Water is an essential element for life and crucial to survival. South Africa is a semi-arid country and therefore water should be protected and managed effectively by all residents of the country. In the 1830s the Mooi River was the key reason for the Voortrekkers to establish Potchefstroom at a locality adjacent to this river. The Voortrekkers noticed the dolomitic outcroppings in the vicinity, but still opted to reside next to the river for it provided easily accessible water and fertile soil. Since the 1830s water legislation regulating the management and use of the water in the Mooi River has been amended innumerable times to bring us to the current situation of Potchefstroom’s water (mis)management by the role-players and stakeholders of the water source. As a resident of Potchefstroom, the researcher has a keen interest in the origin of the city’s water sources, the re-routing of the water from the origin to the water purification unit via the open-on-top cement canal system, and the overall management of these canals and their servitudes. In order to conduct a research study on the Mooi River’s water re-routing canals and servitudes, the following research methods were applied: The researcher performed a comprehensive literature review, conducted fieldwork, held interviews with landowners and experts in the geographical area of the Mooi River Valley, and performed statistical analyses as well as content analyses of the findings. Some of the most alarming findings include the lack of co-operative governance between water users and – authorities, and the current public management and disaster risk management challenges in the re-routing of water from Klerkskraal Dam down to the water purification plant of Potchefstroom. It is recommended that the major stakeholders of the Mooi River Valley, e.g. the disaster management centre in Potchefstroom, the Department of Water and Sanitation’s (DWS) regional offices in Potchefstroom, as well as the Tlokwe Local Municipality need to join forces for a combined effort to accomplish the overarching research objective of achieving improved cooperative municipal governance and Integrated Water Resources Management (IWRM) to eventually ensure the safe and effective re-routing of water from the Klerkskraal Dam to the Potchefstroom water purification plant. Note: Since July 2014 the Department of Water Affairs (DWA) has changed to the Department of Water and Sanitation (DWS). / MA (Public Management and Governance), North-West University, Potchefstroom Campus, 2015

The geological sequestration of carbon dioxide (CO2) is one of the options of controlling the greenhouse gas emissions. However, leakage of CO2 from the storage reservoir is a risk associated with geological sequestration. Over longer times, large-scale groundwater motion may cause leakage of dissolved CO2 (CO2aq). The objectives of this thesis are twofold. First, the modelling study analyzes the leakage of CO2aq along the conducting pathways. Second, a relatively safer mode of geological storage is investigated wherein CO2aq is injected in a carbonate reservoir. A reactive transport model is developed that accounts for the coupled hydrological transport and the geochemical reactions of CO2aq in the porous media. The study provides a quantitative assessment of the impact of advection, dispersion, diffusion, sorption, geochemical reactions, temperature, and heat transport on the fate of leaking CO2aq. The mass exchange between the conducting pathway and the rock matrix plays an important role in retention and reactions of leaking CO2aq. A significant retention of leaking CO2aq is caused by its mass stored in aqueous and adsorbed states and its consumption in reactions in the rock matrix along the leakage pathway. Advection causes a significant leakage of CO2aq directly from the reservoir through the matrix in comparison to the diffusion alone in the rock matrix and advection in a highly conducting, but thin fracture. Heat transport by leaking brine also plays an important role in geochemical interactions of leaking CO2aq.  Injection of CO2aq is simulated for a carbonate reservoir. Injected CO2-saturated brine being reactive causes fast dissolution of carbonate minerals in the reservoir and fast conversion of CO2aq through considered geochemical reactions. Various parameters like dispersion, sorption, temperature, and minerals reaction kinetics are found to play important role in the consumption of CO2aq in reactions. / <p>Research Funders:</p><p>(i) Higher Education Commission (HEC) of Pakistan</p><p>(ii) Lars Erik Lundberg Scholarship Foundation, Sweden</p>

