Investigations on the determination of 137Cs sources in the Ignalina NPP environment air and the evaluation of changes of the long-term trend of 137Cs activity concentrations in the Ignalina NPP ground-level air were carried out in this dissertation. Radionuclide activity concentrations in the air and deposition were measured in the Ignalina NPP impact zone in 2004-2009. Results show, that in recent years annual 137Cs activity concentrations in the ground-level air in the Ignalina NPP region change with the half-time of 30 years. Observed episodic increases in 137Cs activity concentrations in the air correlate well with air mass transport trajectories that intersect territories, polluted with 137Cs after the accident at the Chernobyl NPP. The growth of radioactive aerosol particles in the oversaturated water vapour of the operating RBMK reactor has been investigated. In the one contour nuclear power plant coolant water steam, noble gas radionuclides decay into alkaline and earth-alkali metals, which become condensation nuclei and due to the absorption of water molecules in several minutes grow into radioactive aerosol particles. The classical method of the radionuclide activity determination in aerosol particle samples, collected on filters, was supplemented with experiments on the leaching of aerosol particles using the distilled water and measurements of radionuclide activities in samples before and after the experiment. Results show that the quantity of 137Cs and 60Сo in... [to full text] / Disertacijoje nustatyti 137Cs patekimo į Ignalinos AE aplinkos orą šaltiniai ir įvertinti ilgamečiai 137Cs aktyvumo koncentracijų ore pokyčiai. Radionuklidų aktyvumo koncentracijos ore ir iškritose matuotos nuo 2004 iki 2009 metų Ignalinos AE poveikio zonoje. Gauta, kad metinės 137Cs aktyvumo koncentracijos pažemio ore pastaraisiais metais kinta su 30 metų mažėjimo pusiau trukme. Stebėta, kad šuoliški 137Cs aktyvumo koncentracijų pažemio ore padidėjimai koreliuoja su oro masių pernašos trajektorijomis, kertančiomis teritorijas, užterštas po avarijos Černobylio AE. Nustatytas radioaktyvių aerozolio dalelių augimas prisotintuose vandens garuose veikiančio RBMK reaktoriaus kondensatoriuje. Vieno kontūro atominės elektrinės aušinamame vandens gare inertinių dujų radionuklidai, skildami virsta šarminių ir žemės šarminių metalų elementais, tampa aerozolio gamybos centrais, absorbuoja vandens molekules ir per keliolika minučių ant jų, kaip kondensacijos branduolių, išauga radioaktyvios aerozolio dalelės. Klasikinis radionuklidų aktyvumo aerozolio dalelių, surinktų filtrais, bandiniuose nustatymas papildytas išplovimo distiliuotu vandeniu eksperimentais, matuojant radionuklidų aktyvumą bandiniuose iki ir po eksperimento. Gauta, kad 137Cs ir 60Сo dalis aerozolio dalelių, surinktų veikiančio reaktoriaus ventiliaciniame ore, tirpioje frakcijoje buvo 74 17 %, atitinkamai, o neveikiančio reaktoriaus ventiliaciniame ore 22 % ir 67  5 %. 60Co aktyvumo koncentracijos AE fakele... [toliau žr. visą tekstą]

Disertacijoje nustatyti 137Cs patekimo į Ignalinos AE aplinkos orą šaltiniai ir įvertinti ilgamečiai 137Cs aktyvumo koncentracijų ore pokyčiai. Radionuklidų aktyvumo koncentracijos ore ir iškritose matuotos nuo 2004 iki 2009 metų Ignalinos AE poveikio zonoje. Gauta, kad metinės 137Cs aktyvumo koncentracijos pažemio ore pastaraisiais metais kinta su 30 metų mažėjimo pusiau trukme. Stebėta, kad šuoliški 137Cs aktyvumo koncentracijų pažemio ore padidėjimai koreliuoja su oro masių pernašos trajektorijomis, kertančiomis teritorijas, užterštas po avarijos Černobylio AE. Nustatytas radioaktyvių aerozolio dalelių augimas prisotintuose vandens garuose veikiančio RBMK reaktoriaus kondensatoriuje. Vieno kontūro atominės elektrinės aušinamame vandens gare inertinių dujų radionuklidai, skildami virsta šarminių ir žemės šarminių metalų elementais, tampa aerozolio gamybos centrais, absorbuoja vandens molekules ir per keliolika minučių ant jų, kaip kondensacijos branduolių, išauga radioaktyvios aerozolio dalelės. Klasikinis radionuklidų aktyvumo aerozolio dalelių, surinktų filtrais, bandiniuose nustatymas papildytas išplovimo distiliuotu vandeniu eksperimentais, matuojant radionuklidų aktyvumą bandiniuose iki ir po eksperimento. Gauta, kad 137Cs ir 60Сo dalis aerozolio dalelių, surinktų veikiančio reaktoriaus ventiliaciniame ore, tirpioje frakcijoje buvo 74  22 % ir 67  17 %, atitinkamai, o neveikiančio reaktoriaus ventiliaciniame ore – 24  5 % ir 20  5 %. 