Soil bottles and soil slurry experiments were conducted to investigate the effect of some additives on the aerobic and anaerobic biodegradation of chlorinated aliphatic hydrocarbons; tetrachloroethylene (PCE), trichloroethylene (TCE) and dichloroethylene (DCE) in a contaminated soil from Startvätten AB Linköping Sweden. For the aerobic degradation study the soil sample was divided into two groups, one was fertilised. The two groups of soil in the experimental bottles were treated to varying amount of methane in pairs. DCE and TCE were added to all samples while PCE was found in the contaminated soil. Both aerobic and anaerobic experiments were conducted. For aerobic study air was added to all bottles to serve as electron acceptor (oxygen). It was observed that all the samples showed a very small amount of methane consumption while the fertilised soil samples showed more oxygen consumption. For the chlorinated compounds the expected degradation could not be ascertained since the control and experimental set up were more or less the same. For the anaerobic biodegradation study soil slurry was made with different media i.e. basic mineral medium (BM), BM and an organic compound (lactate), water and sulphide, phosphate buffer and sulphide and phosphate buffer, sulphide and ammonia. To assure anaerobic conditions, the headspace in the experimental bottles was changed to N2/CO2. As for the aerobic study all the samples were added DCE and TCE while PCE was found in the contaminated soil. The sample without the soil i.e. the control was also given PCE. It was observed that there was no clear decrease in the GC peak area of the pollutants in the different media. The decrease in GC peak area of the pollutants could not be seen, this may be so because more susceptible microorganisms are required, stringent addition of nutrients and to lower the risk of the high concentration of PCE and petroleum products in the soil from Startvätten AB.

Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs.

This research studies variations in biodiesel upon addition of different concentrations of antioxidant and petrodiesel additives. Oxidation onset temperature, oxidation induction time, oxidative stability, thermal stability, crystallization onset temperature and moisture retention properties of the biodiesel, with and without antioxidants have been studied. Antioxidants like BHT, BHA, PrG, Vit E and Vit C were added to the biodiesel during the study. These samples were analyzed using the PDSC, TGA, DSC and TGA-SA instrumentation. The results of this research show an improvement in the OOT, OIT and Oxidative stability of biodiesel with the addition of antioxidants and by blending the biodiesel with different amounts of Petro-diesel. A significant improvement in oxidative stability of biodiesel has been observed with the addition of antioxidants and petrodiesel. There was no significant change noticed in the thermal stability, crystallization and the moisture retention properties of biodiesel. I hope that this research would help improving the oxidative stability of the biodiesel. The results from the analysis made in this study would also be helpful in designing a better antioxidant and aid in improving the present experimental methods for the OIT and thermal analysis.

Combustion of fossil fuels has contributed to many environmental problems including acid deposition. The Clean Air Act (CAA) was created to reduce ecological problems by cutting emissions of sulfur and nitrogen. Reduced emissions and rainfall concentrations of acidic ions have been observed since the enactment of the CAA, but soils continue to receive some acid inputs. Soils sensitive to acid deposition have been found to have low pH, a loss of base cations and a shift in the mineral phase controlling the activity of Al3+ and/or SO42-. If inputs continue, soil may be depleted of base cations and saturated with Al and could cause low forest productivity. Soil solutions from lysimeters were taken in the Daniel Boone National Forest to evaluate potential impacts of acid deposition. In addition, tree-ring growth and chemical analysis created a timeline of forest health and ion accumulation. Physicochemical characteristics of the soils revealed that sites were very low in base saturation and pH and high in exchangeable acidity. Soil solution data indicated that sites periodically received high acid inputs leading to saturation of Al in soils and the formation of Al-hydroxy-sulfate minerals. Given these conditions, long-term changes in soil chemistry from acid deposition are acknowledged.

