Intrusion-related, carbonate rock–hosted replacement deposits are an important source of global base metal production that includes: Cu-Zn skarn, Zn-Pb-Ag carbonate replacement and Ag-base metal deposits. These deposits are located in multiple geological settings and are commonly associated with low-grade Cu-Mo calc-alkaline porphyry districts. Visible alteration halos to these deposits range from ten to hundreds of metres around high temperature skarn deposits, being small to imperceptible around the distal relatively low temperature members of this clan. Patterns of visible and cryptic alteration are described and constrained in this study particularly around paleo-fluid flow zones at different distances and elevations from the ore centre. This was done in order to identify the large-scale zonation, mechanisms, and effects of fluid infiltration especially into the distal portions of these deposits. The main alteration tracers employed included mineralogy, major and trace element geochemistry, oxygen and carbon isotopes, and the fluorescent signature of calcite veins associated with the fluids conduits. Two areas were selected for this study: the large Cu-Zn Antamina skarn and the Ag-base metal Uchucchacua vein deposits in the Peruvian Central Andes as these deposits represent the end-members of the polymetallic carbonate rock-hosted deposits and hence, provide an excellent opportunity to examine the margins and upper sections of these hydrothermal systems. Geochronological analyses of intrusive dikes were used to establish the magmatic and hydrothermal evolution associated with mineralization, as well as the genetic linkage between proximal and distal portions of the mineralizing system at Antamina. Oxygen, carbon and strontium isotope data of vein minerals is also used to constrain the temperature of the fluids proximal and distal to the magmatic centre. Chemical data of fluorescent and non-fluorescent veins were used to determine the main activators of fluorescence and to constrain its relationship with mineralizing fluids. In summary, results of this research identify a large-scale zonation of visible and cryptic alteration around paleo-fluid flow zones demonstrating the linkage between Ag-base metal veins, replacement and skarn deposits. Anomalous halos determined throughout Antamina and Uchucchacua deposits may contribute to the development of a more systematic exploration methodology for these types of deposits.

The solid oxide fuel cell (SOFC) is a potential high efficient electrochemical device for vehicles, auxiliary power units and large-scale stationary power plants combined heat and power application. The main challenges of this technology for market acceptance are associated with cost and lifetime due to the high temperature (700-1000 oC) operation and complex cell structure, i.e. the conventional membrane electrode assemblies. Therefore, it has become a top R&amp;D goal to develop SOFCs for lower temperatures, preferably below 600 oC. To address those above problems, within the framework of this thesis, two kinds of innovative approaches are adopted. One is developing functional composite materials with desirable electrical properties at the reduced temperature, which results of the research on ceria-based composite based low temperature ceramic fuel cell (LTCFC). The other one is discovering novel energy conversion technology - Single-component/ electrolyte-free fuel cell (EFFC), in which the electrolyte layer of conventional SOFC is physically removed while this device still exhibits the fuel cell function. Thus, the focus of this thesis is then put on the characterization of materials physical and electrochemical properties for those advanced energy conversion applications. The major scientific content and contribution to this challenging field are divided into four aspects except the Introduction, Experiments and Conclusions parts. They are: Continuous developments and optimizations of advanced electrolyte materials, ceria-carbonate composite, for LTCFC. An electrolysis study has been carried out on ceria-carbonate composite based LTCFC with cheap Ni-based electrodes. Both oxygen ion and proton conductance in electrolysis mode are observed. High current outputs have been achieved at the given electrolysis voltage below 600 oC. This study also provides alternative manner for high efficient hydrogen production.  