Ce travail a pour but l'étude de la stabilité des minéraux sulfatés et carbonatés dans les sédiments marins au cours de la diagenèse précoce (températures inférieures à 70°C et enfouissement maximal de 2 kilomètres). La première partie présente l'étude pétrographique et géochimique de concrétions dolomitiques contenant de la calcite et des sulfates (célestine et barytine), dans le delta éocène du Sobrarbe (Espagne). Nous déterminons l'ordre d'apparition des minéraux ainsi que leurs conditions de formation dans un contexte tectonique actif. Dans la deuxième partie, l'état de saturation des eaux interstitielles des sédiments marins par rapport aux carbonates et sulfates est calculé en utilisant l'intégralité de la base de données ODP/IODP (14000 échantillons). Pour les sulfates (célestine, gypse), la saturation est fréquente et caractérisée par l'équilibre chimique. Ce travail montre comment la modélisation des interactions eau/roche peu expliquer la présence de minéraux diagénétiques

L'écoulement ductile d'une roche, en présence de fluide, peut s'effectuer par transfert de matière autour de domaines constituants cette roche, sous l'effet de différences de contrainte normale, ou de différences d'énergie élastique, plastique, ou de surface. Les stylolites, schistosités, fentes ou cavités colmatées,témoignent de ce fluage par dissolution-cristallisation dans la croûte supérieure. Différents modèles théoriques en ont été établis, avec des vitesses de déformation limitées par chacun des processus successifs de la transformation (cinétique des réactions solide/fluide, ou vitesse des transferts par diffusion ou infiltration). Puis ces modèles ont été testés en distinguant l'effet de plusieurs paramètres (géométrie des domaines, conditions P.T., nature des matériaux, valeurs des coefficients de transfert) . Pour l'aspect expérimental on a réalisé des dissolutions-cristallisations du quartz et de la calcite, autour de cavités ou autour de grains sous contrainte, en maintenant ces minéraux plusieurs mois au contact de fluides chauds et sous pression (eau, Na OH, NH4 CI) . Différentes forces motrices peuvent intervenir (énergie de surface autour des cavités, contrainte normale autour des grains). Différents processus peuvent limiter les vitesses des déformations (cinétique de réaction pour les cavités, vitesse de diffusion pour les grains). Pour l'aspect naturel. des analyses chimiques comparatives au sein de roches à déformation hétérogène (plissement, cisaillement, poinçonnement, boudinage) permettent de faire un bilan des quantités transférées. On montre que !e transfert peut s'effectuer par diffusion ou par infiltration, sous de faibles déviateurs de contrainte, avec une mobilité variable des minéraux selon les conditions P.T . Les possibilités et les conditions du transfert imposent en priorité le type de modèle de dissolution-cristallisation et la vitesse de cette déformation. On discute de l'initiation et du développement des zones de dissolution et de cristallisation et de l'acquisition d'un litage tectonique dont l'orientation, la géométrie et les compositions reflètent les conditions de la déformation. Des applications sont données pour des processus voisins (métamorphisme, diagenèse) et pour des problèmes particuliers (déformation interne des roches, concentration des minéralisations, glissement asismique des failles).

Two hydrogeologic models explore reflux dolomitization using two outcrop datasets at different scales to constrain transient boundary conditions and heterogeneous petrophysical properties. A platform-scale petrophysical model of the Permian San Andres Formation was built from outcrop and subsurface data following a reservoir modeling approach that preserves outcrop heterogeneity and incorporates a sequence stratigraphic framework. This model was used as input for hydrogeological simulations of hypersaline fluid flow and solute transport during the accumulation and compaction of the platform. Boundary conditions change over time, as relative sealevel fluctuations drive sedimentation, depositional environment migration, topographic gradients, and location, size and salinity of the brine source. The potential volume and distribution of dolomite formed is inferred by a magnesium mass-balance. The composite result of reflux events at various orders of