Laccase (benzenediol:oxygen oxidoreductase, EC 1.10.3.2), a multi-copper-containing oxidoreductase enzyme, is able to catalyze the oxidation of various low-molecular weight compounds, specifically, phenols and anilines. Due to their high stability, selectivity for phenolic substructures, and mild reaction conditions, laccases are attractive for fine chemical synthesis. In this study, new green domino syntheses were developed by conducting the reaction in an aqueous medium, an environmentally-friendly solvent, and using laccase as a biocatalyst. The first study presents a work on the synthesis of naphthoquinones in the aqueous medium. Herein, laccase was used to oxidize o- and p-benzenediols to generate o- and p-benzoquinones in situ. These quinones then underwent Diels-Alder and oxidation reactions to finally generate napthoquinone products. This reaction system can yield naphthoquinones in up to 80% yield. The next part of this thesis reports the cascade synthesis of benzofuran derivatives from the reaction of catechols and 1,3-dicarbonyl compounds via oxidation-Michael addition in the presence of laccase and Sc(OTf)3/SDS in an aqueous medium. Depending on the substrates, one-pot yields of benzofurans averaged 50-79%. From an environmental concern, this system still produced a hazardous waste from the transition metal catalyst. Therefore, the development of alternative methodologies to replace the lanthanide metal catalyst in this synthesis is a high priority to enhance the overall green chemistry aspect. As a consequence, lipase was used as a catalyst to replace Sc(OTf)3 for the synthesis of benzofuran derivatives. In addition, this catalytic system was also used to catalyze the reaction of anilines and catechol. In the last part of this thesis, laccase was applied to the modification of high-lignin softwood kraft pulp. This modification demonstrates the potential of laccase-facilitated grafting of amino acids to high lignin content pulps to improve their physical properties in paper products which resulted from the increase of carboxylic acid group of the fibers. In this study, a variety of amino acids were examined. Laccase-histidine treatment provided the best yield of acid groups on pulp fiber and was used in the preparation of handsheets for physical strength testing. Laccase-histidine-treated pulp showed an increase in the strength properties of the resulting paper.

Thallium is a highly toxic element that humans are exposed to mainly by consumption of drinking water and vegetables grown in soil with high thallium content but also through inhalation of particles in the air. Thallium is also present in fossil fuels, alloys, and in electronic utilities. The increasing use of the element and emissions from notably energy production has lead to a higher load on the surface of the Earth. This study aims at increasing the knowledge about the behaviour of thallium in aquatic environments. Focus has been on the redox chemistry of thallium in relation to its mobility, which is of great importance because Tl(I) and Tl(III) have very different properties in this respect. The relationship between Tl(I) and Tl(III) in surface waters from contaminated and uncontaminated environments was examined by ion chromatography connected on line to ICP-MS (inductively coupled plasma mass spectrometry). It was found in controlled systems that even though Tl(III) is thermodynamically unstable under fresh water conditions Tl(I) was oxidised in the presence of light and iron(III). This was also confirmed in field studies. When lake water samples were exposed to light, Tl(I) was oxidised and thallium was lost from the solution. The most likely explanation for this was adsorption of thallium to particle surfaces. The concentration of thallium in Swedish lakes and soil were measured. In unpolluted lakes the concentration ranges between 4.5-12 ng/l, the sediment concentration was 0.07-1.46 mg/kg. The anthropogenic load was found to have increased since the end of the Second World War although concentrations above background were found since the early industrialisation. In contaminated areas the concentration in soil ranges from 0.64-88 mg/kg, high concentrations were found in systems with alum shale and in soil exposed to runoff from a lead and zinc enrichment plant. The mobilisation of thallium from solid phases in contaminated areas was dependent on pH and about 50% of the leachable content was mobilised already at pH 5-6. Once it had been released to water it was highly mobile. These conditions suggest that in a large part of the Swedish environment a high mobility of thallium can be expected.

This thesis studied the viability of recycling filter substrates as soil amendments after being used in on-site systems for phosphorus (P) removal from wastewater. Focus was put on the materials Filtra P and Polonite, which are commercial products used in compact filters in Sweden. A prerequisite for this choice was to review filter materials and P sorption capacity. The filter substrates (Filtra P, Polonite and wollastonite tailings) were recycled from laboratory infiltration columns as soil amendments to a neutral agricultural soil and to an acid meadow soil to study their impacts on soil properties and yield of barley and ryegrass. The amendments tended to improve the yield and showed a liming effect, significantly increasing soil pH and the availability of P. In another experiment, samples of Filtra P and Polonite were equilibrated in batch experiments with the two soils in order to study the P dynamics in the soil-substrate system.  Batch equilibrations confirmed the liming potential of Filtra P and Polonite and showed that improved P availability in soils was strongly dependent on substrate P concentration, phase of sorbed P, and soil type. Finally, samples of Polonite used for household wastewater treatment were recycled as soil amendments to a mountain meadow and to an agricultural field for wheat cropping. The liming effect of Polonite was confirmed under field conditions and the results were similar to those of lime for the mountain meadow soil. However, the results were quite different for the agricultural field, where Polonite did not affect soil pH or any other chemical and physical soil properties investigated and had no impact on wheat yield and quality. The results from field experiments suggested that Polonite can be safely recycled to meadows and cropping fields at rates of 5-10 ton ha-1 but long-term studies are needed to forecast the effects of accumulation. / QC 20100708