60Co aktyvumo koncentracijos AE... [toliau žr. visą tekstą] / Investigations on the determination of 137Cs sources in the Ignalina NPP environment air and the evaluation of changes of the long-term trend of 137Cs activity concentrations in the Ignalina NPP ground-level air were carried out in this dissertation. Radionuclide activity concentrations in the air and deposition were measured in the Ignalina NPP impact zone in 2004-2009. Results show, that in recent years annual 137Cs activity concentrations in the ground-level air in the Ignalina NPP region change with the half-time of 30 years. Observed episodic increases in 137Cs activity concentrations in the air correlate well with air mass transport trajectories that intersect territories, polluted with 137Cs after the accident at the Chernobyl NPP. The growth of radioactive aerosol particles in the oversaturated water vapour of the operating RBMK reactor has been investigated. In the one contour nuclear power plant coolant water steam, noble gas radionuclides decay into alkaline and earth-alkali metals, which become condensation nuclei and due to the absorption of water molecules in several minutes grow into radioactive aerosol particles. The classical method of the radionuclide activity determination in aerosol particle samples, collected on filters, was supplemented with experiments on the leaching of aerosol particles using the distilled water and measurements of radionuclide activities in samples before and after the experiment. Results show that the quantity of 137Cs and 60Сo in... [to full text]

The effects of some associated minerals on thiosulfate gold leaching were studied through thermodynamic analysis and leaching experiments on composite ore samples containing various minerals and a reference silicate gold ore. In the leaching test on the reference gold ore, about 93% of gold was extracted within 3.0 hours. The presence of various amount of pyrite, pyrrhotite, chalcopyrite, arsenopyrite, chalcocite, bornite, and some lead species, has significant detrimental effects. Under reduced oxygen conditions, the thiosulfate consumptions could be significantly reduced. High gold extractions (i.e. >= 90%) were observed in the leaching tests with reduced dissolved oxygen (i.e., 0.7% oxygen in the supplied gas) in the absence or in the presence of sulfide minerals such as pyrite, pyrrhotite, arsenopyrite and chalcopyrite. High copper concentration and a pre-aeration step was also found to largely increase the gold extractions under such conditions. Thiosulfate-copper-ethylenediamine system was found effective in the leaching of gold. The leaching kinetics was significantly slower than that of the conventional thiosulfate-copper-ammonia leaching. The consumption of thiosulfate, however, was largely reduced. This leaching system worked effectively on the reference gold ore within a wider pH range (e.g., 6-11), with or without ammonia. The presence of ammonia in a low concentration improved the leaching rate but also increase the consumption of thiosulfate. Comparable gold extractions were observed in the leaching of the composite ores containing various sulfide minerals, such as pyrite, pyrrhotite, chalcocite, galena and chalcopyrite. The leaching of gold in the presence of iron sulfides was also improved by applying chemical additives, such as, carbonate, calcium, galena, phosphate, and additional hydroxide anion. It is proposed that these additives either passivated the harmful surface of sulfide minerals or masked some detrimental aqueous species. Finally, some improved leaching methods concluded in this study were applied on a few industrial ore samples in order to demonstrate the effectiveness of these methods. It was found that by comprehensively applying these improved thiosulfate leaching strategies, satisfactory gold extractions and thiosulfate consumption results were archived on these ores. / Thesis (Ph.D, Mining Engineering) -- Queen's University, 2008-09-18 11:48:38.672

Most waste generated in South Africa is sent to landfills for disposal, and although it is confined in specific areas, it can potentially affect both above and below ground water resources, impacting environmental and public health. This is particularly relevant in a country where water supplies are limited and groundwater resources are prone to pollution. The primary objective of this study was to assess the performance of an upflow packed-bed bioreactor purposedesigned for the treatment of leachates produced by landfills in the Durban Metropolitan Area (DMA). The effect of parameters such as the nature of the biofilm support matrix, aeration rate and recycle rate on the efficacy of the system were investigated. Another major aim of the project was to develop a low maintenance technology that could, nonetheless, bioremediate leachate effectively at minimum cost. This aspect of process design is a crucial factor in areas where there is a shortage of both funds and skilled labour. The