The risk of crude oil exposure to the early life stages (ELS) of fish is difficult to assess, given the complexity of the chemical composition of different oils. The aromatic portion of crude oil contains polycyclic aromatic hydrocarbons (PAH), which are known to be toxic. In 2004, an “effects-driven” fractionation research program was initiated in an attempt to better identify toxic constituents of two unique crude oils, Alaskan North Slope Crude (ANSC; medium-heavy crude) and Scotia Light (SCOT; light crude). The ANSC contained much more PAH than SCOT. These oils induced cytochrome P4501A1 (CYP1A) enzymes in juvenile rainbow trout (Oncorhynchus mykiss) and caused blue-sac disease (BSD) and mortality in larval Japanese medaka (Oryzias latipes). Four unique fractions (F1-F4) were produced from both oils via low temperature vacuum distillation. The F3 contained an array of unsubstituted and alkyl-PAH, and was responsible for most of the CYP1A induction and chronic toxicity associated with whole oil. Cold acetone extraction (CAE) of F3 produced 2 new sub-fractions (F3-1 and F3-2). The F3-1 was rich in alkyl-PAH, was a potent CYP1A inducer, and was chronically toxic to ELS of fish. The F3-1 was further separated into five more sub-fractions via normal phase HPLC (F3-1-1 – F3-1-5). Neither F3-1-1 nor F3-1-2 induced CYP1A or produced BSD, but F3-1-2 was lethal. The F3-1-3, 4, and 5 were all potent CYP1A inducers and were all chronically toxic. Induction of CYP1A proved to be an effective tool for tracing potentially toxic PAH throughout fractionation (Chapter 2), and sub-fractions rich in alkyl-PAH caused the most BSD and mortality (Chapter 3). Alkyl-homologues of phenanthrene, fluorene, naphthobenzothiophene (NBT), pyrene, and chrysene are perhaps the most toxic of the known constituents present in crude oil. The ANSC sub-fractions were more toxic than the SCOT ones, indicating that heavier crude oils with a higher proportion of intermediate-sized alkyl-PAH may be more toxic than lighter crude oils that are comprised of fewer of these compounds. / Thesis (Master, Biology) -- Queen's University, 2007-12-20 13:18:50.794 / This research was accomplished with funding assistance from the Nationmal Oceanic and Atmospheric Administration (NOAA), Petroleum Research Atlantic Canada (PRAC), Environment Canada, and the Department of Fisheries and Oceans.

To minimize the damage caused by oil spills, responders may chemically disperse floating oil into the underlying water before it contacts shorelines and wildlife. Quantifying this strategy’s net ecological and commercial benefits requires an analysis of its effects on subsurface ecosystems and biota. Unfortunately, spill-responders have little empirical data on which to base such an analysis. Herein I report the effects of dispersed oil to early life stages of Atlantic herring (Clupea harengus). Medium South American crude oil (MESA) dispersed with Corexit 9500 caused blue sac disease (BSD) in embryos, but not in free-swimming embryos. The ages of embryos were negatively correlated with their sensitivity to oil, making those that were freshly fertilized the most sensitive. However, sensitivity was also high after hatch. Free-swimming embryos displayed signs of narcosis following brief exposure to dispersed oil. Gametes were also tested; dispersed oil dramatically impaired fertilization success. Toxicity was a function of concentration and duration of exposure, as well as of the life stage exposed. When the duration of exposure was < 24 h, gametes and free-swimming embryos were the most sensitive life stages (i.e. responded to the lowest concentrations). For durations > 24 h, young embryos (< 1 day old) were most sensitive. The results are presented as toxicity models that incorporate developmental stage, oil concentration, and exposure duration. Current effects-forecasting models for oil dispersion are based on published chronic toxicity data, which do not account for the effects of exposure duration and developmental events on toxicity. Thus, the results will better-enable modelers to estimate the effects of realistic exposures to dispersed oil in various locations, including spawning shoals. / Thesis (Master, Biology) -- Queen's University, 2009-04-26 12:55:12.266

