Increased groundwater usage, rainfall decline and activities such as mining have resulted in the acidification of certain wetlands in the south-west of Western Australia. This study investigated the influence of pH, the factor most commonly associated with acidification, on the invertebrate and diatom community structure of 20 wetlands in the south-west region of Western Australia. Few studies in Western Australia have investigated both biotic groups, particularly in relation to pH. Consequently, this study examined the comparative sensitivity of the two biotic groups to pH in order to identify the most effective biotic tool for assessing the ecological impacts of pH decrease. The wetlands included in this study displayed a wide range of pH from acidic (pH < 6.5) to alkaline (pH > 7.5). Other environmental parameters were also variable. Separation of the wetlands into three pH groups; Group 1 – acidic, Group 2 – circumneutral and Group 3 – alkaline, demonstrated that the acidic Group 1 wetlands generally had higher electrical conductivity than the remaining groups. This was probably due to the association of many Group 1 sites with mining and acid sulphate soils. Seasonal trends in environmental variables across the three pH groups were mostly unclear although some trends were evident within the individual pH groups. The study showed that invertebrate community structure differed in response to pH. However, the results also demonstrated that invertebrate distribution patterns were influenced by other factors. / Potential indicator species identified from the study included Macrothrix indistincta and Tanytarsus fuscithorax/semibarbitarsus which were abundant in acidic waters and Alona quadrangularis which was common in circumneutral sites. Taxa such as Calamoecia tasmanica subattenuata were common over a wider range of pH (acidic to circumneutral) but may still have potential to act as indicators of pH decline. Diatom community structure was also shown to be influenced by pH, with the variable identified as a major determinant of diatom distribution patterns. Nitzschia paleaeformis and Navicula aff. cari were generally recorded from acidic wetlands and are potentially useful as indicators of low pH conditions. Brachysira brebissonii and Frustulia magaliesmontana were also identified as species with the potential to indicate pH decline. In contrast, taxa including Gomphonema parvulum, Staurosira construens var. venter and Nitzschia palea were generally associated with moderate to high pH levels. A comparative study of the two biotic groups using multivariate analyses revealed that diatoms were more sensitive to pH than invertebrates. Further investigation with a larger number of environmental variables would be necessary to ascertain the other factors primarily influencing invertebrate community structure. Nonetheless, the findings imply that diatoms and invertebrates differ in their responsiveness to various environmental factors and may provide complementary information on the integrity of a system. Multivariate analyses on an expanded data-set of 40 sites found that pH accounted for the greatest amount of variation in the data and was conducive to the development of a diatom-based pH inference model. / The strongest model was produced using weighted averaging (WA) with classical deshrinking. While the model displayed a high correlation coefficient, the prediction error was also relatively high, probably as a result of the comparatively small and heterogeneous data-set. Incorporation of the data into a larger training set would be likely to improve the predictive ability. Applications for the model include pH reconstructions or use in monitoring programs. The current study has shown that pH is an important variable influencing both invertebrate and diatom community structure in wetlands in the south-west of Western Australia. However, the greater sensitivity of diatoms to pH suggests that they would be the most effective tool for the biological monitoring of pH in wetlands threatened or impacted by acidification. An integrated monitoring program including both diatoms and invertebrates may provide additional information on the impacts of pH decline and the overall integrity of the systems and should be investigated further.

