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This thesis involves the design, synthesis and testing of organic hydrophobic ligands. They would act as co-collectors in froth flotation processes to enhance the recovery of sulfidic minerals which have undergone some oxidation on processing and are not efficiently collected by the commercial reagents used in froth flotation. Strong and selective binding to iron(III) oxide/hydroxide surfaces, e.g. goethite, over unwanted silicaceous material was considered essential criteria for such new cocollectors. A general overview of froth flotation processes is given in Chapter 1 as well as a description of the analytical techniques used in this thesis and the features that the ligands must have to act as co-collectors. On the basis of the strong binding to iron(III) surfaces of the organic ligand Irgacor 419®, used commercially as a corrosion inhibitor for iron, this compound was studied as a potential co-collector. Adsorption isotherms were determined by UV-Vis spectroscopy for two carboxylic acids that may also bind strongly to goethite, the results of which are discussed in Chapter 2. Chapter 3 involves the measurement of the strength of binding of one the most widely used type of collectors for sulfide ores, potassium ethyl xanthate. Complications in the analysis of materials in solution by both ICP-OES and UV-Vis spectroscopy arose due to the instability of potassium ethyl xanthate in solution, making determination and interpretation of isotherms difficult. The determination of adsorption isotherms for 2-mercaptobenzothiazole, which showed weak binding to goethite as well as to silica, and the mode of binding of 2-mercaptobenzothiazole on copper(I) surfaces is reported in Chapter 4. A crystal structure was obtained in which four units of 2-mercaptobenzothiazole bridge two nickel atoms through the nitrogen atom and the exocyclic sulfur and is considered as a model for binding to sulfidic minerals. Chapter 5 looks at the strength of binding to goethite and silica of various hydroxamic acids. Benzohydroxamic acid was initially selected for study since hydroxamates are known to act as collectors for oxidized materials. Unpredictably, benzohydroxamic acid showed strong binding to a goethite surface and did not release any iron from the surface into solution, which would have been predicted due to its known strong chelating abilities to iron(III). The X-ray structure determination of the first example of a dinuclear Fe(III) hydroxamate complex showed this to have -oxo bridge formed by the hydroxamate unit and supports multisite attachment between this ligand and the surface, as suggested by adsoption isotherms. Simple models based on this dinucleating motif provide plausible modes of multisite attachment to a goethite surface. Competitive binding studies provided a way of ranking the ability to bind to goethite of acetohydroxamic acid, which was not suitable for analyses by either ICP-OES or UV-Vis spectroscopy. Of the ligands studied in this chapter acetohydroxamic acid was found to bind most strongly to goethite followed by benzohydroxamic acid. In Chapter 6, the attachment to goethite and silica of a series of phosphonic acids is investigated. All show a very high binding strength to goethite. Froth flotation experiments at a laboratory scale are described in Chapter 7. The types of ligand that showed strong binding to goethite in adsorption isotherms experiments were tested as co-collectors in different ores and conditions. There is not a simple correlation between adsorption isotherm data and flotation performance as co-collectors because other factors, besides strength of binding, affect the system. Benzohydroxamic acid was the ligand that increased the grade/recovery of the process in all the cases studied. Irgacor 419® enhances the grade/recovery curve for Palabora ore and phenyl malonic acid for Kennecott ore. These results support the original proposition that it may be possible to increase the recovery of oxidized particles substantially by using a blend of collectors which includes a compound to target the oxidized sites.