The gas chromatograms of crude oil hydrocarbons reveal both resolved and unresolved components. The unresolved feature is commonly referred to as the unresolved complex mixture (UCM). UCMs are thought to result from the co-elution of complex mixtures of hydrocarbons with similar chemical properties and become more obvious as resolved components are removed by processes such as weathering and refining. Consequently UCMs are a prominent feature in oil-polluted sediments, biodegraded crudes and refineiT products. The characterisation of both aliphatic and aromatic unresolved complex mixtures (UCMs) of hydrocarbons, as well as their possible effects on the environment, is described. An aliphatic hydrocarbon UCM isolated from the base oil of Silkolene 150 lubricating oil was characterised by a combination of micro vacuum-distillation and oxidative degradation. Vacuum-distillation produced six distillate cuts and a residue which were all highly unresolved by GC (ca. 951/6). The average molecular weight of each cut was determined by probe CIMS (310 - 440 Daltons), and varied by -20 Daltons. Cr03 oxidation of each fraction yielded similar distributions of n-monocarboxylic acids, ketones and lactones as well as C02 (ca. 6%). The resolved products of oxidation suggest that the aliphatic UCM is a rather homogeneous mixture of highly branched alkanes. However a significant amount of the products remain unresolved (UCMox.; ca. 70-95%). A retro -structural analysis approach, using an aromatic UCM oxidant (Ru04), combined with a mass balance approach, was used to characterise aromatic UCMs. Following reproducibility studies and the analysis of authentic aromatic compounds, the method was applied to the characterisation of unresolved aromatic refinery oil fractions and a suite of aromatic UCM distillate fractions. Selected refinery oils were separated into mono-, di-, tri- and tetraaromatics by BPLC and shown to be mainly unresolved by GC (ca. 80%). Ru04 oxidation of these fractions yielded DCM soluble products (24 - 74%), water soluble products (0 - 10%) and C02 (12 -78%). The principal resolved products in each oxidation were monocarboxylic acids and dicarboxylic acids which were used to reconstruct precursor compounds. Vacuum-distillation of Tia Juana Pesado crude (Venezuela) gave six cuts and a residue which were analysed by GC, 1H NMP, UV and probe CIMS to obtain molecular weight (171 - 301 Daltons) and broad structural information whilst Ru04 oxidation was used to obtain molecular information via the retro -structural analysis approach. This showed that the aromatic UCM was in fact highly aliphatic and contained alkyl and cycloalkyl tetralins. A significant advancement in the quantitative characterisation of UCMOx. and subsequently the characterisation of aromatic UCMs was made. Ion cyclotron resonance spectrometry (ICR) was used to characterise the Ru04 oxidation products of selected refinery fractions. Analysis of the oxidation products of a monoaromatic refinery fraction indicated the presence of monocarboxylic acids (Cl - C21; 58%) and alicyclic carboxylic acids (C7 - C19; 16%), a hydrogenated monoaromatic sample contained monocarboxylic acids (Cl - C20; 30%), dicarboxylic acids (C2 - C11,7%) and alicyclic carboxylic acids (C7 - C18; 11%) , whilst a diaromatic fraction contained monocarboxylic acids (C10 - C19; 7%), alkyl phthalic acids (C8 - C17', 17%) and cycloalkyl phthalic acids (C11 - C15; 3%). Retro -structural analysis suggests that the nonhydrotreated monoaromatic UCM is mainly comprised of alicyclic and alkyl substituted benzenes, the monoaromatic UCM isolated from the hydrotreated oil of alky'l and cycloalkyl substituted tetralins and the diaromatic fraction of alkyl and cycloalkyl naphthalenes. This was supported by, FIMS analysis of the fractions prior to oxidation. As an investigation of the environmental toxicity of UCMs, the effect of a saturated aliphatic UCM, and its chemical oxidation products, on the feeding rate of mussels (Mytilus edulis), was investigated. The UCM had little effect, whilst oxidation resulted in an increase in toxicity. The non-toxic nature of the hydrocarbons was attributed to their low aqueous solubility, whilst oxidation resulted in the formation of products NNith a greater solubility, which were sufficiently hydrophobic to be narcotic toxicants. Parts of this work have been published [Thomas et al., (1993) Organic Geochemistry, Falch Hurtigtrykk, Non%-ay(A bstract), 717-719; Thomas et al., (1995) [Vater Research. 29,371-382]. iv