The work described in this dissertation focused on chemistry related to the use of aqueous sodium hydroxide as a treatment in the processing of wheat straw. A major emphasis was the comprehensive evaluation of straw component partitioning due to sodium hydroxide (NaOH) processing. This was evaluated over a range of NaOH concentrations (0­‐10%, w/v), all at 50°C, 5 h treatment period, and 3% solid loading. Solid and liquid phases resulting from NaOH treatments were evaluated. Total solids recovered in the NaOH­‐treated solid phase ranged from 47.4­‐88.0%. Overall carbohydrate recovery in the combined solid and liquid phases was negatively correlated with the alkali concentration of the treatment liquor. The glucan content of the NaOH‐treated solid phase ranged from 37.2­‐67.4%. Glucan recovery in the solid phase was relatively high in all cases, the minimum value being ~98%. Increasing amounts of xylan partitioned into the liquid phase as sodium hydroxide concentrations increased – it ranged from 31­‐83% of the xylan being recovered in the soluble phase. Carbohydrate analyses of the pretreated liquor revealed that the majority of carbohydrate loss from the solid fraction could be recovered in the liquid phase in form of oligomers and monomers due to alkaline degradation. The interconversion of glucose, fructose, and mannose under the alkaline condition played an important role in the presence of those sugars. Increase in NaOH concentration contributed to increase in amount of cellulose­‐derived and hemicellulose‐derived oligomers in the pretreated liquor. All oligomers except fructooligomers in NaOH pretreated liquor were higher than those found in water extraction at 50°C, 5 h. Total carbohydrate recovery from the solid and liquid fractions was as high as 99% for glucose and glucan in 5% NaOH treatment and 80‐95% for xylose and xylan in 1-­10% NaOH treatment. The presence of NaOH as extraction reagent dramatically induced lignin and ash removal from the pretreated solid with up to 63% acid insoluble lignin (AIL) and 87% ash extraction. Solid fractions resulting from NaOH pretreatments (up to 5% NaOH) were tested for their susceptibility to enzymatic saccharification using cellulase and cellulase/xylanase enzyme preparations. The cellulase/xylanase enzyme preparation was found to be more effective at cellulose saccharification than the cellulase enzyme preparation alone. Maximum glucose yield, which corresponded to the 5% NaOH treatment, was 82% over the standard 48 h saccharification period. Extended saccharifications times to 120 h showed that the conversion yield approached 90%. Sequential treatments of the straw (i.e. initial alkali treatment – first enzyme saccharification – second alkali treatment ‐ second enzyme treatment) revealed the NaOH treatment has the potential to render essentially all (~99%) of the straw glucan susceptible to enzyme saccharification. This suggests that the layered molecular arrangement of cellulose, hemicellulose, and lignin in the cell wall impacts biomass recalcitrance and glucan conversion yield. The other major focus of this dissertation research was the characterization of alkali neutralization, which occurs during the aqueous alkali processing of wheat straw. The approach taken was to evaluate the time course of alkali uptake and to determine the underlying nature of alkali uptake. The knowledge generated from this study is useful for understanding the nature of the alkali‐induced chemistry that is at the heart of alkali processing of agricultural byproducts, foods, and forest products. Alkali uptake/acid generation measurements were monitored for wheat straw suspensions at pH 11 and 30°C. The first phase of alkali uptake corresponded to the 30‐second time period over which the pH of the wheat straw suspension was adjusted from its original pH (~6.6) to pH 11. Alkali neutralization during this period was attributed to the instantaneous ionization of solvent accessible Bronstad acids. Following pH adjustment to 11.0, the time course of subsequent alkali uptake was recorded. The time course appeared biphasic. The early phase, which corresponded to the relatively rapid uptake of alkali, was evident during the first 24 hours. The later phase, which was characterized by the relatively slow uptake of alkali, was maintained for the length of the study (up to 96 hours). Alkali uptake during the early phase of the time course appears to be determined by the rate of hydrolysis of readily accessible esters – primarily acetic acid esters (acetyl groups). Alkali uptake during the later phase of the time course appears to be impacted by the rate of alkali penetration into the straw and the rate of production of alkali‐induced acid degradation products. The uptake of alkali in the pH adjustment phase was ~ 120 μEq per gram wheat straw, the uptake of alkali in the early phase of time course was ~ 1,064 μEq per gram wheat straw, and the rate of uptake in the later phase of the time course 6.10 μEq per gram wheat straw per hour. Amount of acetyl groups, ferulic acid, and p-­coumaric acid generated during 96-­h pretreatment revealed that they are major esters being hydrolyzed under the studied condition. Combined, these ester-­derived acids contributed up to ~ 28% of overall alkali uptake. In addition, alkaline degradation products quantified in this study showed additional ~ 28% contribution to the overall alkali uptake. / Graduation date: 2012