Antimony (Sb) is an element of increasing concern as an environmental contaminant. Geothermal systems are a potential source of Sb in the fresh waters of New Zealand’s North Island, but little is known about the element’s behaviour within geothermal fluids, and even less about the eventual fate of geothermally produced Sb. The purpose of this thesis was to determine the factors controlling geothermal Sb behaviour in a range of environments, in order to begin to develop an understanding of the eventual fate of Sb produced from geothermal systems. Factors controlling Sb precipitation at two New Zealand geothermal power stations, were determined using field measurements and geochemical model predictions. Approximately 75 % of the incoming Sb, which ranged from 960 – 1650 μg/kg in the incoming fluids was removed from solution within the Ngawha and Rotokawa power stations. It was found that changes in pH and temperature were the most important factors controlling stibnite (Sb2S3) precipitation. Thermodynamic databases could be used to model this precipitation process, once updated with recent published Sb2S3 solubility data. The mobility of Sb from Sb2S3 precipitates in geothermal features at Wai-O-Tapu and Waimangu, two New Zealand geothermal fields, were investigated. At Wai-O-Tapu, daytime variations in aqueous Sb concentrations from the discharge of Champagne Pool may be due to to changing sulfide-sulfate equilibria coupled with photosynthetic bacterial processes. While daytime concentrations of Sb approached 200 μg/kg, most of the Sb remobilised by such mechanisms appears to be removed by adsorption onto suspended particulate material (SPM) or reprecipitation (as Sb2S3) in an anoxic, low pH lake feature downstream. Concentrations of Sb in the discharge from Alum Lake were below the analytical detection limit (<0.2 μg/kg). At Waimangu, these daytime fluctuations were not observed in the discharge of Frying Pan Lake, and concentrations of Sb were ~13 μg/kg. In the absence of any downstream acidic waters, no precipitation was observed and only minor adsorption onto SPM was observed. Most of the Sb produced from Frying Pan Lake is therefore transported into Lake Rotomahana, the system’s receiving environment. Natural Sb removal processes in receiving (non-geothermal) environments were also assessed. In the Waikato River, Sb concentrations were low (~1 μg/kg), compared to those observed in geothermal environments studied. The most important process was adsorption to SPM, which is enhanced at low (< 5) pH conditions, or in the anoxic base of stratified lakes. In Lake Ohakuri, which was stratified during the summer of 2007, there was also the potential for the removal of Sb as Sb2S3 in the presence of sulfide species that form in the anoxic layer. There was evidence that the adsorption of Sb changes with changing Fe concentrations in suspended particulate material, and therefore Sb adsorption was higher in winter than in summer. The behaviour of Sb was conservative in the Port Waikato estuary at the mouth of the river. Throughout the research, Sb was compared to arsenic (As), a metalloid previously thought to exhibit behaviour similar to Sb in aquatic environments. It was found that while any removal processes shown to affect Sb will also affect As, the inverse did not necessarily apply. Arsenic will adsorb more readily to SPM than Sb and, while there was evidence for bioaccumulation of As by geothermal algae and freshwater macrophytes, there was no such evidence for Sb. Therefore, if geothermally-derived Sb and As did ever significantly contaminate a downstream environment, it should not be assumed that the processes mitigating As contamination will necessarily also apply to Sb.

Antimony (Sb) is an element of increasing concern as an environmental contaminant. Geothermal systems are a potential source of Sb in the fresh waters of New Zealand’s North Island, but little is known about the element’s behaviour within geothermal fluids, and even less about the eventual fate of geothermally produced Sb. The purpose of this thesis was to determine the factors controlling geothermal Sb behaviour in a range of environments, in order to begin to develop an understanding of the eventual fate of Sb produced from geothermal systems. Factors controlling Sb precipitation at two New Zealand geothermal power stations, were determined using field measurements and geochemical model predictions. Approximately 75 % of the incoming Sb, which ranged from 960 – 1650 μg/kg in the incoming fluids was removed from solution within the Ngawha and Rotokawa power stations. It was found that changes in pH and temperature were the most important factors controlling stibnite (Sb2S3) precipitation. Thermodynamic databases could be used to model this precipitation process, once updated with recent published Sb2S3 solubility data. The mobility of Sb from Sb2S3 precipitates in geothermal features at Wai-O-Tapu and Waimangu, two New Zealand geothermal fields, were investigated. At Wai-O-Tapu, daytime variations in aqueous Sb concentrations from the discharge of Champagne Pool may be due to to changing sulfide-sulfate equilibria coupled with photosynthetic bacterial processes. While daytime concentrations of Sb approached 200 μg/kg, most of the Sb remobilised by such mechanisms appears to be removed by adsorption onto suspended particulate material (SPM) or reprecipitation (as Sb2S3) in an anoxic, low pH lake feature downstream. Concentrations of Sb in the discharge from Alum Lake were below the analytical detection limit (<0.2 μg/kg). At Waimangu, these daytime fluctuations were not observed in the discharge of Frying Pan Lake, and concentrations of Sb were ~13 μg/kg. In the absence of any downstream acidic waters, no precipitation was observed and only minor adsorption onto SPM was observed. Most of the Sb produced from Frying Pan Lake is therefore transported into Lake Rotomahana, the system’s receiving environment. Natural Sb removal processes in receiving (non-geothermal) environments were also assessed. In the Waikato River, Sb concentrations were low (~1 μg/kg), compared to those observed in geothermal environments studied. The most important process was adsorption to SPM, which is enhanced at low (< 5) pH conditions, or in the anoxic base of stratified lakes. In Lake Ohakuri, which was stratified during the summer of 2007, there was also the potential for the removal of Sb as Sb2S3 in the presence of sulfide species that form in the anoxic layer. There was evidence that the adsorption of Sb changes with changing Fe concentrations in suspended particulate material, and therefore Sb adsorption was higher in winter than in summer. The behaviour of Sb was conservative in the Port Waikato estuary at the mouth of the river. Throughout the research, Sb was compared to arsenic (As), a metalloid previously thought to exhibit behaviour similar to Sb in aquatic environments. It was found that while any removal processes shown to affect Sb will also affect As, the inverse did not necessarily apply. Arsenic will adsorb more readily to SPM than Sb and, while there was evidence for bioaccumulation of As by geothermal algae and freshwater macrophytes, there was no such evidence for Sb. Therefore, if geothermally-derived Sb and As did ever significantly contaminate a downstream environment, it should not be assumed that the processes mitigating As contamination will necessarily also apply to Sb.