In this dissertation, three related issues concerning empirical time series models for energy financial markets and the stock market were investigated. The purpose of this dissertation was to analyze the interdependence of price movements, focusing on the forecasting models for crude oil prices and the hedging models for gasoline prices, and to study the change in the contemporaneous causal relationship between investors' activities and stock price movements in the Korean stock market. In the first essay, the nature of forecasting crude oil prices based on financial data for the oil and oil product market is examined. As crack spread and oil-related Exchange-Traded Funds (ETFs) have enabled more consumers and investors to gain access to the crude oil and petroleum products markets, I investigated whether crack spread and oil ETFs were good predictors of oil prices and attempted to determine whether crack spread or oil ETFs were better at explaining oil price movements. In the second essay, the effectiveness of diverse hedging models for the unleaded gasoline price is examined using futures and ETFs. I calculated the optimal hedge ratios for gasoline futures and gasoline ETF utilizing several advanced econometric models and then compared their hedging performances. In the third essay, the contemporaneous causal relationship between multiple players' activities and stock price movements in the Korean stock market was investigated using the framework of a DAG model. The causal impacts of three players' activities in regard to stock return and stock price volatility are examined, concentrating on foreign investor activities. Within this framework, two Korean stock markets, the KSE and KOSDAQ markets, are analyzed and compared. Recognizing the global financial crisis of 2008, the change in casual relationships was examined in terms of pre- and post-break periods. In conclusion, when a multivariate econometric model is developed for multi-markets and multi-players, it is necessary to consider a number of attributes on data relations, including cointegration, causal relationship, time-varying correlation and variance, and multivariate non-normality. This dissertation employs several econometric models to specify these characteristics. This approach will be useful in further studies of the information transmission mechanism among multi-markets or multi-players.

O processo de destilação do petróleo bruto é geralmente sujeito à atividade corrosiva dos equipamentos pelos ácidos, naturalmente presentes no petróleo. Este problema da corrosão pode ser atenuado pela adição de misturas de aminas neutralizantes que são inibidores da corrosão. Porém, esta adição significa um custo adicional ao processamento de petróleo. Para reduzir este custo direto da injeção de aminas o presente trabalho tem como objetivo aplicar a minimização do custo de misturas de aminas, utilizando dois diferentes métodos numéricos de otimização. Para isto foi utilizado um software desenvolvido no Laboratório Virtual de Predição de Propriedades (LVPP), onde os seguintes parâmetros operacionais são levados em consideração: temperatura de formação de sal, temperatura de orvalho do vapor d’água e pH do condensado da mistura. Esses parâmetros operacionais foram calculados e utilizados como restrições de desigualdade em otimizações com os métodos de Nelder-Mead (NM) e enxame de partículas (PSO). A escolha desses dois métodos numéricos foi devido a apresentarem características diferentes de busca do ótimo da função objetivo. O método NM apresenta caráter de busca local e o método PSO caráter de busca global. Assim, as duas restrições de desigualdade de otimização aplicadas foram: 1) o pH do condensado da mistura deve ser maior ou igual ao valor ótimo de 6,5; 2) a temperatura de formação de sal deve ser menor que temperatura do ponto de orvalho do vapor d’água. Quatro diferentes casos foram estudados, com estimativas iniciais das misturas escolhidas para satisfazer os itens 1) e 2). Os parâmetros operacionais calculados para as misturas