The assemblage of ca. 6–4 Ma volcanic rocks exposed at the Sagehen Research station in the Truckee-Tahoe region of the northern Sierra Nevada, United States, is interpreted to be, within the Ancestral Cascades volcanic arc, a Lassen-type stratovolcano complex. Sagehen is of particular importance because it is one of the few Tertiary arc volcanic centres in California which has not been heavily glaciated during the Pleistocene. The volcanic rocks are variably porphyritic or aphanitic, including abundant plagioclase with clinopyroxene and amphibole. The rocks range from basalt to basaltic-andesite to andesite in composition. Basalts are olivineand clinopyroxene-bearing with minor phenocrysts of plagioclase. The basaltic-andesites are primarily pyroxene bearing while the andesites contain pyroxene-, plagioclase- and hornblende porphyritic phases. Sagehen arc lavas are calc-alkaline and enriched in the large ion lithophile elements and depleted in High Field Strength Elements. The basalts are depleted in Zr and Hf while the andesites are enriched with Zr and Hf relative to the middle rare earth elements. Compared to previously studied Ancestral Cascade arc samples, Sagehen region basalts have lower 143Nd/144Nd isotopic values that do not correspond to proposed mantle-lithosphere mixing lines, while the andesite samples appear to represent the interplay of these two components on a 87Sr/86Sr vs. 143Nd/144Nd. The trace element data and isotopic plots suggest that the melts that produced the basalts are from subduction modified mantle wedge peridotites that ponded near the base of the lithosphere similar to the generation of other subduction related calc-alkaline lavas along convergent continental margins. The andesitic samples appear to be the result of further modification through crustal assimilation as seen in the higher isotopic Sr contents in the andesites and Ce/Smpmn vs. Tb/Ybpmn plots. Finally, the proposed map units from Sylvester & Raines (2007) were found to contain various geochemical facies based on the samples collected indicating that some map units may have to be redefined or sub-divided.

The Marathon PGM-Cu deposit is hosted by the Coldwell alkaline complex, which consists predominantly of gabbro and syenite and was emplaced at 1108 Ma as part of the Mid-Continent Rift System. Mineralization at the Marathon PGM-Cu deposit is hosted by the Two Duck Lake Gabbro (TDLG), a fresh olivine-bearing gabbro. The Marathon deposit contains several zones of mineralization including the Basal Zone, the Main Zone and the W-Horizon. The W-Horizon is a high-grade PGE zone characterized by low S, low Cu/Pd and high Cu/Ni. The sulphide mineral assemblage is predominantly chalcopyrite and bornite. This contrasts with the Main Zone where the dominant sulphide mineral assemblage is chalcopyrite and pyrrhotite. The Main Zone contains higher S, higher Cu/Pd and shows a decrease in Cu/Pd and pyrrhotite/chalcopyrite from base to top. Four drill holes were selected for detailed analysis to characterize the W-Horizon style of mineralization. Detailed petrographic study of the pristine and largely unaltered TDLG shows that wide spread hydrothermal alteration is not responsible for the mineralization. Detailed outcrop mapping shows that the TDLG intruded as a series of multiple intrusions in a dynamic magmatic system. Geochemical studies through the W-Horizon show that the mineralization is not the result of crystallization in a layered intrusion. The results of geochemical assays and electron microprobe analysis of olivine grains show that the chemistry through the TDLG hosting the W-Horizon is erratic. This data supports the TDLG intruding as a series of sills in a dynamic conduit environment. The calculated sulphide metal tenors for the W-Horizon are higher than can be explained by closed system R Factor models. Multistage dissolution upgrading in an open system is examined as the process forming the W-Horizon. This model is able to produce the sulphide metal tenors observed in the W-Horizon. Sulphur loss also affects grades and tenors and was examined through geochemical and petrological data. The change in sulphide mineral assemblage from a pyrrhotite and chalcopyrite (S-rich) to chalcopyrite and bornite (S-poor) supports S-loss. Whole rock S and Se contents are also analyzed to investigate S loss, a lower S/Se indicates that sulphur has been removed from the system. Average S/Se values are ~800 for the W-Horizon, ~1980 for the Main Zone and ~1700 in unmineralized samples. The very low S/Se observed within the W-Horizon supports S-loss. Sulphur loss in a dynamic magmatic conduit system is proposed for the formation of the W-Horizon mineralization. In this model sulphur undersaturated basaltic magma interacted with an immiscible sulphide liquid in a magma conduit, resulting in the dissolution of sulphide into the basaltic melt and PGE enrichment.