stratigraphic hierarchy is a complex dolomite pattern that resembles that observed on San Andres outcrops. Dolostone bodies across the platform may be generated by different combinations of favorable conditions, including proximity to the brine source, zones of higher permeability, permeability contrasts, and latent reflux. A meter-scale reactive transport model of the Albian Upper Glen Rose Formation simulates deposition of three high-frequency cycles punctuated by three brine reflux events. The simulator determines flow, solute and reactive transport along the flow paths, revealing the spatial and temporal distribution of calcite dissolution, and precipitation of dolomite and sulfate. The model recreates fully and partially dolomitized cycles within the time and lithological constrains on Glen Rose outcrops. Our results show that the distribution of dolomite within a high-frequency cycle may be the net result of intercycle processes, whereby dolomitizing fluids sourced from younger cycles flow across stratigraphically significant boundaries. We also show that variations in dolomite abundance and the unfulfilled dolomitization potential control the contemporaneous propagation of multiple dolomite fronts and the coalescence of discrete dolomite bodies. Results show that reflux is an effective and efficient mechanism to dolomitize carbonate formations that progresses simultaneously with sediment accumulation. Dolomitization is the cumulative result of many short-lived reflux events, sourced in different locations and times, and amalgamation of successive dolostone bodies. This model contrasts with previous studies that approached dolomitization of a carbonate platform as a discrete reflux event and current interpretations that relate dolomite bodies to their most immediate stratigraphic surfaces. / text

Σημαντικός αριθμός μνημείων και έργων τέχνης είναι κατασκευασμένα από πέτρα, μάρμαρο κατά πρώτο λόγο, και έπειτα από ασβεστόλιθο και από άλλα πυριτικά υλικά. Η παρούσα εργασία επικεντρώθηκε στη μελέτη της διάλυσης του μαρμάρου σε διάφορες συνθήκες με απώτερο στόχο την αποκάλυψη του μηχανισμού της φυσικοχημικής αυτής διεργασίας τόσο για την περίπτωση ασβεστιτικών όσο και δολομιτικών μαρμάρων. Η κατανόηση του μηχανισμού του προβλήματος είναι απαραίτητη για την κατάλληλη προσέγγιση και επιλογή των μεθόδων προστασίας. Έτσι, στην παρούσα εργασία επιχειρήθηκε: α) Ο προσδιορισμός του μηχανισμού διάλυσης από πειράματα μέτρησης της κινητικής της διάλυσης του μαρμάρου σε ακόρεστα ως προς το βασικό συστατικό (ασβεστίτης, δολομίτης) διαλύματα και σε διαφορετικές συνθήκες ακορεστότητας. β) Η αναστολή της διάλυσης με την προσθήκη υδατοδιαλυτών τασιενεργών ουσιών και η διερεύνηση του μηχανισμού δράσης τους. γ) Η δημιουργία δυνητικά προστατευτικών επικαλύψεων των επιφανειών του (ασβεστιτικού) μαρμάρου με στρώματα ανόργανων αλάτων. δ) Η σύγκριση των αποτελεσμάτων μέτρησης του ρυθμού διάλυσης τόσο παρουσία όσο και απουσία προσθέτων ουσιών με βιβλιογραφικές αναφορές, και αποτελέσματα από πειράματα υπαίθριας έκθεσης και από πειράματα έκθεσης δοκιμίων σε συνθήκες επιταχυνόμενης διάβρωσης σε θάλαμο αλατονέφωσης (παρουσία και άλλων παραγόντων, όπως μικροοργανισμοί, μικροβιοκτόνες ενώσεις). Ο στόχος της σύγκρισης αυτής ήταν η επιλογή του καταλληλότερου μοντέλου για την αξιόπιστη δοκιμή νέων υλικών και μεθόδων προστασίας του μαρμάρου. Για τη διεξαγωγή των δοκιμών, επιλέχθηκαν τρεις τύποι μαρμάρου που απαντώνται σε μνημεία και γλυπτά στην Ευρώπη: Carrara (ασβεστίτης >98%), Πεντελικό (ασβεστίτης >98%) και Ekeberg (δολομίης ~93%). Τα διαλύματα που χρησιμοποιήθηκαν στις μετρήσεις, κινητικής της διάλυσης ήταν ακόρεστα ως προς ασβεστίτη και παρασκευάζονταν με την αραίωση κατάλληλων όγκων stock διαλυμάτων CaCl2, MgCl2, NaHCO3, NaCl, και η αρχική τιμή του pH ρυθμιζόταν στο 8.25 με προσθήκη 0.01N NaOH. Μετά την αποκατάστασης ισορροπίας στα ακόρεστα διαλύματα εργασίας, γινόταν προσθήκη ακριβώς ζυγισμένης σκόνης μαρμάρου ή η εμβάπτιση των δοκιμίων (στερεωμένων σε ειδικό στήριγμα). Τρεις μέθοδοι χρησιμοποιήθηκαν για τις μετρήσεις της κινητικής της διάλυσης του μαρμάρου: συνθήκες ελεύθερης μεταβολής (free drift), συνθήκες σταθερού pH (pH-stat), συνθήκες σταθερού κορεσμού. Για τα ασβεστιτικά μάρμαρα, οι μετρήσεις του ρυθμού διάλυσης τόσο του μαρμάρου (κονιοποιημένου ή δοκιμίων) όσο και της πρότυπης ένωσης αναφοράς (ασβεστίτης) συναρτήσει της ακορεστότητας των διαλυμάτων έδειξαν γραμμική εξάρτηση. Σε όλες τις περιπτώσεις, οι ρυθμοί που υπολογίσθηκαν ήσαν