Compatible and high active electrode development for ceria-carbonate composite electrolyte based LTCFC. A symmetrical fuel cell configuration is intentionally employed. The electro-catalytic activities of novel symmetrical transition metal oxide composite electrode toward hydrogen oxidation reaction and oxygen reduction reaction have been experimentally investigated. In addition, the origin of high activity of transition metal oxide composite electrode is studied, which is believed to relate to the hydration effect of the composite oxide. A novel all-nanocomposite fuel cell (ANFC) concept proposal and feasibility demonstration. The ANFC is successfully constructed by Ni/Fe-SDC anode, SDC-carbonate electrolyte and lithiated NiO/ZnO cathode at an extremely low in-situ sintering temperature, 600 oC. The ANFC manifests excellent fuel cell performance (over 550 mWcm-2 at 600 oC) and a good short-term operation as well as thermo-cycling stability. All results demonstrated its feasibility and potential for energy conversion. Fundamental study results on breakthrough research Single-Component/Electrolyte-Free Fuel Cell (EFFC) based on above nanocomposite materials (ion and semi-conductive composite) research activities. This is also the key innovation point of this thesis. Compared with classic three-layer fuel cells, EFFC with an electrolyte layer shows a much simpler but more efficient way for energy conversion. The physical-electrical properties of composite, the effects of cell configuration and parameters on cell performance, materials composition and cell fabrication process optimization, micro electrochemical reaction process and possible working principle were systematically investigated and discussed. Besides, the EFFC, joining solar cell and fuel cell working principle, is suggested to provide a research platform for integrating multi-energy-related device and technology application, such as fuel cell, electrolysis, solar cell and micro-reactor etc. This thesis provides a new methodology for materials and system innovation for the fuel cell community, which is expected to accelerate the wide implementation of this high efficient and green fuel cell technology and open new horizons for other related research fields. / <p>QC 20131122</p>

The study of outcrop modeling is located at the interface between two fields of expertise, Sedimentology and Computing Geoscience, which respectively investigates and simulates geological heterogeneity observed in the sedimentary record. During the last past years, modeling tools and techniques were constantly improved. In parallel, the study of Phanerozoic carbonate deposits emphasized the common occurrence of a random facies distribution along single depositional domain. Although both fields of expertise are intrinsically linked during outcrop simulation, their respective advances have not been combined in literature to enhance carbonate modeling studies. The present study re-examines the modeling strategy adapted to the simulation of shallow-water carbonate systems, based on a close relationship between field sedimentology and modeling capabilities. In the present study, the evaluation of three commonly used algorithms Truncated Gaussian Simulation (TGSim), Sequential Indicator Simulation (SISim), and Indicator Kriging (IK), were performed for the first time using visual and quantitative comparisons on an ideally suited carbonate outcrop. The results show that the heterogeneity of carbonate rocks cannot be fully simulated using one single algorithm. The operating mode of each algorithm involves capabilities as well as drawbacks that are not capable to match all field observations carried out across the modeling area. Two end members in the spectrum of carbonate depositional settings, a low-angle Jurassic ramp (High Atlas, Morocco) and a Triassic isolated platform (Dolomites, Italy), were investigated to obtain a complete overview of the geological heterogeneity in shallow-water carbonate systems. Field sedimentology and statistical analysis performed on the type, morphology, distribution, and association of carbonate bodies and combined with palaeodepositional reconstructions, emphasize similar results. At the basin scale (x 1 km), facies association, composed of facies recording similar depositional conditions, displays linear and ordered transitions between depositional domains. Contrarily, at the bedding scale (x 0.1 km), individual lithofacies type shows a mosaic-like distribution consisting of an arrangement of spatially independent lithofacies bodies along the depositional profile. The increase of spatial disorder from the basin to bedding scale results from the influence of autocyclic factors on the transport and deposition of carbonate sediments. Scale-dependent types of carbonate heterogeneity are linked with the evaluation of algorithms in order to establish a modeling strategy that considers both the sedimentary characteristics of the outcrop and the modeling capabilities. A surface-based modeling approach was used to model depositional sequences. Facies associations were populated using TGSim to preserve ordered trends between depositional domains. At the lithofacies scale, a fully stochastic approach with SISim was applied to simulate a mosaic-like lithofacies distribution. This new workflow is designed to improve the simulation of carbonate rocks, based on the modeling of each scale of heterogeneity individually. Contrarily to simulation