The mechanical pulping industry has been developing throughout the years, due to competitive prices in the electricity market and good accessibility of wood. This has made it possible for such and “expensive” process to further develop. Today, with increasing electricity prizes, it is of great interest to reduce electrical consumption in mechanical pulping industry, since the process consumes large amounts of electricity. Braviken paper mill is starting up a new thermomechanical pulping line, scheduled for start-up in August 2008, which aims to reduce electrical consumption. The new line will include chip pre-treatment equipment such as an impregnator, an Andrtiz Impressafiner (Screw press), a high intensity primary stage refines double disc (DD), and a new low consistency refiner (LC), significantly bigger than those earlier available on the market. This master´s thesis is one out of three Master´s thesis made at Braviken paper mill during spring 2008. They all are connected, and are investigating the possibility to reduce electric energy consumption within TMP production. Master´s thesis concerning high consistency refining was done by Dino Muhic, “High consistency refining of mechanical pulps during varying refining conditions”, and low consistency refining written by Fredrik Johansson “Increased energy efficiency in low consistency refining”. Chip pre-treatment is to be used to reduce electrical consumption. Mechanical pre-treatment, such as using an Andrtiz Impressafiner demolishes the chips while also making it possible to impregnate the chips with chemicals, the later giving additional possibilities to reduce electricity consumption. Chemical chip pre-treatment decreases the lignin softening temperature, which benefits the refining process, yielding longer and less damaged fibers that will create a fibrous pulp with reduced electrical energy input.The goal for this study was to investigate the effect of alkaline-peroxide on chip pre-treatment by using a design of experiment method, in terms of electric energy consumption for the process, strength properties, opacity and ISO-brightness within the pulp/sheets. The trials were built up as a factorial experiment, with two factors, alkaline and peroxide, with two levels each (high and low). The high level for alkaline was 15 kg/t and 10 kg/t for the low level, and the high level for peroxide was 10 kg/t and 5 kg/t for the low level. This resulted in four trials with two zero-points, and two reference pulps, one normal TMP, thermomechanical pulp, and the other TMP with pressafiner and water. The trials showed that adding alkaline-peroxide clearly had an impact on pulp properties, such as increased strength properties, fiber length improvements and less shives could be found in the alkaline-peroxide treated pulps. The yield was highest for the normal TMP, about 99% and it decreased with increasing alkaline addition, the lowest value was achieved for the pulps containing the highest dose of alkaline, about 95%. The optical properties were more or less as expected. Opacity had the highest value for the pulps that had been made from chips with the highest total alkaline level. The ISO brightness was highest for pulps containing low level of alkaline. It could not be decided if the electricity demand had been reduced for the chemically treated pulps; it actually had the opposite effect as expected. The chemically treated pulps demanded a higher SEC, specific energy consumption, compared to the reference pulps. This result could have depended on the small pilot plant high consistency refiners at CTP, Centre technique du papier, Grenoble, France, due to the plate size and what kind of plats that were used. To do trials like this and to be able to draw correct conclusions relevant for a full scale plant, bigger refiners might give a more comparable result. It was clear that the fiber properties had improved, which could be the key to reduce electricity when LE- (low-energy) plates are used in the HC-refiner. A higher intensity could be used and electricity energy could be saved.