της αυτής τάξης μεγέθους με τους αντίστοιχους ρυθμούς του καθαρού ασβεστίτη. Η θερμική κατεργασία του Πεντελικού μαρμάρου οδήγησε σε σημαντική αύξηση του ρυθμού διάλυσης, και η εξάρτηση των μετρούμενων ρυθμών, R, από τον σχετικό υπερκορεσμό, σ, ήταν μη γραμμική, με n>1. Για το δολομιτικό μάρμαρο Ekeberg, από το διάγραμμα του ρυθμού διάλυσης συναρτήσει της σχετικής ακορεστότητας σ, η προσαρμογή των δεδομένων στην R=kdσn έδωσε την τιμή n=2, οπότε εξήχθη το συμπέρασμα, ότι το στάδιο που καθορίζει τη διάλυση του δολομιτικου μαρμάρου είναι η επιφανειακή διάχυση. Μετρήθηκε και η διαλυτότητα τόσο του δολομιτικού όσο και των λοιπών τύπων μαρμάρου. Τα ασβεστιτικά μάρμαρα Πεντελικό και κρυσταλλίνα Θάσου έδωσαν τιμές για το γινόμενο διαλυτότητας κοντά στην αντίστοιχη τιμή για τον καθαρό ασβεστίτη (8.48) ενώ τα υπόλοιπα ασβεστιτικά (Carrara, Σπηλιά, Διονύσου) έδωσαν υψηλότερες τιμές διαλυτότητας. Τα δύο δολομιτικά μάρμαρα έδωσαν την αυτή τιμή για τη σταθερά διαλυτότητας, η οποία ευρίσκεται εντός των ορίων τιμών που έχουν αναφερθεί στην βιβλιογραφία για στοιχειομετρικό δολομίτη. Σε όλες τις περιπτώσεις ο ρυθμός διάλυσης του μαρμάρου βρέθηκε ότι ελέγχεται από την επιφανειακή διάχυση των δομικών λίθων στο οριακό στρώμα του υγρού. Η ρόφηση κάποιας ουσίας πάνω στο στερεό θα μπορεί να δεσμεύει τα ενεργά κέντρα και θα έχει αποτελεσματική δράση στην επιβράδυνση της διάλυσης. Έγινε μελέτη ρόφησης ουσιών με ιοντιζόμενες φωσφορικές και φωσφονικές ομάδες σε σκόνες των μαρμάρων Πεντελικού, Carrrara και Ekeberg (ισόθερμοι ρόφησης). Το HEDP μελετήθηκε σε μεγαλύτερη έκταση, τόσο γιατί η παρουσία του στα ακόρεστα διαλύματα είχε ως αποτέλεσμα τη σημαντικότατη αναστολή της διάλυσης, όσο και διότι ως ουσία με ιονιζόμενες δραστικές ομάδες αποτελεί μοντέλο για την μελέτη της επίδρασης ανάλογων ουσιών σε κρυσταλλικά στερεά τα οποία διαθέτουν κατιόντα μετάλλων στην επιφάνειά τους. Η προσθήκη του αναστολέα HEDP στα ακόρεστα διαλύματα είχε ως αποτέλεσμα τη μείωση του ρυθμού διάλυσης σε ανάλογο βαθμό με την προ-ρόφησή του. Η προσθήκη του HΕDP στα ακόρεστα διαλύματα, έδωσε μικρότερους ρυθμούς διάλυσης σε σύγκριση με τους αντίστοιχους ρυθμούς οι οποίοι ελήφθησαν από δείγματα στα οποία η ουσία αυτή είχε προ-ροφηθεί στο στερεό (πειράματα σε σκόνες και δοκίμια ασβεστιτικών μαρμάρων). Το HEDP εκτός από την επιβράδυνση της διάλυσης (ακόμα και κατά 80-90 %), βρέθηκε ότι είχε αρνητική επίδραση στη μορφολογία των κρυστάλλων του μαρμάρου. Ο στόχος της επόμενης σειράς πειραμάτων ήταν η δημιουργία επικαλύψεων σε συμπαγή δοκίμια μαρμάρου. Οι επικαλύψεις αυτές, αποτελούντο από ανόργανα άλατα, μικρότερης διαλυτότητας σε υδατικά διαλύματα, σε σύγκριση με τον ασβεστίτη. Τα διαλύματα αντιδραστηρίων κατεργασίας (HCl, ΕDTA, γαλακτικού οξέος, oξικού οξέος, H3PO4, HEDP, NTMP , N(phosphomethyl-) imino diacetic acid) εφαρμόσθηκαν με: α) επίχριση με πινέλο, β) επίθεση εμποτισμένων υφασμάτων, γ) εμβάπτιση των δοκιμίων στα αντίστοιχα διαλύματα. Αποτελεσματικότερος τρόπος εφαρμογής ήταν η εμβάπτιση. Ο χαρακτηρισμός των επιφανειών, και των αντίστοιχων επιστρώσεων και η ταυτοποίησή τους έγινε με XRD, FΤ-IR και SEM. Στην συνέχεια, τα σύνθετα υλικά (μάρμαρο+επικάλυψη), υποβλήθηκαν σε πειράματα διάλυσης σε διαλύματα ακόρεστα ως προς ασβεστίτη προκειμένου να δοκιμασθεί η αποτελεσματικότητά τους στην προστασία της επιφάνειας του μαρμάρου από τη διάβρωση. Η επεξεργασία με φωσφορικό οξύ, είχε ως αποτέλεσμα την δημιουργία παχέος στρώματος διένυδρου, όξινου φωσφορικού ασβέστιου (CaHPO42H2O, DCPD). Με δεύτερη εμβάπτιση σε διάλυμα όξινου φωσφορικού νατρίου η υδρόλυση των αρχικά σχηματισθέντων κρυστάλλων DCPD, οδήγησε στον σχηματισμό ψευδομορφικών κρυστάλλων OCP οι οποίοι και σχηματίζουν στρώμα περίπου 100 μm, το οποίο καλύπτει πλήρως την επιφάνεια του μαρμάρου και παρουσιάζει εξαιρετική πρόσφυση στην επιφάνεια. Οι δοκιμές διάλυσης σε ακόρεστα διαλύματα, έδειξαν ότι διαλύεται μόνο η επικάλυψη. Υπαίθρια Έκθεση. Επαληθεύθηκε η ανασταλτική δράση του HΕDP στην διάλυση των δοκιμίων του μαρμάρου τα οποία εκτέθηκαν στους σταθμούς υπαίθριας έκθεσης. Γενικά, οι τασιενεργές ουσίες που δοκιμάσθηκαν προστάτευσαν τα δοκίμια του μαρμάρου σε μεγαλύτερο βαθμό από τις υδρόφοβες ουσίες γεγονός το οποίο υπογραμμίζει την σημασία της αλληλεπίδρασης ουσίας-υποστρώματος και το οποίο είναι σε συμφωνία με τα ευρήματα από τα πειράματα που διεξήχθησαν στους αντιδραστήρες batch.. Θάλαμος αλατονέφωσης. Σε συνθήκες επιταχυνόμενης διάβρωσης, επαληθεύθηκε για μια ακόμα φορά η ανασταλτική δράση ουσιών όπως το HΕDP, οι οποίες