glass 132 l packed-bed upflow bioreactor was evaluated by measuring its efficiency in terms of chemical oxygen demand (COD) and biological oxygen demand (BOD) reduction and ammonia removal. The bioreactor could be configured as a batch-type system, which was useful for comparing operating conditions; or as a continuous cascade system, which was used to assess its overall performance. Different biofilm support matrices viz. various grades of pine bark, plastic bioballs and ceramic noodles were evaluated in 22 l batch-type reactors. Leachates from five landfill sites were remediated during the course of the study, and only the leachate from Shongweni landfill, which had a remarkably low BOD:COD ratio (0.05), was intractable and could not be successfully treated; even in flask trials designed to test strategies such as augmentation of microflora and biostimulation. The other leachates investigated were from the Umlazi, Marianhill, Bisarsar Road (all general sites) and Bul-Bul Drive (a semi-hazardous site) landfills, all of which were remediated to some degree. Originally, leachate from the Umlazi landfill site was used, but it became unavailable when the site closed enforcing the use of other leachates for the remainder of the investigation. Leachates from Marianhill, Bisarsar Road and Bul-Bul Drive were treated simultaneously in duplicate operating the six-chambered bioreactor in the batchtype configuration. The highest COD removal efficiency (49 %) was obtained in the chambers treating the Bul-Bul Drive leachate, which was therefore used for further investigations. This leachate had the highest BOD:COD ratio and was therefore expected to be the most suited to biological remediation. The bioreactor performed best when plastic bioballs were used as biofilm support matrix with a relatively low level of aeration, although the uncomposted form of pine bark was used initially as the support matrix because it is inexpensive and readily available in South Africa. However, although satisfactory COD reduction (30 – 61 %) and ammonia removal (87 – 98 %) was achieved when the Umlazi leachate was treated, the possibility of compounds leaching out of the bark and affecting the quality of the treated leachate was a concern. Also, pine bark would be prone to mechanical degradation in a full scale operation. Of the other solid support matrices tested using the Bul-Bul leachate, COD removal efficiencies were superior with plastic bioballs (60 %) than with pine bark chips (29 %). The former therefore became the preferred biofilm support matrix. Aeration level did influence bioremediation of the Umlazi landfill leachate since those chambers aerated with an aquarium pump (0.05 – 0.1 litres air/litre leachate/min; 60 % COD removal) performed better than those aerated with a blower (0.6 -0.7 litres air/litre leachate/min; 42 % COD removal) and those that remained unaerated (44 % COD removal). Recycle rate did not significantly affect bioremediation, but the performance of the system was higher when operated in batch mode (up to 60 % influent COD removal), rather than in continuous flow-through (cascade) mode when only 37 % of the influent COD in the Bul-Bul leachate was removed. Under the latter conditions, most of the reduction occurred in the first four chambers and very little biodegradation occurred in the final two chambers. The cascade-mode will require some refinement to enhance the COD removal efficiencies achieved. However, it did eliminate 89 % of the BOD present in the raw leachate, producing a treated effluent with a consistent BOD:COD ratio of 0.05. The COD removal efficiencies achieved covered a wide range from a minimum of 23 % with Marianhill leachate to a maximum of 63 % with leachate from Bul-Bul Drive. These results are comparable with many of those reported by other authors treating landfill leachate. Up to 98 % of the ammonia was removed when the Umlazi leachate was treated. However, ammonia removal from the other leachates tested was erratic. Although the treated leachate from this system could not be released into the environment without further remediation, the reduction in concentration of pollutants would allow its return to the local water supply via a wastewater treatment plant. This was achieved without temperature and pH regulation or addition of extraneous nutrient sources. A cost-effective, low maintenance technology such as this one would be a useful tool for the treatment of effluents such as landfill leachate in countries like South Africa where although water conservation is urgently required, resources for highly sophisticated effluent remediation are often not readily available. / Thesis (Ph.D.)-University of KwaZulu-Natal, Pietermaritzburg, 2011.