de aminas apresentaram valores de pH abaixo dos valores considerados aceitáveis. Isso exigiu a implementação de uma condição de pH que aumentasse seu valor até a condição satisfatória, conforme restrição 1). A outra condição referente a restrição 2) foi satisfeita no cálculo das misturas para todos os casos estudados, exceto para o caso 2, de modo que a água na fase líquida arraste os sais potencialmente formados. Caso essa condição não fosse cumprida ocorreria a precipitação desses sais incrustando à superfície interna das tubulações e equipamentos, ocasionando um ataque corrosivo. As otimizações dos custos das misturas foram calculadas utilizando-se os próprios dados das misturas, com as condições dos itens 1) e 2) satisfeitas, como estimativa inicial. Para todos casos estudados, o método PSO foi capaz de obter resultados com custos menores que a metade do valor obtido com o método NM. / Crude distillation equipment is usually subject to the corrosive activity of acids. This problem can be mitigated by the addition of amines. With the addition of amines to this process a cost is generated, therefore to reduce this cost of neutralizing the amines the present work applies two different optimization methods, Nelder-Mead (NM) and Particle Swarm Optimization (PSO). This was accomplished using an in house software, developed in the Virtual Laboratory of Property Prediction (LVPP), where the following operating conditions are taken into account: salt formation temperature, condensation temperature of the water and pH of the condensate of the mixture. The operational parameters were calculated and used as inequality constraints in optimizations with both Nelder-Mead (NM) and a particle swarm optimization (PSO) methods. Two inequality constraints were considered: 1) The condensate pH of the mixture should be higher or equal than 6.5; 2) The salt temperature should be less than the dew temperature of water vapor. Four different cases were studied, throught estimates initials of the mixtures to satisfy items 1) and 2). It has been found that the operating parameters calculated for several amine mixtures produced pH values below the one considered optimal. This required the implementation of a pH condition that would increase its value up to the condition satisfactory, in accordance with restriction 1). The other condition concerning restriction 2) was satisfied in the calculation of the mixtures for all studied cases, except to case 2, through which the water in the liquid phase entrains the salts formed. If this condition were not met, the precipitation of salts would occur on the internal surface of pipes and equipments, causing a corrosive attack. The cost optimizations of the amine mixtures were calculated using their own data, with the constraints of items 1) and 2) satisfied by an initial estimate. Of all the cases studied, the PSO method obtained results with costs lower than half values obtained with the NM method.

In this thesis, we analyze volatility spillovers between crude oil and food commodities. The principal hypothesis assumes crude oil to behave as a production factor of the agricultural food commodities, thence we are looking for appropriate price effects. We mainly employ wavelet coherence and partial wavelet coherence, which provide us with valuable insight into the commodities nexus, without any strict restraints and assumptions levied on our data. Secondly, we build a DCC-GARCH model in order to model the presumed volatility spillovers. We also perform several simple benchmark analyses, in particular we test for Granger causality and we compute the Pearson correlation coefficients. Our data sample, including 10 commodities and 2 indices, covers the latest decade, significantly widening the existing contextual literature. Our results are mostly compliant with related literature, especially regarding the crude oil-fuels bundle and food commodities bundle, respectively. Considering the main research question of volatility spillovers between food commodities and crude oil, our results are indicating reasonably strong relationships with crude oil for soybeans and corn, leaving cotton and wheat rather on the verge of strong relationship and finding cattle to be completely unrelated. Main merits of the thesis...