μπορούν να αλληλεπιδράσουν με το μάρμαρο. Είναι αξιοσημείωτο ότι τα αποτελέσματα των μετρήσεων της κινητικής της διάλυσης τα οποία ελήφθησαν από την υπαίθρια έκθεση δοκιμίων ήσαν συγκρίσιμα με τα αποτελέσματα των μετρήσεων σε αντιδραστήρες τύπου batch. . Η μέθοδος μέτρησης της κινητικής της διάλυσης σε ακόρεστα διαλύματα και σε συνθήκες σταθερού κορεσμού, έχει τη δυνατότητα σε μικρό σχετικά χρονικό διάστημα να δώσει ικανοποιητικές πληροφορίες σχετικά με τη συμπεριφορά των δοκιμίων μαρμάρου σε διαβρωτικό περιβάλλον αλλά και να χρησιμεύσει σε δοκιμές ελέγχου και προκαταρκτικής αξιολόγησης (screening) σειράς υποψήφιων για την προστασία του μαρμάρου ουσιών. / A significant number of historic monuments and artworks have been made of stone, mainly of marble, lime and silicate materials. The work in the present thesis, is focused on the investigation of the kinetics of marble dissolution under various conditions. These studies contribute to the understanding of the mechanism of dissolution, for of calcitic and dolomitic marbles. Understanding the mechanism of the problem is essential for the selection and the implementation of methods for the protection of monuments. More specifically, in the present work it was attempted to achieve the following tasks: a) Determination of dissolution mechanism, through measurements of the kinetics of marble dissolution in solutions undersaturated with respect to the main component (calcite, dolomite) under various undersaturation conditions at controlled conditions. b) Dissolution inhibition by addition of water soluble compounds and investigation of the mechanism of their interaction with the calcitic surfaces. c) Formation of potentially protective coatings on marble surface consisting of sparingly soluble inorganic salts. d) Comparison of marble dissolution rates (in the presence and in the absence of different water soluble substances) with the respective values reported in the literature and with results from marble specimens exposed outdoors or under accelerated weathering conditions in a salt spray chamber (with or without other agents, including colonization with microorganisms, treatment with biocides). The aim of this comparison was the selection of the best model for the reliable testing of novel methods and materials for the protection of marble. Three marble types were selected in the present investigation. These types have been frequently used as building materials in monuments and sculptures in Europe: Carrara (>98% calcite), Pentelic (>98% calcite) and Ekeberg (>93% dolomite). A number of compounds were selected for the investigation of their effectiveness of protection against marble weathering due to wet precipitation: VPA3-7 (surfactant) and HEDP (organophosphorus compounds), Hydrophase superfici (hydrophobic substannce) and Algophase  (biocide). To study the effect of microorganisms on the weathering of marble specimens exposed outdoors, they were inocculated with a bacteria culture consisting of (Geodermatophilus sp BC 508 isolated from limestone rock (Noto, Syracuse, Italy) , Micromonospora sp. BC 562 isolated from Pentelic marble), fungi (Coniosporium apolliniis MC518 isolated from marble from Tarragona Cathedral (Spain) and Coniosporium uncinatum MC557 isolated from Carrara marble statue (Messina, Italy).) The aim of the measurements of the rates of marble dissolution in solutions undersaturated with respect to calcite, as a function of the relative undersaturation was the attainment of a better understanding for the mechanism underlying marble dissolution. Undersaturated working solutions were prepeared by dilution of proper stock solutions of CaCl2, MgCl2, NaHCO3, NaCl, and pH was initially adjusted to 8.25 with 0.01N NaOH. After equilibration of undersaturated solutions in the reactor, known amount of marble was introduced, either in powder form (suspension) or in rod form (fixed on special scaffold). Depending on the control of the parameters possible the following types of experiments were done and the dissolution rates were measured: free drift (all variables change with the exception of temperature), constant pH (pH only is kept constant), constant undersaturation (the activities of all species in the undersaturated solutions are kept constant). The dissolution rates of calcitic marble (both in powders and slabs) and calcite powder showed linear dependence on the relative undersatutation. In all cases, the rates of dissolution were of the same order of