methods applied in literature, the present study considers that the use of one single simulation technique is unlikely to correctly model the natural patterns and variability of carbonate rocks. The implementation of different techniques customized for each level of the stratigraphic hierarchy provides the essential computing flexibility to model carbonate systems. Closer feedback between advances carried out in the field of Sedimentology and Computing Geoscience should be promoted during future outcrop simulations for the enhancement of 3-D geological models. / Das Modellieren von geologischen Aufschlüssen liegt der Schnittstelle zwischen zwei geo-logischen Teildisziplinen, der Sedimentologie und der geologischen Modellierung. Hierbei werden geologische Heterogenitäten untersucht und simuliert, welche im Aufschluss beobachtet wurden. Während der letzten Jahre haben sich die Werkzeuge und die Technik der Modellierung stetig weiter-entwickelt. Parallel dazu hat die Untersuchung der phanerozoischen Karbonatablagerungen ihren Fokus auf gemeinsamen Vorkommen von zufälligen Faziesverteilungen in beiden Ablagerungs-gebieten. Obwohl beide Teildisziplinen durch die Aufschlussmodellierung eigentlich verbunden sind, wurden ihre jeweiligen Vorteile in der Literatur nicht miteinander verbunden, um so eine Verbesserung ähnlicher Studien zu erreichen. Die vorliegende Studie überprüft erneut die Modellierungsstrategie, angepasst an die Simulation von Flachwasser-Karbonat-Systemen und basierend auf einer engen Beziehung zwischen Sedimentologie und Modellierung. Die vorliegende Arbeit behandelt erstmals die Evaluierung der drei am häufigsten verwendeten Algorithmen „Truncated Gaussian Simulation (TGSim)“, „Sequential Indicator Simulation (SISim)“ und „Indicator Kriging (IK)“, um sie visuell und quantitativ mit dem entsprechenden Aufschluss zu vergleichen. Die Ergebnisse zeigen, dass die Heterogenität von Karbonatgesteinen nicht komplett mit nur einem Algorithmus simuliert werden kann. Die Eigenschaften jedes einzelnen Algorithmus beinhalten Vor- und Nachteile, sodass kein Algorithmus alle Beobachtungen aus dem Aufschluss widerspiegelt. Die zwei Endglieder im Spektrum der Ablagerungsbedingungen von Karbonaten, eine flachwinklige, jurassische Karbonat-Rampe (Hoher Atlas, Marokko) und eine isolierte, triassische Plattform (Dolomiten, Italien), wurden untersucht, um einen kompletten Überblick über die verschiedenen Heterogenitäten in Flachwasser-Karbonat- Systemen zu erhalten. Sedimentologische und statistische Analysen wurden für die verschiedenen Typen, Morphologien, Verteilungen und Assoziationen von Karbonatablagerungen durchgeführt und mit paläogeografischen Rekonstruktionen kombiniert und zeigen ähnliche Ergebnisse. Im Beckenmaßstab zeigen die Faziesassoziationen, bestehend aus Fazieszonen mit ähnlichen Ablagerungsbedingungen, einen linearen und kontinuierlichen Übergang zwischen den einzelnen Ablagerungsbereichen. Im Gegensatz dazu zeigt für einzelne Lithofaziestypen im Maßstab einzelner Schichten eine mosaikartige Verteilung, bestehend aus einer Anordnung räumlich unabhängiger Lithofazieszonen entlang des Ablagerungsprofils. Das Ansteigen der räumlichen Unordnung von der beckenweiten Ablagerung zur Ablagerung einzelner Schichten resultiert aus dem Einfluss autozyklischer Faktoren bei der Ablagerung von Karbonaten. Die Skalenabhängigkeit von Karbonat-Heterogenität ist mit der Auswertung der Algorithmen verknüpft um eine Modellierungsstrategie zu etablieren, welche sowohl die sedimentären Charakteristiken des Aufschlusses als auch die Modellierfähigkeit berücksichtigt. Für die Modellierung der Ablagerungssequenzen wurde ein flächenbasierter Ansatz verwendet. Die Faziesassoziationen wurden durch die Benutzung des TGSim-Algorithmus simuliert, um die regulären Trends zwischen den einzelnen Ablagerungsgebieten zu erhalten. Im Bereich der verschiedenen Lithofazien wurde mit dem SISim-Algorithmus, ein voll stochastischer Ansatz angewendet, um die mosaikartige Verteilung der Lithofazies-Typen zu simulieren. Dieser neue Arbeitsablauf wurde konzipiert, um die Simulierung von Karbonaten auf Basis der einzelnen Heterogenitäten in verschiedenen Größenordnungen zu verbessern. Im Gegensatz zu den in der Literatur angewendeten Simulationsmethoden berücksichtigt diese Studie, dass eine einzelne Modellierungstechnik die natürlichen Ablagerungsmuster und Variabilität von Karbonaten wahrscheinlich nicht korrekt abbildet. Die Einführung verschiedener Techniken, angepasst auf die verschiedenen Ebenen der stratigrafischen Hierarchie, liefert die notwendige Flexibilität um Karbonatsysteme korrekt zu modellieren. Eine enge Verknüpfung zwischen den Fortschritten auf dem Gebieten der Sedimentologie und dem Gebiet der modellierenden Geowissenschaften sollte weiterhin bestehen, um auch zukünftig bei der Simulation von geologischen Gelände-Aufschlüssen eine Verbesserung der 3-D-Modellierung zu erreichen.

