they are mixed with the ODNs at pH 4. However, the ODNs are protected to a much lower degree when the EAK-ODN aggregates are prepared at pH 7. The EAK-ODN aggregates prepared at pH 7 are found to dissociate more easily than those prepared at pH 4 when they are incubated with exonuclease I solution at pH 9.5. These results suggest that the ODN protection afforded by the EAK-ODN aggregates is correlated with their structural stability after being incubated with the nuclease solution. The stability of the EAK-ODN aggregates after dilution is determined by UV-Vis absorption. No detectable dissociation of the aggregates is observed over 20 hrs after a 5- and 10-fold dilution of the solution in the same buffer used for their preparation. The EAK-ODN aggregates remain stable after the solutions are centrifuged, and re-dissolved in fresh buffer solutions. The ability of an EAK matix to protect ODNs from nuclease degradation together with its biocompatibility and low-toxicity suggests that EAK self-assembling peptides could be used as carriers for gene delivery.

The present research seeks to study the decrease in diffusivity rate as relative humidity (RH) decreases and modeling drying shrinkage of hardened cement paste as a poroviscoelastic respose. Thin cement paste strips of 0.4 and 0.5 w/c at age 3 and 7 days were measured for mass loss and shrinkage at small RH steps in an environmental chamber at constant temperature. Non-linear drying diffusion rate of hardened cement was modeled with the use of Fick's second law of diffusion by assuming linearity of diffusion rate over short drops of ambient relative humidity. Techniques to determine drying isotherms prior to full equilibration of mass loss, as well as converting mass loss into concentration of water vapor were developed. Using the measured water vapor diffusivity, drying shrinkage strain was modeled by the theory of poroviscoelasticity. This approach was validated by determining viscoelastic properties from uniaxial creep tests considering the effect of aging by the solidification theory. A change in drying diffusion rate at different RH was observed in the 0.4 and 0.5 w/c pastes at different ages. Drying diffusion rate decreases as RH drops. This can be attributed to a change in diffusion mechanisms in the porous media at smaller pore radius. Shrinkage modeling with an average diffusion coefficient and with determined viscoelastic parameters from creep tests agreed well compared to the shrinkage data from experiments, indicating that drying shrinkage of cement paste may be considered as a poroviscoelastic reponse.

The objective of this study was to investigate the removal of mercury chloride in flue gas emitted from municipal waste incinerator (MWI) by the adsorption of powdered activated carbon derived from the pyrolysis of waste tires (PAC-T). This study focused on the removal efficiency of mercury chloride and the adsorption capacity of PAC-T. The operation parameters investigated included temperature (30¢J and 150¢J) and powdered activated carbon injection rate (0.1, 0.2 and 0.3 g/hr). Experimental tests were conducted by the following three steps¡G the adsorption column test, the adsorption isotherm simulation, and the removal efficiency test in a pilot plant. The adsorption capacity of PAC-T for various inlet mercury chloride concentrations (55~215£gg/m3) at room temperature (30¢J) were 811~2,188£gg-HgCl2/g-PAC, while the absorption capacity of PAC-T at 150¢J were 214~700£gg-HgCl2/g-PAC which were lower than those at room temperature. It suggested that the adsorption capacity of PAC-T decreased as adsorption temperature increased. Furthermore, the adsorption of mercury chloride by PAC-T was an unfavorable adsorption isotherm. The adsorption column tests were performed to assess the rate of mercury chloride uptake by PAC-T at 30 and 150¢J. Results from the adsorption isotherm simulation indicated that mercury chloride at room temperature (30¢J) can be simulated by the Redlich and Peterson isotherm. However, the adsorption of mercury chloride at 150¢J can be simulated by the Langmuir isotherm. Experimental results from the pilot tests indicated that the removal efficiency of mercury chloride increased gradually with retention time and then leveled off as retention time was higher than thirty minutes. Moreover, the removal efficiency of mercury chloride increased dramatically as PAC-T injection rate increased from 0.1 to 0.3 g/hr. The highest removal efficiency of mercury chloride which can be achieved by waste-tire derived powdered activated carbon (PAC-T) and commercial powdered activated carbon (PAC-C) were 86.5% and 98.9%, respectively. In general, PAC-T was comparative to PAC-C for the removal of mercury chloride from flue gas on the basis of both physical and chemical properties and removal efficiency of mercury chloride.