A new type of fuel cell that combines the advantages of a proton exchange membrane fuel cells and anion exchange membrane fuel cells operated with methanol is demonstrated. Two configurations: one with a high pH anode and low pH cathode (anode hybrid fuel cell (AHFC)),and another with a high pH cathode and a low pH anode (cathode hybrid fuel cell (CHFC)) have been studied in this work. The principle of operation of the hybrid fuel cells were explained. The two different hybrid cell configurations were used in order to study the effect of the electrode fabrication on fuel cell performance. Further, the ionomer content and properties such as the ion exchange capacity and molecular weight were optimized for the best performance. A comparison of the different ionomers with similar properties is carried out in order to obtain the best possible ionomer for the fuel cell. An initial voltage drop was observed at low current density in the AHFC, this was attributed to the alkaline anode and the effect of the ionomers with the new cationic groups were studied on this voltage drop was studied. These ionomers with the different cationic groups were studied in the CHFC design as well. Finally, the use of non platinum catalyst cathode with the CHFC design was also demonstrated for the first time.

<p> </p><p><p>The mechanical pulping industry has been developing throughout the years, due to competitive prices in the electricity market and good accessibility of wood. This has made it possible for such and “expensive” process to further develop. Today, with increasing electricity prizes, it is of great interest to reduce electrical consumption in mechanical pulping industry, since the process consumes large amounts of electricity. Braviken paper mill is starting up a new thermomechanical pulping line, scheduled for start-up in August 2008, which aims to reduce electrical consumption. The new line will include chip pre-treatment equipment such as an impregnator, an Andrtiz Impressafiner (Screw press), a high intensity primary stage refines double disc (DD), and a new low consistency refiner (LC), significantly bigger than those earlier available on the market. This master´s thesis is one out of three Master´s thesis made at Braviken paper mill during spring 2008. They all are connected, and are investigating the possibility to reduce electric energy consumption within TMP production. Master´s thesis concerning high consistency refining was done by Dino Muhic, “<em>High consistency refining of mechanical pulps during varying refining conditions</em>”, and low consistency refining written by Fredrik Johansson “I<em>ncreased energy efficiency in low consistency refining</em>”.</p><p><p>Chip pre-treatment is to be used to reduce electrical consumption. Mechanical pre-treatment, such as using an Andrtiz Impressafiner demolishes the chips while also making it possible to impregnate the chips with chemicals, the later giving additional possibilities to reduce electricity consumption. Chemical chip pre-treatment decreases the lignin softening temperature, which benefits the refining process, yielding longer and less damaged fibers that will create a fibrous pulp with reduced electrical energy input.The goal for this study was to investigate the effect of alkaline-peroxide on chip pre-treatment by using a design of experiment method, in terms of electric energy consumption for the process, strength properties, opacity and ISO-brightness within the pulp/sheets. The trials were built up as a factorial experiment, with two factors, alkaline and peroxide, with two levels each (high and low). The high level for alkaline was 15 kg/t and 10 kg/t for the low level, and the high level for peroxide was 10 kg/t and 5 kg/t for the low level. This resulted in four trials with two zero-points, and two reference pulps, one normal TMP, thermomechanical pulp, and the other TMP with pressafiner and water.</p><p>The trials showed that adding alkaline-peroxide clearly had an impact on pulp properties, such as increased strength properties, fiber length improvements and less shives could be found in the alkaline-peroxide treated pulps. The yield was highest for the normal TMP, about 99% and it decreased with increasing alkaline addition, the lowest value was achieved for the pulps containing the highest dose of alkaline, about 95%. The optical properties were more or less as expected. Opacity had the highest value for the pulps that had been made from chips with the highest total alkaline level. The ISO brightness was highest for pulps containing low level of alkaline. It could not be decided if the electricity demand had been reduced for the chemically treated pulps; it actually had the opposite effect as expected. The chemically treated pulps demanded a higher SEC, specific energy consumption, compared to the reference pulps. This result could have depended on the small pilot plant high consistency refiners at CTP, Centre technique du papier, Grenoble, France, due to the plate size and what kind of plats that were used. To do trials like this and to be able to draw correct conclusions relevant for a full scale plant, bigger refiners might give a more comparable result. It was clear that the fiber properties had improved, which could be the key to reduce electricity when LE- (low-energy) plates are used in the HC-refiner. A higher intensity could be used and electricity energy could be saved.</p></p></p>