The temporal fate of selected parameters, including redox potential; pH; phenol; nitrates; sulphates; copper and zinc, of a young synthetic acetogenic phase landfill leachate was assessed by perfusing a series of sequential soil (Hutton) microcosms (arrays) at two hydraulic loading rates (HLR). We chose HLRs that were representative of areas in South Africa with typically elevated rainfall (Pietermaritzburg – HLRh) and one with relatively low rainfall (Kimberley – HLRl). Preliminary phenol, copper, and zinc adsorption investigations on gamma radiation sterilized soil and unsterilized soil revealed superior adsorption rates for each compound in the unsterilized soil. This revealed the importance of the biological component of soil in phenol, copper, and zinc attenuation in soil. The results presented in this thesis suggest that the HLR of leachate into soil arrays contributes to significant differences in the fate of the landfill leachate parameters mentioned earlier. In addition, we assessed the temporal and spatial succession of bacterial community diversity in each of the soil arrays by polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE). Prior to this, we compared two soil DNA isolation techniques, the modified method of Duarte et al. (1998) (Bead Beat) and the commercial Mo-Bio UltraClean™ Soil DNA isolation kit (Kit). The DNA isolated by the Kit method was significantly superior regarding purity and absence of DNA fragmentation. However, the Bead Beat method produced a significantly higher yield per reaction before further purification with Wizard™ Clean-Up columns produced DNA extracts of similar purity at the cost of a significant reduction in DNA yield. The Kit method was chosen for future DNA isolation and PCR-DGGE based on the quality of the PCR amplicons generated from the Kit isolated DNA. PCR-DGGE was further optimized by comparing the efficiency and sensitivity of a silver stain against ethidium bromide. Silver stain generated DGGE gels with greater number of bands (species richness – S) and stronger band signal intensities. Captured DGGE fingerprints generated data that were subjected to the Shannon-Weaver Index (H’) and the associated Shannon-Weaver Evenness Index (EH) to measure the change in spatial and temporal bacterial diversity. There was a significant shift in S and H’ for both HLRs but a significant change in EH was only observed for HLRh. Furthermore, a temporal comparison of S and H’ between both HLRs revealed significant differences throughout the investigation. Canonical Correspondence Analysis (CCA) revealed spatial distribution of bacterial community diversity with depth. Effects of phenol concentration, redox potential, and pH of the effluent leachate on bacterial community diversity was tentatively assessed by three-dimensional graphical representation on PlotIT 3.2 software. Bacterial community diversity showed a decrease with elevated pH and phenol concentration along with decreasing redox potentials for both HLRs. While this study reveals the spatial and temporal dynamics of bacterial community diversity in situ, it provides important evidence with respect to: (i) the effects of rainfall / leaching rates (HLR) on spatial and temporal bacterial community succession; (ii) the importance of the biological component in natural attenuation; (iii) the ability of soil, previously unexposed to landfill leachate, to initiate natural attenuation of phenol and other leachate constituents; (iv) the capacity of PCRDGGE to fingerprint successional changes in bacterial community diversity, (v) and the potential to clone and sequence selected members of bacterial associations for future reference in environmental remediation strategies. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2008.