Isotherms of one atom thick film of adsorption for propane on purified Hipco single-walled carbon nanotube were experimentally studied at 6 different temperatures ranging from 190K up to 280K. In these isotherm measurements, two substeps were clearly present at temperatures between 190K and 220K. For propane adsorption, two different groups of binding energy sites on the nanotubes were determined by the outcome. Also, we found that those substeps were gradually smearing as the temperature increases. These features of propane adsorption were compared to the same features that were present for the case of ethane and butane adsorption on the same sample. In comparison, high binding energy sites revealed by low pressure substeps were clearly visible in all the cases. However, the high pressure substep that represents a low binding energy site, external surface site, was smearing as carbon chain length of adsorbed alkanes increase. For the case of butane adsorption, the substep was not pronounced in the alkanes' isotherms at the relative temperatures. We also determined a decrease in the values of specific surface area of the nanotubes and an increase in the values of binding energies of alkanes on the substrate were increased as the sizes and lengths of linear carbon alkanes were increased.

>Magister Scientiae - MSc / There are huge amount of natural clinoptilolite available in South Africa which can be utilised for wastewater treatment of ammonia and chromium if their characteristics are properly known. However, these deposits have not been well characterised but in this study, the untreated clinoptilolite materials were fully characterised using techniques such as SEM-EDS, HRTEM-SAED, XRD, XRF, FTIR and BET. After acid pretreatment with several extractions, the pretreated samples were again characterised using the above mentioned techniques. These pretreated materials were used for NH₄⁺ and Cr³⁺ adsorption of wastewater. The three natural South African clinoptilolite samples used in this study were from ECCA Holdings (ESC and EHC samples) and Pratley (PC sample) deposits obtained from Western Cape and KwaZulu-Natal Province respectively. This study revealed that the chemical composition and mineral phases of South African clinoptilolites vary considerably from site to site, even clinoptilolite mined from the same deposit sites. The XRD analyses showed that Pratley clinoptilolite (PC) was the most pure clinoptilolite sample (81.41 %) compared to the purity of EHC (67.88 %) and ESC (44.0 %) sample. The ECCA Holdings untreated clinoptilolite samples contained dense phases such as quartz which was not found in Pratley sample. Quartz was found to be the most dominant impurity in both ECCA Holding sample. The cation exchange capacity (CEC) of ESC, EHC and PC samples were found to be 1.23, 1.81 and 2.90 meq/g respectively and these results were compared to that of XRF analyses. The acid solutions of 0.02 and 1.0 M HCl were used to pretreat natural clinoptilolite to determine the optimum acid concentration and number of extractions required to fully replace the exchangeable cations. The pretreatment results showed that 0.02 M HCl was the optimum acid concentration for acid pretreatment of clinoptilolite samples. Between 7 and 22 extractions were required to remove Na⁺, K⁺, Ca²⁺ and Mg²⁺ without causing much dealumination of the framework. Sodium ion was found to be weakly bound cation in the clinoptilolite framework, since it could be completely exchanged by H⁺ after 7 extractions with 0.02 M HCl acid solution. Potassium ion was found to be strongly bound in the clinoptilolite framework since it could not be completely exchanged during the acid pretreatment process even after 22 extractions. The HRTEM-SAED and BET results showed that ESC, EHC and PC were all polycrystalline and microporous materials respectively. It was found that the adsorption capacity of the treated Pratley clinoptilolite sample was increased by 36 % for NH₄⁺ removal, compared to that of the untreated PC sample. The adsorption study results showed that the pretreatment of clinoptilolite samples using 150 mL volumes of 0.02 M HCl with 7 acid extractions at 25 °C for ESC pretreated and EHC pretreated. The pretreatment of PC sample at 22 extractions could remove high percentage of NH₄⁺ (98.11 %) within a short contact time of 10 min. The pretreated Pratley clinoptilolite sample was found to be the best NH₄⁺ adsorbent (98.11 % NH₄⁺ removal) compared to EHC treated (93.89 % NH₄⁺ removal) and ESC treated (75.00 % NH₄⁺ removal) clinoptilolite samples. However, acid-pretreated Pratley clinoptilolite did not sufficiently remove Cr³⁺ (16.10 %) from synthetic wastewater showing that it is not a good adsorbent for this particular metal ion removal. Despite several studies that have been conducted on clinoptilolite, no study has been carried out on the pretreatment and comparison of sorption capacity of different South African clinoptilolites for the removal of NH₄⁺ from wastewater. This study has been able improve on the acid-pretreatment procedure for clinoptilolite. This study demonstrated that it is not only the acid concentration that is important but also the number of extractions needed to remove all the exchangeable cations from the clinoptilolite framework. This study has also been able to prove that South African clinoptilolite can treated ammonia from wastewater.

Steel slag is a by-product from steel production and has potential to act as a sorbent for several contaminants. Contaminated water is a global problem and cheap and simple remediation solutions are often sought. The potentials are many to use an industrial residue for water purification purposes e.g. low cost. The absorption efficiency was evaluated for two different steel slags further divided into two grain sizes, <0.9 mm and 0.9-2 mm. Laboratory experiments was conducted for three anionic elements; bromine, chromate and molybdate. Controlled parameters were; time, sorbent amount and sorbate concentration. The sorption was primarily dependent on the grain size and the smaller grain size had a higher sorption of all three tested anionic species. Unfortunately the results are partially affected by the release of the tested elements from the sorbent itself.