magnitude with the rates corresponding to (synthetic) calcite powder. Thermal pretreatment of pentelic marble powder resulted to higher dissolution rates. In this case, the dependence of the rates measured with respect to the relative undersatutation was found to be non-linear, (R=Kdσn , n>1). In the case of Ekeberg marble, the dependence of the rates of dissolution on the relative undersatutation was found to be non-linear, as well with n = 2. It may therefore be concluded that the dissolution is surface diffusion controlled. In the present work, solubilities for different types of marbles investigated in aqueous solutions were calculated from measurements of specimens equilibrated with electrolyte solutions over a time period exceeding the 2 years. For Pentelic and Crystallina Thassou marbles, values of solubility products were close to the value of pure calcite, while those for the rest of the calcitc marbles (Carrara, Spilia, Dionysoy) were higher. For the dolomitc marbles Ekeberg and Thassos White, the values obtained were almost identical and close to the values reported for stoichiometric dolomite. In all cases, the rate of dissolution was found to be controlled by surface diffusion. The adsorption of a substance on marble surface could possibly affect the dissolution process. The adsorption of substances posessing ionisable phosphate and phosphonate groups on marble powders (Pentelic, carrara, Ekeberg) was investigated through the respective adsorption isotherms. HEDP was mainly studied in this section, because its presence in undersaturated solutions inhibited dissolution to a large extent, and also because it could be considered as a model substance for the investigation of the effect of substances with similar functional groups on crystalline solids with metal cations on their surface. The presence of HEDP in the undersaturated solutions resulted in the reduction of the marble dissolution rates, proportionally to the extent of HEDP adsorption on the substrate. The dissolution rates obtained were lower than those obtained in experiments were HEDP was pre-adsorbed on the substrate (both in marble powder and in marble rod tests). HEDP showed strong inhibition effect (even by 80-90%) but also showed negative effect on the morphology marble crystallites. The aim of the next series of experiments was the formation of coatings on pentelic marble slabs. The coatings tested in the present investigation, consisted of inorganic salts , less soluble than calcite. Treatment solutions (HCl, ΕDTA, lactic acid, H3PO4, HEDP, NTMP , N(phosphomethyl-) imino diacetic acid) were applied by:a) brush, b) impregnated patch and c) immersion. The most effective way was impregnation. XRD, FT-IR and SEM were used for the characterization of the surfaces and of the composition of the coatings. The “new” composite (marble + coating) materials were then subjected to dissolution experiments in solutions undersaturated with respect to calcite. Treatment of marble with phosphoric acid resulted in formation of a thick layer of CaHPO42H2O, DCPD. Following a second treatment with sodium hydrogen phosphate solution, the iniatially formed DCPD crystals were hydrolyzed to pseudomorfic OCP crystals, resulting to a layer of 100 um thickness with complete coverage of the surface and good adhesion on the substrate. Dissolution experiments showed that only the coating was dissolved. T Outdoors exposure. The inhibiting effect of HEDP on dissolution was verified in the case of the exposed marble specimens. The surfactant substances tested seemed to protect the specimens more than the hydrophobic compounds, which empasizes the importance of substance-substrate interaction and is in good agreement with batch experiment results. Salt spray chamber. The inhibiting effect of HEDP on dissolution was again verified in the case of the marble specimen exposedunder accelerated weathering conditions. Results of the measurements of the kinetics of marble dissolution obtained from outdoors exposure tests of marble slabs, were comparable to those obtained from batch reactor experiments. Measurement of dissolution kinetics in working solutions under constant undersaturation conditions is a method capable of providing satisfactory information on the behaviour of marble specimen under weathering conditions and a useful tool on testing and evaluating the efficiency of candidate protective methods and products in a short time (suitable as preliminary screening tool).