Fanny Creek drains from Island Block opencast coal mine, near Reefton on the West Coast of the South Island of New Zealand, and is impacted by acid mine drainage (AMD). The objectives of this study were to characterise drainage chemistry in Fanny Creek catchment, and to determine optimal passive treatment strategies for Fanny Creek AMD for future pilot or full-scale application. This was undertaken by monthly monitoring in Fanny Creek catchment between February 2008 and January 2009 to collect drainage chemistry and flow data. Laboratory trials of suitable passive AMD treatment systems were conducted and their treatment performance assessed to select and design optimal passive treatment strategies for Fanny Creek AMD. Oxidation of pyrite in Brunner Coal Measure sediments at Island Block mine generates AMD. Fanny Creek originates from a number of AMD seeps on the eastern waste rock slope of Island Block mine. Seeps have low pH (<3.23) and a single detailed metal analysis indicates drainage is enriched with aluminium and iron, and contains elevated concentrations of manganese, copper, nickel, zinc and cadmium relative to applicable water quality criteria such as ANZECC guidelines. Acidity and metal loadings of drainage in the catchment indicates AMD from the northern waste rock slope contributes most of the acidity (~70%) and metal (60%) in Fanny Creek, and acts to re-dissolve additional metals upon mixing with drainage from other slopes. The most suitable location for a passive AMD treatment system in Fanny Creek catchment is on the Waitahu Valley floor, near monitoring site R12, because this allows for sediment removal prior to a treatment system. Fanny Creek AMD at site R12 was characterized in detail because this data assists with selection and design of passive AMD treatment systems. Fanny Creek at site R12 contains on average 6.0 mg/L aluminium, 1.3 mg/L iron, 3.1 mg/L manganese, 0.49 mg/L zinc, 0.14 mg/L nickel, 0.0071 mg/L copper and 0.00048 mg/L cadmium. Average pH at site R12 was 3.95, calculated acidity averaged 42.7 mg CaCO₃/L, and flow rate ranged from 1.5 L/s to about 30 L/s. Acidity and metal generation from Island Block mine increases linearly with flow in the catchment, and therefore Fanny Creek drainage chemistry is not significantly affected by rainfall dilution. Natural attenuation of AMD occurs by addition of un-impacted alkaline drainage from Greenland Group basement rocks, wetland ecosystem processes, and geochemical reactions along Fanny Creek that decrease acidity and metal concentrations before AMD discharges into the Waitahu River. During low flow conditions (summer months), surface flow of AMD into the Waitahu River does not occur because of subsurface flow loss. Three suitable passive AMD treatment options for Fanny Creek AMD were selected and trialed at ‘bench top’ scale in a laboratory. These included a sulfate reducing bioreactor (SRBR), a limestone leaching bed (LLB), and an open limestone channel (OLC). The potential to mix Waitahu River water with Fanny Creek to neutralize AMD was also investigated. Fanny Creek AMD was employed for laboratory trials, and influent flow rates into SRBR, LLB and OLC systems were regulated to assess performance at different hydraulic retention times (HRT). Optimal HRTs for future treatment system designs were determined from effective AMD treatment thresholds, and include 51 hours, 5 hours and 15 hours for SRBR, LLB and OLC systems, respectively. To determine optimal treatment options for Fanny Creek AMD the effectiveness of each trial option was compared to applicable water quality criteria, and scale up implications of treatment options was assessed. The SRBR system had most effective AMD treatment, with water quality criteria achieved for metals, greatest alkalinity generation, and highest pH increase. However, a full scale SRBR system has significant size requirements, and long term treatment performance may be limited. The LLB system decreased metals to below, or just slightly above criteria for all metals, and has significantly smaller size requirements compared to a SRBR system. The OLC system was least effective, with effluent above water quality criteria for all metals except iron, and with lowest alkalinity generation. The Waitahu River is capable of neutralizing AMD because it is slightly alkaline. The flow volume of river water required for neutralization is between 65 L/s and 140L/s, which can be gravity fed to mix with Fanny Creek. These results indicate that either a LLB treatment system or the Waitahu River Mixing option are the optimal passive treatment strategies for Fanny Creek AMD. On site pilot scale testing of SRBR and LLB systems, and the Waitahu River Mixing option is recommended because of AMD treatment uncertainty, and to more accurately select and design full scale passive treatment strategies.