The main purpose of this thesis was to find ways to maintain a low level of light‐induceddiscolouration at an increased addition of mechanical and chemimechanical pulps in coated highqualityfine paper and magazine paper grades. Current technology allows the production of highyieldpulps such as thermomechanical and chemimechanical pulps with properties suitable formanufacturing high‐quality paper or paperboard with a low basis weight. Coating of woodcontainingpaper will probably be necessary for photo‐stability reasons if lignin‐containing pulps areto be used as the main fibre furnish in long‐life and high‐value products.In order to find the most suitable pulp for this purpose, light‐induced discolouration of a variety ofpaper samples from unbleached and bleached softwood and hardwood pulps was studied under bothaccelerated and long‐term ambient light‐induced ageing conditions. Hardwood high‐yield pulps,especially aspen pulps, were proven to be more photo‐stable compared to softwood pulps. Hardwoodpulps should therefore be the first choice for applications where a high permanence is desirable.Evaluating ageing characteristics using the CIELAB colour system showed that accelerated ageingconditions tend to mainly increase the b* value and decrease the L* value (i.e. yellow the pulp),whereas long‐term ambient ageing also increases the a* value, which makes the pulp more reddish.A new method for studying the influence of the UV‐screening properties of coating layers on abase paper was developed, and used to investigate the effect of pigment, pigment size distribution,binder and UV‐absorbing additives. The coat weight and pigment type were found to be the mostimportant factors for reducing the transmittance of UV‐radiation. Coating colours containing kaolinpigments had a lower UV‐transmittance than calcium carbonate pigments. Of the calcium carbonates,precipitated calcium carbonates were better than ground calcium carbonates and the difference wasgreater at higher coat weights. The particle size distribution should preferable be narrow. When thebest pigment (bleached kaolin) and the best binder (styrene butadiene latex) were combined withtitanium dioxide, the UV‐transmittance could be reduced by about 90% at a coat weight of ~10 g/m2.At a coat weight close to 20 g/m2, the transmittance was close to zero. This shows that it is possible tomore or less fully protect a double coated base paper from harmful UV‐radiation, when the coatinglayer has an optimum composition for that purpose. A prerequisite to reach so far is that the coatinglayer has an even coat weight.