Antimony (Sb) is an element of increasing concern as an environmental contaminant. Geothermal systems are a potential source of Sb in the fresh waters of New Zealand’s North Island, but little is known about the element’s behaviour within geothermal fluids, and even less about the eventual fate of geothermally produced Sb. The purpose of this thesis was to determine the factors controlling geothermal Sb behaviour in a range of environments, in order to begin to develop an understanding of the eventual fate of Sb produced from geothermal systems. Factors controlling Sb precipitation at two New Zealand geothermal power stations, were determined using field measurements and geochemical model predictions. Approximately 75 % of the incoming Sb, which ranged from 960 – 1650 μg/kg in the incoming fluids was removed from solution within the Ngawha and Rotokawa power stations. It was found that changes in pH and temperature were the most important factors controlling stibnite (Sb2S3) precipitation. Thermodynamic databases could be used to model this precipitation process, once updated with recent published Sb2S3 solubility data. The mobility of Sb from Sb2S3 precipitates in geothermal features at Wai-O-Tapu and Waimangu, two New Zealand geothermal fields, were investigated. At Wai-O-Tapu, daytime variations in aqueous Sb concentrations from the discharge of Champagne Pool may be due to to changing sulfide-sulfate equilibria coupled with photosynthetic bacterial processes. While daytime concentrations of Sb approached 200 μg/kg, most of the Sb remobilised by such mechanisms appears to be removed by adsorption onto suspended particulate material (SPM) or reprecipitation (as Sb2S3) in an anoxic, low pH lake feature downstream. Concentrations of Sb in the discharge from Alum Lake were below the analytical detection limit (<0.2 μg/kg). At Waimangu, these daytime fluctuations were not observed in the discharge of Frying Pan Lake, and concentrations of Sb were ~13 μg/kg. In the absence of any downstream acidic waters, no precipitation was observed and only minor adsorption onto SPM was observed. Most of the Sb produced from Frying Pan Lake is therefore transported into Lake Rotomahana, the system’s receiving environment. Natural Sb removal processes in receiving (non-geothermal) environments were also assessed. In the Waikato River, Sb concentrations were low (~1 μg/kg), compared to those observed in geothermal environments studied. The most important process was adsorption to SPM, which is enhanced at low (< 5) pH conditions, or in the anoxic base of stratified lakes. In Lake Ohakuri, which was stratified during the summer of 2007, there was also the potential for the removal of Sb as Sb2S3 in the presence of sulfide species that form in the anoxic layer. There was evidence that the adsorption of Sb changes with changing Fe concentrations in suspended particulate material, and therefore Sb adsorption was higher in winter than in summer. The behaviour of Sb was conservative in the Port Waikato estuary at the mouth of the river. Throughout the research, Sb was compared to arsenic (As), a metalloid previously thought to exhibit behaviour similar to Sb in aquatic environments. It was found that while any removal processes shown to affect Sb will also affect As, the inverse did not necessarily apply. Arsenic will adsorb more readily to SPM than Sb and, while there was evidence for bioaccumulation of As by geothermal algae and freshwater macrophytes, there was no such evidence for Sb. Therefore, if geothermally-derived Sb and As did ever significantly contaminate a downstream environment, it should not be assumed that the processes mitigating As contamination will necessarily also apply to Sb.