Geologic sequestration of anthropogenic carbon dioxide (CO2) greenhouse gas emissions is an engineering solution that potentially reduces CO2 emissions released into the atmosphere thereby limiting their effect on climate change. This study focuses on Woodside field as a potential storage and sequestration site for CO2 emissions. The Woodside field is positioned on a doubly plunging, asymmetrical anticline on the northeast flank of the San Rafael Swell. Particular focus will be placed on the Permian White Rim Sandstone, Black Box Dolomite and Black Dragon Member of the Triassic Moenkopi Formation as the reservoir/seal system to store and sequester CO2 at Woodside field. The White Rim Sandstone, the primary target reservoir, is divided into three stratigraphic intervals based on facies analysis: a lower sand sheet facies (about 60 ft or 18 m), a thick middle eolian sandstone facies (about 390 ft or 119 m), and an upper marine reworked facies (about 70 ft or 21 m). Porosity and permeability analyses from the outcrop indicate good reservoir quality in the eolian sandstone and reworked facies. Porosity in the White Rim Sandstone ranges from 7.6 to 24.1% and permeability reaches up to 2.1 D. The maximum combined thickness of the three facies is 525 ft (160 m) at Woodside field providing a significant volume of porous and permeable rock in which to store CO2. The Black Box Dolomite is the secondary potential reservoir for CO2 storage at Woodside field and has a gross thickness up to 76 ft (23 m). The Black Box Dolomite is divided into four lithofacies: a basal nodular dolomudstone (8.2 -15 ft or 3.5-4.5 m), a dolowackestone (25-37 ft or 7.5-11 m), a dolomitic sandstone (0-8.2 ft or 0-2.5 m), and an upper sandy dolowackestone (0-16 ft or 0-4.9 m). Porosity and permeability analyses indicate reservoir potential in the dolowackestone, dolomitic sandstone, and sandy dolowackestone lithofacies. Porosity in the Black Box Dolomite ranges from 6.6 to 29.2% and permeability reaches up to 358 mD. The nodular dolomudstone lithofacies has relatively poor reservoir quality with porosity up to 9.4% and permeability up to 0.182 mD. This lithofacies could act as a baffle or barrier to fluid communication between the White Rim Sandstone and Black Box Dolomite. The Black Dragon Member of the Triassic Moenkopi Formation will serve as the seal rock for the relatively buoyant CO2 stored in the underlying formations. The Black Dragon Member is comprised of four lithofacies: a chert pebble conglomerate; an interbedded sandstone, siltstone, and shale; a trough cross-stratified sandstone, and an oolitic and algal limestone. The Black Dragon Member has a maximum thickness of 280 ft (85 m) at Woodside field. Mudstone beds contain from 0.16 to 0.47% porosity. QEMSCAN analysis indicates several minerals within shale beds that may react with a CO2-rich brine including calcite (18.73 to 23.43%), dolomite (7.56 to 7.89%), alkali feldspar (4.12 to 4.43 %), glauconite (0.04 to 0.05%), and plagioclase (0.03 to 0.04%). Silty mudstones comprise 75% of this member at Black Dragon Canyon. Volumetric estimates for Woodside field were calculated based on the 10th, 50th, and 90th percent probabilities (P10, P50, and P90). The White Rim Sandstone is the primary target reservoir and has capacity to hold 2.2, 8.8, or 23.7 million metric tonnes (P10, P50, and P90 respectively) of CO2 within the structural closure of Woodside field. The Black Box Dolomite may hold 0.5, 1.8, or 4.5 million metric tonnes, respectively of additional CO2 within the structural closure of Woodside field. These two formations combined have the capacity to store up to 28.3 million metric tonnes (P90) of CO2.