A CO2 emission analysis and system investigation of a direct fuel cell waste energy recovery and power generation system (DFC-ERG) for pressure letdown stations was undertaken. The hybrid system developed by FuelCell Energy Inc. is an integrated turboexpander and a direct internal reforming molten carbonate fuel cell system in a combined circle. At pressure letdown stations, popularly called city gates, the pressure of natural gas transported on long pipelines is reduced by traditional pressure regulating systems. Energy is lost as a result of pressure reduction. Pressure reduction also results in severe cooling of the gas due to the Joule Thompson effect, thus, requiring preheating of the natural gas using traditional gas fired-burners. The thermal energy generated results in the emission of green house gases. The DFC-ERG system is a novel waste energy recovery and green house gas mitigation system that can replace traditional pressure regulating systems on city gates. A DFC-ERG system has been simulated using UniSim Design process simulation software. A case study using data from Utilities Kingston’s city gate at Glenburnie was analysed. The waste energy recovery system was modelled using the design specifications of the FuelCell Energy Inc’s DFC 300 system and turboexpander design characteristics of Cryostar TG120. The Fuel Cell system sizing was based on the required thermal output, electrical power output, available configuration and cost. The predicted performance of the fuel cell system was simulated at a current density of 140mA/cm2, steam to carbon ratio of 3, fuel utilization of 75% and oxygen utilization of 30%. The power output of the turboexpander was found to strongly depend on the high pressure natural gas flowrate, temperature and pressure. The simulated DFC-ERG system was found to reduce CO2 emissions when the electrical power generated by the DFC-ERG system replaced electrical power generated by a coal fired plant. / Thesis (Master, Chemical Engineering) -- Queen's University, 2010-08-31 02:02:11.392

It is the study of banded iron formations (BIFs) that provides understanding into the conditions of the Earth's oceans and atmosphere during the Archean and Early Proterozoic. The aim of this thesis is to provide a detailed mineralogical and geochemical understand of BIFs from two separate localities separated by the Archean Proterozoic boundary. Close attention is paid to their carbonate and iron oxide mineralogy.The BIFs of the 2.7 Ga Manjeri Formation, Zimbabwe and 2.4 Ga Itabira Group, Brazil were both precipitated from oxygenated mixed marine-hydrothermal fluids. This is demonstrated by the presence of nano-hematite inclusions in the chert (Itabira and Manjeri) and dolomite (Itabira only) laminae, which is interpreted as the oldest mineral phase within the samples. Additionally, focused ion beam transmission electron microscopy (FIB-TEM) reveals the presence of nano ferrihydrite platelets within the dolomitic BIFs (carbonate itabirite). The dolomite is interpreted to be a primary phase precipitated at higher temperatures (~100°C) from CO2-rich hydrothermal fluids. Positive Eu anomalies in both formations indicate a hydrothermal component, likely to be the source of the reduced iron. Facies changes in both units are the result of transgression/regression and post depositional hydrothermal events mask primary conditions. Iron-rich carbonates in both facies have different origins; diagenetic (Itabira) and post depositional hydrothermal (Manjeri). However, the iron-rich carbonates of both formations have negative ∂13C values, indicating that at least part of the carbon in the carbonates is of organic origin. Curie Balance analyses into the carbonate itabirite reveals that maghemite is the transformation product of the ferrihydrite when dolomite decomposes at ~790°C. The maghemite has a Curie temperature between 320 and 350°C and is stable up to temperatures of 925°C.FIB-TEM investigations into the martitisation process revealed two possible mechanisms from two martite samples, from Brazil and India. Depending of the cause of the martitisation, here found to be deformation and hydrothermalism, the martitisation occurs respectively via either: 1. Ordering of point defects caused by vacancies in the spinel structure of maghemite, due to the removal of excess Fe3+ ions during the oxidation of magnetite, to form twins. It is in this twinning that the martitisation mechanism occurs.2. Grain boundary migration by hematite at the expense of magnetite is due to the presence of fluid along the crystal interfaces, where maghemite forms due to excess Fe3+ produced during martitisation of the magnetite, moving towards the surface of the magnetite crystals.

Le glycérol est un coproduit de la filière des biocarburants obtenu par transestérification destriglycérides. Avec le développement des biocarburants, la production de glycérol est en pleine croissance.La consommation de glycérol comme additif dans les industries cosmétique, pharmaceutique et agroalimentairen'augmentant pas de manière aussi significative, l'excédent doit être valorisé. L'une des voies devalorisation est la synthèse du carbonate de glycérol qui est un intermédiaire intéressant pour la chimie fine.La méthode de synthèse utilisée au sein de l'industrie Novance est la carbonylation du glycérol par l'urée enprocédé discontinu. Cette réaction produit, en plus du carbonate de glycérol, une grande quantitéd'ammoniac gazeux extrait du milieu réactionnel par dépression. L'ampleur de ce dégagement gazeux ainsique son irrégularité au cours du temps représente la limitation de production du procédé discontinu. Le sujetde cette étude est de développer le procédé continu de cette synthèse afin de pallier ce problème. Pourréaliser le suivi de la réaction, des méthodes analytiques ont été développées dans un premier temps. Avecces outils, les connaissances du système discontinu ont été approfondies pour déterminer les critères dechoix du procédé continu. Une unité de désorption réactive a été ensuite conçue pour créer un systèmebiphasique gaz-liquide à contre-courant. Une série d'essais préliminaires a permis le développement duprocédé qui a été optimisé par un plan de Doehlert.