The use of lignocellulosic materials to replace fossil resources for the industrial production of fuels, chemicals, and materials is increasing. The carbohydrate composition of lignocellulose (i.e. cellulose and hemicellulose) is an abundant source of sugars. However, due to the feedstock recalcitrance, rigid and compact structure of plant cell walls, access to polysaccharides is hindered and release of fermentable sugars has become a bottle-neck. Thus, to overcome the recalcitrant barriers, thermochemical pretreatment with an acid catalyst is usually employed for the physical or chemical disruption of plant cell wall. After pretreatment, enzymatic hydrolysis is the preferred option to produce sugars that can be further converted into liquid fuels (e.g. ethanol) via fermentation by microbial biocatalysts. However, during acid pretreatment, several inhibitory compounds namely furfural, 5-hydroxymethyl furfural, phenols, and aliphatic acids are released from the lignocellulose components. The presence of these compounds can greatly effect both enzymatic hydrolysis and microbial fermentation. For instance, when Avicel cellulose and acid treated spruce wood hydrolysate were mixed, 63% decrease in the enzymatic hydrolysis efficiency was observed compared to when Avicel was hydrolyzed in aqueous citrate buffer. In addition, the acid hydrolysates were essentially non-fermentable. Therefore, the associated problems of lignocellulose conversion can be addressed either by using feedstocks that are less recalcitrant or by developing efficient pretreatment techniques that do not cause formation of inhibitory byproducts and simultaneously give high sugar yields. A variety of lignocellulose materials including woody substrates (spruce, pine, and birch), agricultural residues (sugarcane bagasse and reed canary grass), bark (pine bark), and transgenic aspens were evaluated for their saccharification potential. Apparently, woody substrates were more recalcitrant than the rest of the species and bark was essentially amorphous. However, the saccharification efficiency of these substrates varied based on the pretreatment method used. For instance, untreated reed canary grass was more recalcitrant than woody materials whereas the acid treated reed canary grass gave a higher sugar yield (64%) than the woody substrates (max 34%). Genetic modification of plants was beneficial, since under similar pretreatment and enzymatic hydrolysis conditions, up to 28% higher sugar production was achieved from the transgenic plants compare to the wild type. As an alternative to the commonly used acid catalysed pretreatments (prior to enzymatic hydrolysis) lignocellulose materials were treated with four ionic liquid solvents (ILs): two switchable ILs (SILs) -SO2DBUMEASIL and CO2DBUMEASIL, and two other ILs [Amim][HCO2] and [AMMorp][OAc]. viii After enzymatic hydrolysis of IL treated substrates, a maximum amount of glucan to glucose conversion of between 75% and 97% and a maximum total sugar yields of between 71% and 94% were obtained. When using acid pretreatment these values varied between 13-77% for glucan to glucose conversion and 26-83% for total sugar yield. For woody substrates, the hemicellulose recovery (max 92%) was higher for the IL treated substrates than compared to acid treated samples. However, in case of reed canary grass and pine bark the hemicellulose recovery (90% and 88%, respectively) was significantly higher for the acid treated substrates than the IL treated samples. To overcome the inhibitory problems associated with the lignocellulose hydrolysates, three chemical conditioning methods were used 1. detoxification with ferrous sulfate (FeSO4) and hydrogen peroxide (H2O2) 2. application of reducing agents (sulfite, dithionite, or dithiothreitol) and 3. treatment with alkali: Ca(OH)2, NaOH, and NH4OH. The concentrations of inhibitory compounds were significantly lower after treatments with FeSO4 and H2O2 or alkali. Using reducing agents did not cause any decrease in the concentration of inhibitors, but detoxification of spruce acid hydrolysates resulted in up to 54% improvement of the hydrolysis efficiency (in terms of sugar release) compared to untreated samples. On the other hand, application of detoxification procedures to the aqueous buffer resulted in up to 39% decrease in hydrolysis efficiency, thus confirming that the positive effect of detoxification was due to the chemical alteration of inhibitory compounds. In addition, the fermentability of detoxified hydrolysates were investigated using the yeast Saccharomyces cerevisiae. The detoxified hydrolysates were readily fermented to ethanol yielding a maximum ethanol concentration of 8.3 g/l while the undetoxified hydrolysates were basically non-fermentable.