Zeolites have been used in agriculture since the 1960s, due to the effectiveness of these crystalline microporous solids as soil amendments for plant growth, their cation exchange capacity (CEC) and slow-release fertilizer properties. Most work on slow-release fertilizers has focused on natural Clinoptilolite, Phillipsite and Chabazite. The aim of this study was to synthesize zeolites, study their effectiveness as soil amendments and their ability to act as controlled release fertilizers to decrease nitrate leaching. Nitrate pollution of groundwater is a major agro-environmental concern. The zeolites Phillipsite and Linde-type F were synthesized from aluminosilicate gels; ion exchanged to introduce ammonium and characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), Thermo-gravimetric analysis (TGA) and Scanning electron microscopy (SEM) techniques, both before and after ion exchange. Ammoniumexchanged Phillipsites (natural and synthetic), ammonium-exchanged synthetic Linde-type F (the zeolite having highest affinity towards ammonium) and ammonium exchanged Phillipsites (high crystalline and high aluminium) were compared with conventional NPK fertilizer.Three glasshouse experiments were performed to study the effects of zeolite-amended soils on maize growth. Ion exchanged synthetic and natural Phillipsites were first used as soil amendments (w/w 2, 4, 8% zeolite to soil). Synthetic Phillipsite, at 2% loading, resulted in the most significant improvement in both plant growth and phased ammonium release. The synthetic ammonium-exchanged zeolites Phillipsite and Linde-type F (at w/w 1, 2, 4%) were then compared; synthetic Phillipsite, at 2% loading, again resulted in the most significant plant growth response with an increase (≥15%) in shoot dry weight and a decrease (≥30%) in nitrate leaching. Experiments using unexchanged synthetic Phillipsite (at w/w 2%), but with added NPK fertilizer, showed increased plant growth and decreased nitrate leaching, compared with parallel experiments containing unexchanged synthetic Linde-type F (at w/w 2%) and a conventional fertilizer amended soil. This revealed the beneficial effect of Phillipsite for soil amendment, even without ion exchange to the ammonium form. To study the physico-chemical properties affecting the release of ammonium from the Phillipsite framework; high crystalline/low aluminium and low crystalline/high aluminium forms were synthesized and ion exchanged. Both forms were introduced as soil amendments (at w/w 1 and 2%) and experiments showed that the lower zeolite crystallinity decreased cation exchange and therefore decreased nitrate leaching. Experimental results from the glasshouse experiments and cation exchange capacity (CEC) experiments suggest that synthetic Phillipsite, at lower loadings (1 and 2% w/w zeolite to soil) have most potential as soil amendments for both plant growth and controlled-release applications. This conclusion is supported by soil leachate and shoots dry weight analysis. Furthermore, Phillipsite, synthesized in a low crystalline and low ammonium form, may be an even better soil amendment for controlled release of ammonium, which will thereby further decrease nitrate pollution.

A fundamental theoretical and experimental study on calcium sulphate scale formation in hydrometallurgical solutions containing various minerals was conducted. A new database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems® software was developed through fitting of existing literature data such as mean activity, heat capacity and solubility data in simple binary and ternary systems. Moreover, a number of experiments were conducted to investigate the chemistry of calcium sulphate hydrates in laterite pressure acid leach (PAL) solutions, containing Al2(SO4)3, MgSO4, NiSO4, H2SO4, and NaCl at 25–250ºC. The database developed, utilized by the MSE model, was shown to accurately predict the solubilities of all calcium sulphate hydrates (and hence, predict scaling potential) in various multicomponent hydrometallurgical solutions including neutralized zinc sulphate leach solutions, nickel sulphate–chloride solutions of the Voisey’s Bay plant, and laterite PAL solutions over a wide temperature range (25–250°C). The stability regions of CaSO4 hydrates (gypsum, hemihydrate and anhydrite) depend on solution conditions, i.e., temperature, pH and concentration of ions present. The transformation between CaSO4 hydrates is one of the common causes of scale formation. A systematic study was carried out to investigate the effect of various parameters including temperature, acidity, seeding, and presence of sulphate/chloride salts on the transformation kinetics. Based on the results obtained, a mechanism for the gypsum–anhydrite transformation below 100°C was proposed. A number of solutions for mitigating calcium sulphate scaling problems throughout the processing circuits were recommended: (1) operating autoclaves under slightly more acidic conditions (~0.3–0.5 M acid); (2) mixing recycled process solutions with seawater; and (3) mixing the recycling stream with carbonate compounds to reject calcium as calcium carbonate. Furthermore, aging process solutions, saturated with gypsum, with anhydrite seeds at moderate temperatures (~80°C) would decrease the calcium content, provided that the solution is slightly acidic.