<p> Inland degradational trends of coastal dolomite pavements (on the Amabel formation near Tobermory Ontario Map 1) were examined in three wave energy settings: passive, intermediate, and active shores. </p> <p>Six pavement property trends were examined to determine the effect of low fetch lengths (7-10 km - Ford 83) and long shallow wave approach (Map 1) on the break-up of passive coastal pavements (south-west Bear's Rump Island): vegetation cover , grike dimensions, fracturing, pitting, shattering and flaking, and soil and rubble depths. </p> <p> Detailed analysis of small scale surface solution features, "karren", was undertaken at five 1 m sample grids on the intermediate average fetch 70-90 km -Grosset 85) Cyprus Lake provincial park pavements. </p> <p> / Thesis / Bachelor of Arts (BA)

Environmental contamination issues related to phosphorus (P) in surface waters substantiates the need to identify minimally-sufficient P fertilization amounts for production of containerized nursery crops and better understand the effect of routine amendments (i.e., dolomite [DL] and micronutrient fertilizer [MF]) added to pine bark substrates on chemical fate of P fertilizer. Four studies were conducted to accomplish two overarching objectives: 1) determine the minimum P fertilization amount and corresponding pore-water P concentration needed to achieve maximal growth of common containerized nursery crops and 2) determine the effect of DL and MF amendments in pine bark on P retention during irrigation and P fractions in substrate pore-water. In a fertigation, greenhouse study, calculated lowest P-fertilizer concentration that sustained maximal growth in Hydrangea paniculata ‘Limelight’ (panicle hydrangea) and Rhododendron ‘Karen’ (azalea) was 4.7 and 2.9 mg·L⁻¹ , respectively, and shoot growth Ilex crenata ‘Helleri’ (holly) was the same when fertilized with 0.5 to 6.0 mg·L⁻¹ P. Porewater P concentrations corresponding with treatments that sustained maximal growth of panicle hydrangea, azalea and holly were as low as 0.6, 2.2 and 0.08 mg·L⁻¹ P, respectively. In a separate study, utilizing low-P controlled-release fertilizers (CRFs), shoot growth of Hydrangea macrophylla ‘P11HM-11’ (bigleaf hydrangea) produced in two ecoregions was maximal when fertilized with as little as 0.3 g CRF-P per 3.8-L container, a 50% P reduction from the industrystandard CRF. Holly required 0.2 or 0.4 g CRF-P depending on ecoregion. Mean pore-water P concentrations that corresponded with highest SDW were 0.8 and 1.2 mg·L⁻¹ for hydrangea and holly, respectively. When irrigating fallow pine bark columns containing CRF for 48 d, amending pine bark with DL and MF reduced orthophosphate-P (OP-P) leachate concentrations by ≈ 70%, most of which was retained within the substrate. In a greenhouse study, containerized Lagerstroemia ‘Natchez’ (crape myrtle) were grown for 91 d in pine bark containing CRF. In pine bark amended with DL and MF, pore-water OP-P and total P concentrations, measured approximately weekly, were reduced by, on average, 64% and 58%, respectively. Total dry weight values of plants grown with DL plus MF or MF-only were 40% higher than those grown with no amendments; however, tissue P amounts and relative P uptake efficiency were the same among plants in these three treatments. Therefore, sorption of OP-P by DL and MF reduced water-extractable OP-P but did not limit P uptake by plants. / Ph. D.

The problem facing the Tlokwe Local Municipality is that it is Constitutional and legislatively obliged to avoid and/or mitigate the impact of potential disasters within its boundaries, through the effective management of potential disaster risks and disasters. The lack of effective risk management tools is especially concerning in the context of the water catchment management of the Mooi River, which is the main water supply of the Tlokwe local Municipality. The Mooi River is exposed to many potential catchment related hazards that could affect the municipality of which the origins are both anthropogenic and natural. Although, many of the impacts on the catchment arise beyond the boundaries and the control of the municipality, this does not relieve the municipality from the responsibility to develop tools to manage the risks. The aim of the study is to assist in addressing the above stated problem through establishing the requirements for a conceptual model for an effective spatial information system that will assist the municipality in effectively managing the potential disaster risks and disasters that may arise in the Mooi River Catchment area that could impact on the Tlokwe Local Municiaplity. The aim gives rise to three-research questions that are formulated as research objectives that are used to identify the conceptual model requirements. The first is to identify and conceptualise the constitutional and legislative obligations in respect of disaster risk management in general and specifically those governing the disaster disk management in the water catchment area for the Mooi River. The study of this objective not only highlight the constitutional and legal obligations that the local municipality is subject to, but provides legislatives remedies that the local municipality can utilise to assist with disaster risks reduction. The second is to identify and conceptualise the generic hazards that are related to water catchment areas (including the related groundwater compartments) and those specific in the Mooi River catchment area. In this section, potential anthropogenic and natural hazards are listed, a methodology for risk and vulnerability analyses is provided, and a concise study of quaternary catchment C23D is provided. The third is to identify and conceptualize the requirements for an effective conceptual model of GIS for Disaster Risk Management in the Tlokwe Local Municipality. An overview of a GIS is provided. The essential components of a generic information system namely, people, software, hardware, procedures and processes, data and telecommunications or networks are discussed. The information and system requirements cumulating from the analyses of the three research questions, serve as the drivers of the goal, outcomes and transformation process of the system as well as the requirements for the conceptual model. In this section: a comparison of the Systems Development Life Cycle (SDLC), Framework for Applied Systems Thinking (FAST), problem solving and the phases addressed in this study; the identification of the conceptual model requirements; and a concise systems conceptualisation of an effective GIS is provided. As the, mini-dissertation focuses on the needs for a conceptual model, the additional activities required before the system can be implemented are identified and formulated as recommendation that provide the opportunity for future research. / M Development and Management, North-West University, Potchefstroom Campus, 2014