<p>In general, the research focuses on sequestration of naphthenic acids (NAs) from simulated oil sands process water (OSPW) conditions using engineered copolymers known as &beta;-cyclodextrin-based polyurethanes. The thesis research is divided into two main parts; <i>i)</i> synthesis and characterization of &beta;-cyclodextrin-based polyurethanes, and <i>ii)</i> sorption studies of the copolymer materials with NAs from aqueous solutions.</p> <o>In the first part, &beta;-cyclodextrin (&beta;-CD) was crosslinked with five types of linker molecules, respectively, under various synthetic conditions. The various diisocyanates investigated as linkers include the following: 1,6-hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (CDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate (PDI) and 1,5-naphthalene diisocyanate (NDI). The polyurethanes (PUs) were systematically designed at different mole ratios of monomers by maintaining &beta;-CD and varying the relative mole ratio of diisocyanate monomer from unity to greater values. Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFTS), solid state ¹³C CP-MAS NMR, solution state ¹H/¹³C NMR spectroscopy, thermogravimetric analysis (TGA), elemental analysis (CHN), nitrogen porosimetry, and a dye-based (p-nitrophenol; PNP, and phenolphthalein; phth) sorption method were used to characterize the copolymer materials. In general, the &beta;-CD PUs were insoluble in water except for &beta;-CD crosslinked with HDI at the 1:1 mole ratio which was moderately water soluble. All techniques show complementary results about the structural and compositional characterization, particularly for the estimation of the ratios between the co-monomers. The optimal preparation of copolymer materials for sorption-based applications occurs for &beta;-CD/linker monomer mole ratios from 1:1 to 1:3. There is a maximum limit of the crosslinking density which is ~ 1:7 (&beta;-CD:linker) according to the steric effects of the substituents in the annular region of &beta;-CD. Also, the copolymers were generally found to be mesoporous with relatively low surface area (BET; ~10¹ m²/g) and they appear to exhibit swelling in aqueous solution due to hydration as observed from the estimation of the dye-based surface areas using PNP. The surface accessibilities of the &beta;-CD inclusion sites ranged between 1-100%, as evidenced by the decolourization of phenolphthalein (phth) due to the formation of 1:1 &beta;-CD/phth inclusion complexes.</p> <p>In the second part, the inclusion of NAs and its surrogates with three well known types of cyclodextrin (&alpha;-, &beta;-, and &gamma;-CD) was confirmed using negative ion mode electrospray ionization (ESI). The CDs were found to form well-defined 1:1 inclusion complexes. The binding constant (K2) of NAs and its surrogates inclusion with &beta;-CD was determined indirectly using the spectral displacement technique and were found to be 10³-10⁴ M^-1 (surrogates) and ~ 10⁴ M^-1 (NAs), respectively. Furthermore, the binding constants were found to increase with an increase of the lipophilic surface area (LSA) of the surrogates. The sorption results of NAs with three different types of &beta;-CD materials (i.e. &beta;-CD PU, &beta;-CD crosslinked with epichlorohydrin (EP) and a silica-based mesoporous material containing &beta;-CD), showed &beta;-CD PU had a greater affinity. The sorption capacity (~ 0 - 75.5 mg NAs/g copolymer) and binding affinity (~10³ - 10⁴ M^-1) of &beta;-CD PUs varied due to the nature of linker monomer and the mole ratio of the co-monomers. Aromatic-based copolymers showed high sorption binding affinity while aliphatic-based copolymers showed a relatively high sorption capacity at the co-monomer ratio. Finally, Syncrude-Derived NAs showed fluorescent characteristics which contradict the classic definition of NAs. Further studies using UV-Vis and fluorescence emission spectroscopy showed potential development of an analytical method that can be used to quantify NAs in OSPW for <i>in-situ</i> field applications.

<p>In general, the research focuses on sequestration of naphthenic acids (NAs) from simulated oil sands process water (OSPW) conditions using engineered copolymers known as &beta;-cyclodextrin-based polyurethanes. The thesis research is divided into two main parts; <i>i)</i> synthesis and characterization of &beta;-cyclodextrin-based polyurethanes, and <i>ii)</i> sorption studies of the copolymer materials with NAs from aqueous solutions.</p> <o>In the first part, &beta;-cyclodextrin (&beta;-CD) was crosslinked with five types of linker molecules, respectively, under various synthetic conditions. The various diisocyanates investigated as linkers include the following: 1,6-hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (CDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate (PDI) and 1,5-naphthalene diisocyanate (NDI). The polyurethanes (PUs) were systematically designed at different mole ratios of monomers by maintaining &beta;-CD and varying the relative mole ratio of diisocyanate monomer from unity to greater values. Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFTS), solid state ¹³C CP-MAS NMR, solution state ¹H/¹³C NMR spectroscopy, thermogravimetric analysis (TGA), elemental analysis (CHN), nitrogen porosimetry, and a dye-based (p-nitrophenol; PNP, and phenolphthalein; phth) sorption method were used to characterize the copolymer materials. In general, the &beta;-CD PUs were insoluble in water except for &beta;-CD crosslinked with HDI at the 1:1 mole ratio which was moderately water soluble. All techniques show complementary results about the structural and compositional characterization, particularly for the estimation of the ratios between the co-monomers. The optimal preparation of copolymer materials for sorption-based applications occurs for &beta;-CD/linker monomer mole ratios from 1:1 to 1:3. There is a maximum limit of the crosslinking density which is ~ 1:7 (&beta;-CD:linker) according to the steric effects of the substituents in the annular region of &beta;-CD. Also, the copolymers were generally found to be mesoporous with relatively low surface area (BET; ~10¹ m²/g) and they appear to exhibit swelling in aqueous solution due to hydration as observed from the estimation of the dye-based surface areas using PNP. The surface accessibilities of the &beta;-CD inclusion sites ranged between 1-100%, as evidenced by the decolourization of phenolphthalein (phth) due to the formation of 1:1 &beta;-CD/phth inclusion complexes.</p> <p>In the second part, the inclusion of NAs and its surrogates with three well known types of cyclodextrin (&alpha;-, &beta;-, and &gamma;-CD) was confirmed using negative ion mode electrospray ionization (ESI). The CDs were found to form well-defined 1:1 inclusion complexes. The binding constant (K2) of NAs and its surrogates inclusion with &beta;-CD was determined indirectly using the spectral displacement technique and were found to be 10³-10⁴ M^-1 (surrogates) and ~ 10⁴ M^-1 (NAs), respectively. Furthermore, the binding constants were found to increase with an increase of the lipophilic surface area (LSA) of the surrogates. The sorption results of NAs with three different types of &beta;-CD materials (i.e. &beta;-CD PU, &beta;-CD crosslinked with epichlorohydrin (EP) and a silica-based mesoporous material containing &beta;-CD), showed &beta;-CD PU had a greater affinity. The sorption capacity (~ 0 - 75.5 mg NAs/g copolymer) and binding affinity (~10³ - 10⁴ M^-1) of &beta;-CD PUs varied due to the nature of linker monomer and the mole ratio of the co-monomers. Aromatic-based copolymers showed high sorption binding affinity while aliphatic-based copolymers showed a relatively high sorption capacity at the co-monomer ratio. Finally, Syncrude-Derived NAs showed fluorescent characteristics which contradict the classic definition of NAs. Further studies using UV-Vis and fluorescence emission spectroscopy showed potential development of an analytical method that can be used to quantify NAs in OSPW for <i>in-situ</i> field applications.

It was been reported that untreated wastes from ferrochrome plants release heavy metals including lead, chromium, copper, cadmium, zinc and nickel in the environment. Some of these metals such as hexavalent chromium are potentially toxic and carcinogenic, and can cause a serious threat to human health. The contamination of terrestrial and aquatic ecosystems by hexavalent chromium is worldwide of major environmental concern, especially in South Africa which is the largest producer of chromite and ferrochrome. Therefore, the pre-treatment of these wastes before landfill is of great importance to prevent the contamination of the ecosystems. In the present study, vermiculite, a natural occurring mineral, has been tested for its adsorption effectiveness in removing Cr(VI) from ferrochrome dust leachate. Batch adsorption studies have been carried out to determine the effect of pH, contact time and adsorbent dose on the removal of Cr(VI). The process was found to be highly pH dependent. The optimum conditions for the removal were found to be at pH 1.5, contact time 2 hours and adsorbent dose 10 g.L-1. According to kinetic and isotherm studies, the process is best fitted by the pseudo-second order kinetic model, and to both Langmuir and Freundlich isotherms. The maximum adsorption capacity was found to be 23.25 mg.g-1. Thermodynamic parameters show the spontaneous and endothermic nature of Cr(VI) adsorption onto vermiculite. / Dissertation (MSc)--University of Pretoria, 2011. / Materials Science and Metallurgical Engineering / unrestricted