The effects of ACQ solution parameters such as copper to quat ratio, pH and copper to ligand ratio on distribution of copper complexes in solution and insoluble precipitates, and on fixation and leaching of copper in treated wood were evaluated. The distribution of ionic complexes, predicted by equilibrium speciation model (MINTEQA2), was related to laboratory fixation and leaching results at controlled ACQ solution parameters. A decrease in the relative proportion of copper in the ACQ formulation from a copper oxide (CuO) to didecyldimethylammonium carbonate (DDACb) ratio of 2:1 to 1:1 and 1:2 resulted in lower copper retention in the treated samples and substantially decreased the amount of copper leached per unit area. For monoethanolamine (Mea) based ACQ, solution parameters which favour a higher proportion of monovalent cationic complex, which consume one reactive site in wood, and the presence of insoluble carbonate precipitate of copper in wood during preservative treatment resulted in higher leach resistance compared to the neutral copper complex present at higher pH. Ammonia (NH3) based ACQ can fix more copper at high pH as there is no chelated neutral complex as in Mea based ACQ; however divalent copper-NH3 complexes may consume two sites to fix in wood. Addition of NH3 in Mea based ACQ at Cu:Mea:NH3 ratio of 1:4:6 at pH 10.6 significantly reduced copper leaching compared to 1:4:0 (without ammonia) at pH 9 due to increased divalent copper-ammonia complexes and decreased neutral copper amine complex at elevated pH. Ammonia addition with a lower proportion of Mea (1:2.5:4 at pH 10.5-10.7), significantly reduced copper leaching compared to 1:4:0 at pH 9; no reduction was observed for ammonia addition in ACQ with a higher proportion of Mea (1:4:4 at pH 10.45). The lower copper leaching from 1:2.5:4 resulted from the higher amount of divalent copper-NH3 complexes at higher pH without compromising the amount of copper precipitated at lower pH. The higher percent copper leached from tetramethylethylenediamine (Tmed) based ACQ compared to Mea and NH3 based ACQ suggested that highly stable complexes tend to stay in solution and do not result in leach resistant copper in the wood.

The project undertook a systematic study of chlorination of titanium oxycarbide and oxycarbonitride with the aim to develop further understanding of kinetics and mechanisms of the chlorination reactions. The project studied titania, ilmenite ores, and synthetic rutile reduced by carbon in argon and nitrogen and chlorinated at different temperatures, gas flow rates and compositions. Chlorination of titanium suboxides, iron and impurities in ilmenite was also examined. Chlorination of titanium oxycarbide Ti(O,C) or oxycarbonitride Ti(O,C,N) can be implemented at 200 to 400 deg.C, while the commercial chlorination process in the production of titanium metal or titania pigment requires 800 to 1100 deg.C. This makes chlorination of Ti(O,C) or Ti(O,C,N) an attractive technology in processing of titanium minerals. Chlorination reaction is strongly exothermal, which increased the sample temperature up to 200 deg.C above the furnace temperature. The chlorination of Ti(O,C) or Ti(O,C,N) was ignited at 150 deg.C to 200 deg.C depending on the sample composition. Their chlorination at 235 deg.C to 400 deg.C was close to completion in less than 30 min. The chlorination rate of titanium oxycarbide or oxycarbonitride increased with increasing gas flow rate. Sample composition had a significant effect on the extent of chlorination. The optimum results were obtained for titanium oxycarbide or oxycarbonitride produced with carbon to titania molar ratio of 2.5; these samples contained no detectable excess of carbon or unreduced titanium suboxides. In chlorination of reduced ilmenite ores and synthetic rutile, Ti(O,C) or Ti(O,C,N), metallic iron and Ti2O3 were chlorinated. The rate and extent of chlorination of titanium increased with increasing carbon to TiO2 ratio. Chlorination of Ti2O3 was slow relative to Ti(O,C) or Ti(O,C,N) and iron; chlorination of impurity oxides such as MgO, SiO2 and Al2O3 was not observed. The project also examined chlorination of Ti(O,C) or Ti(O,C,N) in ilmenite ore and synthetic rutile after removal of iron, which was achieved by aerated leaching of reduced samples in heated flask containing 0.37 M of ammonium chloride solution. Iron removal from the ilmenite ore or synthetic rutile resulted in higher rate and extent of chlorination of titanium oxycarbide or oxycarbonitride.