Magister Scientiae (Biodiversity and Conservation Biology) - MSc (Biodiv and Cons Biol) / This study evaluated the nutritional quality of the forage plants in Namaqualand Granite Renosterveld vegetation in the Kamiesberg uplands of the Leliefontein communal area, South Africa. Determining the quality of forages is one of the most important factors necessary for the effective management of rangelands as it impacts on the nutrient needs of animals and consequently, the grazing capacity in rangelands. The edible portions of various forage plants were collected in the wet and dry seasons in 2012 and 2013 after which the nutritional quality (mineral nutrient content; crude protein (CP); fibre, neutral detergent fibre (NDF) and acid detergent fibre (ADF); dry matter digestibility (DMD); dry matter intake (DMI); metabolizeable energy (ME); and relative forage value (RFV)) as well as the anti-nutritional quality (total phenolics (TP); condensed tannins (CT); and silicon (Si) concentrations) of the plants were determined. Plants were thereafter grouped into their respective growth forms: grasses (15 species), herbs (15 species), leaf succulents (17 species), non-succulents (134 species), reeds (7 species), trees (8 species) and stem succulents (2 species) for statistical analyses. There were generally only a few significant differences for each forage growth form, when comparing the nutritional and anti-nutritional qualities between the two seasons. Certain forage types such as leaf succulents were found to have a high nutritional value in terms of their mineral nutrient content, CP, DMD and ME , but were also found to contain high concentrations of one or more anti-nutritional factors. However, within each season, results showed that for both the nutritional quality and anti-nutritional quality, there was a significant difference between the different growth forms within each season. This suggests that both of these quality parameters are essential in order to draw meaningful conclusions regarding forage quality of these semi-arid rangeland plants. Further research is needed at the species level to determine what plant species are the most nutritious in terms of both nutritional and anti-nutritional quality in order to inform the potential production of these species on a commercial scale.

La formation d’émulsions stables eau/huile lors des processus de récupération et de raffinage du pétrole peut impacter défavorablement l’efficacité de ces opérations. Bien que résines et asphaltènes soient généralement tenus pour responsables de la stabilité des émulsions, la composition exacte des molécules présentes à l’interface eau/huile est en réalité assez mal connue. L’identification de ces molécules et la connaissance de leur influence sur la propriété des interfaces est une étape nécessaire pour mieux prédire les problèmes de stabilité des émulsions dans l’industrie pétrolière. Cette thèse présente des résultats de caractérisation analytique par GPC-ICP-HRMS et FTMS du matériel interfacial (IM) extrait de quatre bruts différents et des espèces transférées dans la phase aqueuse lorsque ces bruts contactent l’eau, ainsi que des propriétés rhéologiques en cisaillement et en dilatation des interfaces eau/huile en présence de ces composés. Les bruts ont été choisis en raison de leur capacité à former des émulsions eau-dans-huile de stabilités différentes. Les mesures d’élasticité de cisaillement ont montré que la majorité des interfaces eau/huile étudiées formaient une structure élastique susceptible de fausser la mesure du module dilatationnel de Gibbs par la méthode d’analyse du profil de goutte. Néanmoins, nous montrons à l’aide de simulations numériques que le module apparent Eapp mesuré dans un tel cas est proche de la somme du module de Gibbs et du module de cisaillement (G) multiplié par 2 du réseau interfacial dès lors que G reste petit (G < 10 mN/m), ce qui est très souvent le cas puisque nous observons que le réseau interfacial formé se rompt lors des expériences de dilatation. Une équation phénoménologique a été développée permettant d’attribuer un temps de relaxation unique aux processus de relaxation qui ont lieu aux interfaces eau/huile, ce qui nous permet de classer les différents systèmes entre eux. Nous avons également étudié les IM extraits des bruts selon la technique chromatographique dite « wet silica method » récemment développée par Jarvis et al. (Energy Fuels, 2015). Les expériences de rhéologie interfaciale confirment que cette méthode permet d’extraire les composés les plus tensioactifs présents aux interfaces eau-brut. Les analyses chimiques montrent que les IM sont partiellement composés d’asphaltènes et suggèrent que les composés contenant du soufre jouent un rôle important dans la stabilité des émulsions. Enfin, nous avons trouvé que les composés hydrosolubles transférés du brut à l’eau ont un