The study focuses mainly on two gas hydrate-related targets, located on the Northern Cascadia Margin, offshore Vancouver Island: (1) a recently identified 70-80-m high carbonate mound, Cucumber Ridge, located ~3.5-km west of Ocean Drilling Program (ODP) Site 889 and Integrated Ocean Drilling Program (IODP) Site U1327, and (2) a large cold vent, Bullseye vent, which is up to ~500 m in diameter and was drilled by IODP at Site U1328. The objective of this thesis is to analyze seismic data that provide indicators of locally focused fluid flow and characteristics of the gas hydrate occurrence associated with these two features. A grid of closely-spaced single channel seismic (SCS) data was collected at Cucumber Ridge in July/August 2001, and deep-towed multichannel seismic (MCS) lines were collected using Deep-towed Acoustics and Geophysics System (DTAGS) at the Bullseye vent area and at Cucumber Ridge in October 2002. The high-resolution SCS data, with a frequency bandpass of 40-150 Hz, recorded coherent reflectivity down to about 400 m beneath the seafloor, and provide excellent images of the subseafloor structure of Cucumber Ridge and of the gas hydrate bottom-simulating reflector (BSR) beneath it. Cucumber Ridge is interpreted to have developed as a structural topographic high in the hanging wall of a large reverse fault formed at the base of the current seaward slope. The fault zone provides pathways for fluids including gas to migrate to the seafloor where diagenetic carbonate forms and cements the near-surface sediments. Over the seismic grid, heat flow was derived from the depth of the BSR. A simple 2-D analytical correction for theoretical heat flow variations due to topography is applied to the data. Across the mound, most of the variability in heat flow is explained by topographic effects, including a local 6 mW/m2 negative anomaly over the central mound and a large 20 mW/m2 positive anomaly over the mound steep side slope. However, just south of the mound, there is a 6-7 mW/m2 positive anomaly in a 2-km-long band that has predominantly flat seafloor. Most of this anomaly is probably unrelated to topographic effects, but rather likely due to warm upward fluid flow along faults or fracture zones. Towed ~300 m above seafloor, the high frequency (220-1k Hz) DTAGS signal can provide high vertical resolution images with increased lateral resolution. The major problems of DTAGS are significant nonlinear variations of the source depths and receivers locations. New routines were developed for optimal DTAGS data processing, mainly including (1) cable geometry estimation by node depths, direct arrivals and seasurface reflections using a Genetic Algorithm inversion method, (2) acoustic image stitching based on accurate relative-source positioning by crosscorrelation of redundant data between two adjacent shots, and (3) velocity inversion of wide-angle traveltimes using a nonlinear global grid search method. The final processed DTAGS images resolve multiple seismic blanking zones and fine details of subseafloor features in the slope sediments. At Bullseye vent, where a 35-m-thick near-surface massive hydrate layer was drilled at U1328, the DTAGS data resolved the upper part of layer as a dipping diffraction zone, likely corresponding to a fracture zone. The inverted velocity structure in upper 100 m sediments successfully revealed a 17-m-thick layer of high velocity (~1650 m/s) just below seafloor, probably related to carbonate presence. A local high velocity zone, with a positive velocity anomaly of ~40-80 m/s in the upper 50 m beneath seafloor, was observed over the ~100-m wide region between U1328 and the deepest part of a seafloor depression; the high velocity zone is consistent with the dipping diffraction zone in the DTAGS image and with the massive hydrate drilled at U1328.