Natural steroid estrogens such as 17beta-estradiol in low nanogram per liter concentrations can adversely affect the reproductive health of aquatic organisms. The overall goal of this research was to quantify the sorption of 17beta-estradiol to three soils considered to be agriculturally productive from different physiographic regions in Virginia to aid in modeling the concentration of estrogens available for transport in runoff from agricultural fields. Batch equilibrium experiments were conducted with various concentrations of 17beta-estradiol (E2) in a background solution of 5 mM calcium chloride and 100 mg/L sodium azide added to four separate soil samples representative of productive agricultural soils from three different physiographic regions of Virginia. Groseclose loam, Myatt sandy loam and Cecil loam were supplied by the Crop and Soil Environmental Sciences Department at Virginia Tech. All soils were collected from the plow layer (0 to 15 cm) except for an additional Cecil soil sample from the Bt horizon. The concentration of E2 in the liquid phase was measured by gas chromatography/mass spectrometry (GC/MS) and was used to find the time to reach equilibrium and to develop sorption isotherms for each soil. The time required to reach equilibrium for all soils was less than 24 hours. A linear isotherm provided the best fit to model the sorption of E2 to Cecil and Myatt soils (R2 = 0.94 and 0.96, respectively). For Groseclose soil, the general form of the Freundlich isotherm fit best (R2 = 0.98), although the linear isotherm also provided a good fit (R2 = 0.93). The sorption of E2 to agricultural soil appears to be related to the organic carbon content of each soil (Pearson coefficient, 0.82). Attempts to analyze and create isotherms for conjugated E2 by deconjugating with metholysis were unsuccessful. / Master of Science

Yes / The adsorption of acid gas, including hydrogen sulfide and carbon dioxide, by superhigh silica ZSM-5 was investigated. Equilibrium adsorption isotherms of high-purity hydrogen sulfide and carbon dioxide were measured experimentally using this new sorbent. In addition, methane and nitrogen adsorption isotherms on this MFI-type zeolite were also measured as representative of other natural gas components. To enhance the reliability of the results, the adsorption pressure has been selected up to 20 bar at three different temperatures. Superhigh silica ZSM-5 for the adsorption of hydrogen sulfide shows an impressive result of 3.04 mmol·g–1 at 12 bar and 283 K. This value was 2.69 mmol·g–1 for carbon dioxide at 21 bar and 283 K. The adsorption capacity of H2S on the ZSM-5 is the highest, and N2 is the lowest; the order of the adsorption capacities of components is H2S > CO2 > CH4 > N2. The adsorption heat of different adsorbates is calculated: 13.7 and 29.5 kJ·mol–1 for H2S and CO2, respectively. Physical adsorption has occurred on high-silica ZSM-5, especially for hydrogen sulfide, and this is a great advantage. By increasing the temperature, the adsorption capacity of components on the ZSM-5 decreases, but due to differences in the adsorption heat of the adsorbate, the ideal selectivity for hydrogen sulfide increases. There is a challenge in the choice of the best condition for H2S removal, as, by increasing the temperature, the adsorption capacity of hydrogen sulfide reduces, but the selectivity of the hydrogen sulfide increases as compared to other gases. This phenomenon is not true for the selectivity of other components.

Monocamadas insolúveis localizadas sobre a superfície de um líquido são sistemas conhecidos e estudados há mais de 100 anos. Elas são formadas quando moléculas anfifílicas são depositadas sobre algum solvente em condições especiais. Quando sofrem compressão isotérmica, tais sistemas exibem um comportamento muito complexo podendo sofrer várias transições de fase nesse processo. Embora, com o surgimento na década de 1990 de técnicas experimentais que proporcionaram um maior ?insight? no entendimento das referidas transições, há muitas questões que permanecem em aberto, principalmente no que diz respeito à influência exercida: pelas conformações intramoleculares; pelas interações entre as moléculas anfifílicas; pelas interações entre as moléculas anfifílicas e as moléculas do solvente sobre as referidas transições. Para ajudar a preencher esta lacuna são necessários modelos moleculares que auxiliem a obtenção da resposta destas questões. É neste contexto que se insere este trabalho, onde três diferentes modelos de campo médio são empregados a fim de se descrever o comportamento das transições de fase sofridas pelas monocamadas no que se refere aos aspectos acima mencionados. Cada modelo é diferente no que diz respeito ao comportamento das caudas hidrofóbicas erguidas em direção ao ar. O emprego de tais modelos proporcionou, em linhas gerais, um melhor entendimento das transições de fase nestes sistemas. / Insoluble monolayers lying on a liquid surface are known for about one century. They are formed when amphiphilic molecules are deposited on some solvent under special conditions. Under isothermal compression, these systems may exhibit a complex behavior suffering several phase transitions. Although with recent experimental development on the area new insights on the phase transitions were obtained, many questions remain unanswered. Some of these questions are related with the influence of some variables like the intramolecular conformations and the interaction between the amphiphilic molecules and the solvent molecules. In order to fill this gap molecular models are a useful and valuable tool. So, it was employed three different mean-field models in order to describe phase transitions of the molecules. The difference between the models relies on the behavior of the hydrophobic tails lifted on the air. Such models proportioned some insight on the phase transitions of the system.