comportement bénéfique, dans le sens où leur présence rend les émulsions eau-dans-brut moins stables. L’analyse FTMS de ces composés montre qu’ils appartiennent aux classes d’hétéroatomes suivant : O2, O3, S1, OS et O2S2 et qu’une partie de ces composés appartient à la classe des asphaltènes. / Crude oil recovery and refining operations rely on high consumption water processes, which may induce the formation of stable water-in-oil emulsions. Although asphaltenes and resins are known to influence the stability of crude oil emulsions, much is still unknown about the real composition of the w/o interfacial layer. Therefore, identifying these molecules and understanding their impact on the w/o interfacial properties are key points for better predicting emulsion problems in the petroleum industry. This thesis presents results on water/oil (w/o) interface characterization using shear and dilatational interfacial rheology as well as results on molecular characterization (GPC-ICP-HRMS and FTMS) of the crude oil interfacial material (IM) and of the amphiphilic crude oil species, which are transferred to the aqueous phase during the emulsification process. Four crude oils forming w/o emulsions of different stability were used in this study. Shear interfacial rheology experiments showed that most of the studied w/o interfaces were capable of forming an elastic interfacial network exhibiting shear elasticity G. A non-null G value interferes on drop deformation and thus on drop shape analysis (DSA) results. Nevertheless, the dilatational elasticity modulus measured by DSA (Eapp) was found to be representative of the sum of the Gibbs modulus plus 2 times G, as long as G  10 mN/m. This condition is generally satisfied since the asphaltene network is broken during dilatational experiments. Consequently, Eapp gives a good approximation of the real Gibbs modulus of the interface. A new phenomenological equation was proposed to fit the dilatational Eapp experimental data, allowing the assignment of a unique characteristic time to describe the w/o interfacial relaxation process and thus sample comparison. The IM of the crude oils was extracted using the “wet silica method” recently developed by Jarvis et al. (Energy Fuels, 2015). Results showed that this method collects the most-surface active compounds that adsorb in the time frame of the extraction procedure. Successive extractions collected species that were larger and less concentrated in the crude oil, but with higher adsorption energies. Molecular characterization revealed that the IM was partially composed of asphaltene compounds, and suggested that sulfur-containing compounds may play a major role in emulsion stability. Lastly, the oil-to-water transferred species were proven to impact the w/o interfacial properties and emulsion stability. Interestingly, concentrating these water-soluble species led to more efficient crude oil dehydration. FTMS analysis of the transferred species revealed that part of the compounds belonged to O2, O3, S1, OS and O2S2 heteroatom classes, and some of them have an asphaltene-type of molecules classification.

O processo de destilação do petróleo bruto é geralmente sujeito à atividade corrosiva dos equipamentos pelos ácidos, naturalmente presentes no petróleo. Este problema da corrosão pode ser atenuado pela adição de misturas de aminas neutralizantes que são inibidores da corrosão. Porém, esta adição significa um custo adicional ao processamento de petróleo. Para reduzir este custo direto da injeção de aminas o presente trabalho tem como objetivo aplicar a minimização do custo de misturas de aminas, utilizando dois diferentes métodos numéricos de otimização. Para isto foi utilizado um software desenvolvido no Laboratório Virtual de Predição de Propriedades (LVPP), onde os seguintes parâmetros operacionais são levados em consideração: temperatura de formação de sal, temperatura de orvalho do vapor d’água e pH do condensado da mistura. Esses parâmetros operacionais foram calculados e utilizados como restrições de desigualdade em otimizações com os métodos de Nelder-Mead (NM) e enxame de partículas (PSO). A escolha desses dois métodos numéricos foi devido a apresentarem características diferentes de busca do ótimo da função objetivo. O método NM apresenta caráter de busca local e o método PSO caráter de busca global. Assim, as duas restrições de desigualdade de otimização aplicadas foram: 1) o pH do condensado da mistura deve ser maior ou igual ao valor ótimo de 6,5; 2) a temperatura de formação de sal deve ser menor que temperatura do ponto de orvalho do vapor d’água. Quatro diferentes casos foram estudados, com estimativas iniciais das misturas escolhidas para satisfazer os itens 1) e 2). Os parâmetros operacionais calculados para as misturas de aminas apresentaram valores de pH abaixo dos valores considerados aceitáveis. Isso exigiu a implementação