Ocean uptake of anthropogenic CO2 causes ocean acidification, a secular, global-scale decline in the pH of seawater. In order to better understand the implications of contemporary acidification for marine organisms and ecosystems, there is a need to better characterise natural variability in carbonate chemistry. In this thesis, climatological seasonal variability of sea surface pH and aragonite saturation state (OmegaA) in the open ocean is indirectly derived from other parameters of the marine CO2 system, namely total alkalinity (TA) and seawater pCO2/fCO2 (pCO2sw/fCO2sw). New monthly sea surface TA, fCO2sw and temperature climatologies are developed for this purpose, utilising newly-released observational synthesis products (PACIFICA for TA and SOCAT v2 for fCO2sw). Two versions of the new SST climatology are developed, referred to as upper and lower SST (USST and LSST), to test sensitivity to the depth range of the input observations. Annual ranges are generally found to be larger for the USST climatology, derived using observations from the upper 2 m, compared to LSST (which is based on deeper observations). Further, a seasonal cycle is found in the monthly average of the differences between these climatologies north of 30 degN, perhaps partly due to seasonal variation in near-surface stratification. The USST seasonal ranges are also found to be generally larger than in two previous SST climatologies, however, difference in the depth distribution of the input measurements is unlikely the main cause. The new monthly sea surface TA climatology extends coverage into the Nordic seas, excluded from previous climatologies. TA seasonality is found to be small outside of regions with large seasonal ranges in salinity. Large seasonal ranges in salinity and TA are found beneath the Intertropical Convergence Zone, in the Antarctic seasonal sea ice zone and in the western Greenland Sea. Non-salinity driven TA seasonality is found to be large in the Gulf of Alaska, eastern equatorial Pacific and western Greenland Sea. Compared to the Lee et al. (2006) TA climatology, substantially lower annual means and seasonal ranges are found for the subarctic Pacific, a region with greatly improved coverage courtesy of PACIFICA. The pH/OmegaA climatologies derived in the final chapter suggest pH seasonality is predominantly temperature driven in the subtropics and mainly driven by variation in salinity normalised dissolved inorganic carbon (sDIC) in the subpolar north Atlantic, western subarctic Pacific and Southern Ocean. Salinity variation is found to only exert a strong influence on pH seasonality in the western Greenland Sea. Climatological seasonal pH ranges are found to be mostly small in the tropics (<0.05), moderate in the subtropics (0.05-0.10) but very large (>0.1) in parts of the Ross, Weddell, Irminger and Iceland Seas and western subarctic Pacific gyre. OmegaA seasonality is found to be predominantly sDIC-driven everywhere except in the western Greenland Sea, with temperature variation generally being of modest influence. Seasonal cycles of pH and OmegaA are found to be in anti-phase where pH is mainly thermally driven and in-phase where pH is mainly sDIC-forced (both pH and OmegaA vary inversely with DIC). Comparison is made between the primary new pH/OmegaA climatology and various open ocean carbonate chemistry time-series. The climatology captures the general form of the climatological seasonal cycles of pH and OmegaA from the time-series, although with some differences in phasing and seasonal range. Analysing the time-series for long-term trends, I find that inter-decadal anthropogenic CO2 uptake driven pH and OmegaA declines can be modulated by trends in temperature, salinity or sTA. Investigation is also conducted into how the amplitude of pH and OmegaA seasonal cycles might change by 2100 for a subpolar and subtropical time-series. Under a high CO2 emissions scenario, the seasonal range of pH is found to be strongly enhanced for the subpolar time-series and moderately reduced for the subtropical time-series, with both being due to changes in seawater buffer capacity. / Graduate / 0425 / 0415 / robdj87@hotmail.com

Scaling in green liquor handling systems is a persistent problem in many kraft mills. Scaling is commonly believed to be the result of pirssonite (Na2Ca(CO3)2∙2H2O) deposition. In this work, scale characterization was performed by analyzing 12 scale samples obtained from 10 kraft mills. Only 4 samples were identified as pirssonite while the remaining consisted of CaCO3. The predominant presence of CaCO3 in the scale samples was found to be the result of selective dissolution of Na2CO3 from pirssonite scale, leaving CaCO3 behind. Experimental studies were also conducted to study pirssonite solubility under green liquor conditions. Results obtained from these studies were used to create and validate a database for pirssonite in the OLI Systems® software to predict its formation. This database was used to generate a family of pirssonite solubility curves that can be used by the kraft mills as operational guidelines to prevent pirssonite precipitation.