Values of the rate constant for the alkaline hydrolysis of methyl acetate in various aqueous-organic solvent mixtures (dimethyl sulfoxide 0<x40.2, dioxane 0 <, x., < 0.2, methyl ethyl ketone 0<x<0.06 and diglyme, i. e. ether-bis (2-methyloxethyl) 0x<0.10) have been determined for the temperatures 15 0 C, 25 0C and 35 0C conductometrically. To interpret these results the approach adapted is to experimentally determine the activity coefficient of the ester (YE ) and the activity of the water (aH20', mechanistically, at least one molecule of water is involved in the rate-determining step) and then to use the Bronsted-Bjerrum equation to determine the residual activity coefficient ratio of the participating ions, y (Yf - for Oil the transition state). Values of YE and aH 20 have been determined by a transpiration method, using gas-chromatographic analysis of the vapours of solutions of methyl acetate in aqueous-organic solvent mixtures of dir. ethyl sulfoxide, dioxane, methyl ethyl ketone and diglyme in the same composition ranges as above, tetrahydrofuran 04x org z<, 0.15, methanol, ethanol and tert-butanol in t1h6e range 04x0.20'at 25oC. These results indicate that on changing org the solvent composition YE varies by a larger factor than is predicted for the ratio YOH-/yýO_ by the Debye-Iluckel approach, and hence is the dominant factor in determining the effects of solvent composition on the rates of the hydrolysis. This is in contradiction to the assumptions of the electrostatic theories of Laidler and Eyring, and of Amis and Jaffe. The gas-chromatographic results also indicate that whilst the concentration of the water varies in each mixture studied, the activity coefficient varies in the opposite way to produce almost constant values of aý, 0* Using the transpiratioii/gas-chromatogralýlic method, the thermodynamic properties of the ternary systems, methyl acetate-water-organic Solvcat, using the organic solvents mentioned above (excepting, diglyme) have been investigated, and the results indicate that the variation of *ýE with solvent composition, for the dilute solutions of ester used, can be estimated from the thermodynamic properties of the binary water-organic solvent mixtures, using the Gibbs-Dahem equation. Single ion activity coefficients in the literature for small negative ions, to represent the OH_ ion, and for large ions, to rep-resent the transition state ion, have been used to explain the experimentally fomd variation of the residual activity coefficient -ratio with solvent composition. Hence, it is concluded that the importance of the parameters involved in the hydrolysis of esters - an ion-molecule reaction - in aqueousorganic solvent mixtures are in the order of Ymolecule > aH 20> YOH_/YM+ -> (dielectric constant), and that the nonelectrostatic effects -- thermodynamic effects - are more important in these studies than the electrostatic effects. From a preliminary investigation of the data in the literature the thermodynamic approach also yields a valid interpretation of the effect of solvent composition on the rates of the acid hydrolysis of esters.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.