de uma condição de pH que aumentasse seu valor até a condição satisfatória, conforme restrição 1). A outra condição referente a restrição 2) foi satisfeita no cálculo das misturas para todos os casos estudados, exceto para o caso 2, de modo que a água na fase líquida arraste os sais potencialmente formados. Caso essa condição não fosse cumprida ocorreria a precipitação desses sais incrustando à superfície interna das tubulações e equipamentos, ocasionando um ataque corrosivo. As otimizações dos custos das misturas foram calculadas utilizando-se os próprios dados das misturas, com as condições dos itens 1) e 2) satisfeitas, como estimativa inicial. Para todos casos estudados, o método PSO foi capaz de obter resultados com custos menores que a metade do valor obtido com o método NM. / Crude distillation equipment is usually subject to the corrosive activity of acids. This problem can be mitigated by the addition of amines. With the addition of amines to this process a cost is generated, therefore to reduce this cost of neutralizing the amines the present work applies two different optimization methods, Nelder-Mead (NM) and Particle Swarm Optimization (PSO). This was accomplished using an in house software, developed in the Virtual Laboratory of Property Prediction (LVPP), where the following operating conditions are taken into account: salt formation temperature, condensation temperature of the water and pH of the condensate of the mixture. The operational parameters were calculated and used as inequality constraints in optimizations with both Nelder-Mead (NM) and a particle swarm optimization (PSO) methods. Two inequality constraints were considered: 1) The condensate pH of the mixture should be higher or equal than 6.5; 2) The salt temperature should be less than the dew temperature of water vapor. Four different cases were studied, throught estimates initials of the mixtures to satisfy items 1) and 2). It has been found that the operating parameters calculated for several amine mixtures produced pH values below the one considered optimal. This required the implementation of a pH condition that would increase its value up to the condition satisfactory, in accordance with restriction 1). The other condition concerning restriction 2) was satisfied in the calculation of the mixtures for all studied cases, except to case 2, through which the water in the liquid phase entrains the salts formed. If this condition were not met, the precipitation of salts would occur on the internal surface of pipes and equipments, causing a corrosive attack. The cost optimizations of the amine mixtures were calculated using their own data, with the constraints of items 1) and 2) satisfied by an initial estimate. Of all the cases studied, the PSO method obtained results with costs lower than half values obtained with the NM method.

Abstract Moisture content control is a very effective way of protecting timber. Treatments with environment-friendly, biodegradable tall oil are known to reduce the capillary water uptake of pine sapwood greatly, but despite the good results achieved there have been two problems that limit the use of tall oil for wood protection, the large amount of oil needed and the tendency for the oil to exude from the wood. This work was undertaken in order to obtain an understanding of the mechanism of wood protection by means of crude tall oil (CTO) and to find technical solutions to the main problems limiting its use for industrial wood protection. It is shown that the emulsion technique is one way of solving the first problem, as it provides high water-repellent efficiency at considerably lower oil retention levels. The fact that water is used as a thinner in this technique instead of the commonly used organic solvents is beneficial from environmental, economic and safety points of view. It is also shown that although the drying properties of CTO are inadequate for use as such in wood preservation, its oxidation and polymerization can be accelerated considerably by means of iron catalysts, which prevent the oil from exuding out of the wood. This also increases the water repellent efficiency of CTO treatment. Most impregnation oils do not dry when applied in large quantities, because they hinder the diffusion of air through the wood, which supplies the necessary oxygen. Limiting of the oil uptake by the means of the emulsion technique disturbs the airflow to a lesser extent, and thus enhances the drying process. Hence, both the emulsion technique and the use of an iron catalyst improve both the water-repellent efficiency of tall oil treatment and the rate of drying of the oil, thus solving the two main problems related to wood impregnation with tall oil in one single-stage treatment which can be used in existing wood preservation plants. This is advantageous from both an industrial and an economic point of view.