Phosphorus (P) pollution of waterbodies is a global issue with detrimental environmental, social and economic impacts. Low-cost and sustainable P removal technologies are therefore required to tackle P pollution, whilst also offering a technique for reclaiming P. Ochre, a waste product from minewater treatment plants (MWTPs), has been proposed as a suitable material for the removal of P from enriched waters due to a high content of Fe, Al, Ca and Mg, which have high affinities for P removal. Whilst a range of studies have been conducted investigating ochre as a P adsorbent, most of these are large-scale field experiments and lack understanding of the underlying processes of P removal by ochre. There have also been very few detailed comparisons of different ochre types. The primary focus of this thesis is thus to provide a process-based understanding of P removal by various ochres, in order to investigate the optimal conditions for the use of ochres in the treatment of aquatic P pollution. Seven ochres from six MWTPs in the UK and Ireland were investigated, one of which was in a pelleted form. The ochres were largely comprised of Al, Ca, Fe and Mg (42-68 % by dry weight), had a high B.E.T. surface area, 56-243 m2 g-1, and contained mineral surfaces with a high affinity for P adsorption, such as goethite and calcite. A novel batch experiment methodology was utilised to calculate the adsorption characteristics of ochre at discrete pH conditions. The variation of these characteristics with pH indicates the importance and requirement for such a method to study adsorption by materials at the expected pH conditions of application. At the pH conditions of wastewater streams (~pH 7), the P adsorption capacities of the ochres, determined from fitting adsorption isotherms, was 11.8–43.1 mg P g-1. Results of P adsorption batch experiments were modelled in ORCHESTRA, wherein P removal by the ochres was described well by adsorption onto hydrous ferric oxides. Three of the ochres contain relatively high calcite contents and due to a poor fit of the model to the observed datasets at high pH conditions, with equilibrium P concentrations lower in the batch experiments than the modelled result, adsorption onto calcite is suggested as a P removal mechanism for these ochres at pH > 7. Environmental application of ochre filters will require P removal under flow-through transport conditions. Column experiments were therefore conducted using two ochres, coarse-grained Polkemmet ochre and Acomb pellets (column volume 1055 cm3, pore space 490-661 cm3, typical pore volumes of experiments: 220-400). P removal efficiency increased with contact time, and the presence of competing ions had only marginal effects on P removal. Resting the column substrate for 48 hours between P applications greatly increased the P removal efficiency of a packed column of Polkemmet ochre, resulting in 81 % of influent P removed over 1000 pore volumes of operation (7.68 mg P g-1). Acomb pellets had a lower P removal efficiency than Polkemmet ochre. It is suggested that the high calcium content of the pellets, as a result of the pelletisation process, has created a substrate where the dominant P removal mechanism at neutral pH conditions is adsorption to calcite, which has slower reaction kinetics than adsorption onto goethite. Therefore, this pelleted ochre requires a higher contact time for adsorption reactions to occur. It is suggested that ochre filters are most suitable for application in situations where flow rate is constant or can be controlled e.g. septic tank effluent. Ochres which dry to a coarse particle size are preferred for use as a substrate as pelletisation requires capital, expertise and can produce substrates with slower P sorption kinetics. Resting the filter substrate between P application regenerates surface sites for adsorption, and filters should be run in parallel to maximise P removal efficiency. Acomb pellets, which are a mix of iron hydroxides and alkaline materials, may have potential application as a permeable reactive barrier substrate to treat P enriched ground waters. Further research utilising fine-grained ochres as an additive to P rich fertilisers or for use in continuously stirred tank reactors is recommended.