>Magister Scientiae - MSc / Titanium dioxide (TiO2) has potential as an adsorbent within the 68Ge/68Ga generator context. To function effectively, three basic requirements are required: optimum 68Ga elution efficiency, stability and removal of the 68Ge breakthrough. After analysis of the 68Ga elution efficiency and the 68Ge breakthrough, two models are proposed, namely; surface modification and molecular imprinted polymer, to address factors influencing 68Ga elution efficiency and minimize 68Ge breakthrough. The surface modifiers that were investigated are 3-aminopolypropyltriethoxy silane (3-APTES), 3-mercaptopropyltrimethoxy silane (3-MPTMS), bis(3-aminopropyl)amine (BAPA) and 2-chloro-4,6-dimethoxy-1,3,5-triazine silane (CDMT). / 2023

<p> Rate of adsorption data for gases on molecular sieve·s and coals have been interpreted using equations for unsteady state diffusion derived from Fick's law for spheres usually, ignoring the amount adsorbed and the shape of the adsorption isotherm. These inappropriate equations result in calculated diffusivities that are too low and activation energies that are too large. </p> <p> Numerical. solutions of Fick's law were made for diffusion and adsorption in a porous sphere of radius R by finite difference methods for the following conditions: a. Diffusion is the rate-controlling step, and the diffusivity, D, is constant. b. Within an increment of the particle the total amount of adsorbate per unit volume, T is related to the "effective" concentration, c, by a Langmuir-like isotherm T = abC/(1 + bC). c. At zero tine the particle containing no adsomate is surrounded by adsozbate of concentration, Co, which remains constant throughout the rate process, and d. Equilibrium is established immediately at the periphery of the sphere. </p> <p> The solutions are obtained in terms of Z = Q/Q and T=(DCo/QR^2) t = kt, where t is time, k is a constant equal to the term within the brackets, and Q and Q are the amounts adsorbed per unit volume at time t and at equilibrium. The quantity within brackets is also a valid expression for linear and Freundlich-like adsorption isotherms and probably holds for other isotherms. Plots of z as a function of T shift systematically as the parameter B = bCo increased from 0, corresponding to a linear adsorption isotherm, to large values; the value of Z at a given T increasing with increasing values of B. For B = 0 the numerical solution is identical with analytical solution for the linear adsorption isotherm which for values of z <0.87 is given by kt = (2/π) { (-1 - πZ/6) - (1 ~πZ/3) ^1/2 } where k = DCo/R^2Q. For large values of B the numerical solutions approach as a limit the parabolic law kt = (1/2) {(1- 2Z/3) - (1- Z) } The value of (1/k~) o.zidt~ at short times increases fran 3.385 for B = 0 to 4 .. 243 for very large values of B.. From experimental data the value of k derived using the equation for B = 0 is 1.56 larger than for the parabolic equation. Hence the values of D obtained from the initial linear portions of t.he rate curve change by only a factor of 1.56 when the type of isotherm is changed from linear to rectangular. </p> <p> Rates of adsorption and the adsorption isotherm were determined for N2 , CH4, co2 , and C2H6 on samples of Linde 4A molecular sieve at several temperatures from -78° to +50°C in a manostatic volumetric aborption apparatus. The Langmuir equation satisfactorily approximatedthe isotherms and the values of B were moderately large at the lower temperatures of each series of experiments, eg., for N2 at -78°C, 10.6; for CH4 at -78°C, 7.3; for co2 at 0°C, 64; for Ci!6 at 0° and 30°C, 37 and 10.3. </p> <p> The rate data plotted as Z against t^1/2 were not linear at short times but curved upward initially before becoming linear. The initial (, nonlinear portion persisted significantly longer than the brief uncertain period at the beginning of the experiment. This phenomena could result from the equilibration at the periphecy of the particles requiring a finite time rather than being instantaneous. </p> <p> An equation based on the parabolic law model and a first order equilibration process was derived, which fits. the experimental data for 0.05 < Z < 0.95. This equation is appropriate only to data with a large value of B, but is probably a reasonable approximation for other rate data. </p> <p> The rates of adsorption for different molecules were co2 > N2 > CH4 > c2H6 · The activation energies for the diffusivity were found to be 4.1 and 6.0 kcal./nole for methane and ethane. The _heats of adsorption were found to be 7.2 and 8.3 kcal/mole for methane and ethane. </p> / Thesis / Master of Engineering (MEngr)