The Early Jurassic coal samples for the study were obtained from CRA Exploration Pty Ltd. (CRAE), drilled in the Gairdner and Mintaja Blocks, Gairdner Range of the Hill River Area, northern Perth Basin, Western Australia. The area is located approximately 280 km north of Perth. The coal measures subcrop in a half- graben bounded by the Lesueur-Peron Fault in the west, and the Warradarge Fault in the east. The coal occurs within the shallow sequence of the Cattamarra Member which is also described as the Cattamarra Coal Measures of the Cockleshell Gully Formation.Six sub-seams of seam G, namely G1 to G6, from the six drill cores, were examined for petrological and geochemical investigation. The coal predominantly comprises of banded, dull banded, and dull lithotypes, with minor bright banded, bright and fusainous types. Based on maceral analyses, the dominant maceral groups are vitrinite and inertinite, whilst the exinite and mineral matter are in minor contents. The vitrinite content has a range between 47.2 % to 73.0 %, and it is composed mainly of telocollinite and desmocollinite. The inertinite is dominated by semifusinite, fusinite, and inertodetrinite, and it has a range from 10.4 % to 24.8 %. The exinite group varies between 7.2 % to 20.8 % in content, and it is represented by sporinite, cutinite, alginite and resinite. The mineral matter dominated by clays and pyrite, ranges between 4.5 % to 20.6 %. The microlithotype analyses shows that the vitrite plus clarite content varies from 47.0 % to 70.0 %, intermediates between 8.0% to 26.0 %, whilst inertite plus durite content is relatively low, varying from 6.55 % to 14.0 %. The maximum reflectance of vitrinite has a value between 0.47 % and 0.53 %, which represents rank at sub-bituminous level based on the Australian rank values and corresponding to the sub-bituminous A and B rank of the ASTM classification and ++ / to the metalignitous type of the Pareek classification. On the basis of carbon and hydrogen content, the coal is categorised as per-hydrous meta- to ortho-lignitous type. The trace elements As, B, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sr, Th, U, V, Y, Zn, and Zr, are spectrographically analysed in the coal ash. The B content in the coal supports the presence of marine influence during peat deposition in the basin.On the basis of lithotype, maceral, microlithotype, trace element distribution, pyrite and total sulphur in the coal, the depositional environment for coal and the coal measures, is interpreted as an upper to lower delta type within a regressive phase of marine transgression.

Mineral matter affect various coal properties as well as the yield and composition of products released during thermal processes. This necessitates investigation of the effect of the inherent minerals on the products derived during pyrolysis, as pyrolysis forms the basis of most coal utilisation processes. A real challenge in this research has been quantifying the changes seen and attributing these effects to specific minerals. Thus far it has been deemed impossible to predict product yields based on the mineral composition of the parent coal. Limited research regarding these aspects has been done on South African coal and the characterisation of pyrolysis products in previous studies was usually limited to one product phase. A novel approach was followed in this study and the challenges stated were effectively addressed. A vitrinite-rich South African coal from the Highveld coal field, was prepared to an undersize of 75 μm and divided into two fractions. HCl/HF acid washing reduced the ash yield from 14.0 wt% d.b. to 2.0 wt% d.b. (proximate analysis). Pyrolysis was carried out with the North-West University (NWU) Fischer Assay setup at 520, 750 and 900°C under N2 atmosphere and atmospheric pressure. The effect of acid washing and the addition of minerals on the derived pyrolysis products were evaluated. Acid washing led to lower water and tar yields, whilst the gas yields increased, and the char yields were unaffected. The higher gas yield can be related to increased porosity after mineral removal as revealed by Brunauer-Emmett-Teller (BET) CO2 adsorption surface area analysis of the derived chars. Gas chromatography (GC) analyses of the derived pyrolysis gases indicated that the acid washed coal fraction (AW TWD) derived gas contained higher yields of H2, CH4, CO2, C2H4, C2H6, C3H4, C3H6 and C4s when compared to the gas derived from the raw coal fraction (TWD). The CO yield from the TWD coal was higher at all final pyrolysis temperatures. Differences in gas yields were related to increased tar cracking as well as lower hydrogen transfer and de-hydrogenation of the acid washed chars. Analyses of the tar fraction by means of simulated distillation (Simdis), gas chromatography mass spectrometry (GC-MS) –flame ionization detection (–FID) and size exclusion chromatography with ultraviolet (SEC-UV) analyses, indicated that the AW TWD derived tars were more aromatic in nature, containing more heavier boiling point components, which increased with increasing final pyrolysis temperature. The chars were characterised by proximate, ultimate, X-ray diffraction (XRD), X-ray fluorescence (XRF), diffuse reflectance infrared Fourier-transform (DRIFT) and BET CO2 analyses. Addition of either 5 wt% calcite, dolomite, kaolinite, pyrite or quartz to the acid washed fraction (AW TWD) was done in order to determine the effect of these minerals on the pyrolysis products. These minerals were identified as the most prominent mineral phases in the Highveld coal used in this study, by XRD and quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) analyses. It was found that mineral activity decreased in the order calcite/dolomite>pyrite>kaolinite>>>quartz. Calcite and dolomite addition led to a decrease in tar yield, whilst the gas yields were increased. Markedly, increased water yields were also observed with the addition of calcite, dolomite and pyrite. Kaolinite addition led to increased tar, char and gas yields at 520°C, whilst the tar yield decreased at 750°C. Pyrite addition led to decreased tar and gas yields. Quartz addition had no noteworthy effect on pyrolysis yields and composition, except for a decrease in char yield at all final pyrolysis temperatures and an increased gas yield at 520°C. Regarding the composition of the pyrolysis products, the various minerals had adverse effects. Calcite and dolomite affected the composition of the gas, tar and char phases most significantly, showing definite catalytic activity. Tar producers should take note as presence of these minerals in the coal feedstock could have a significant effect on the tar yield and composition. Kaolinite and pyrite showed some catalytic activity under specific conditions. Model coal-mineral mixtures confirmed synergism between coal-mineral and mineral-mineral interactions. Although some correlation between the pyrolysis products derived from the model coal-mineral mixtures and that of TWD coal was observed, it was not possible to entirely mimic the behaviour of the coal prior to acid washing. Linear regression models were developed to predict the gas, tar and char yields (d.m.m.f.) with mineral composition and pyrolysis temperature as variables, resulting in R2 coefficients of 0.837, 0.785 and 0.846, respectively. Models for the prediction of H2, CO, CO2 and CH4 yields with mineral composition and pyrolysis temperature as variables resulting in R2 coefficients of 0.917, 0.702, 0.869 and 0.978, respectively. These models will serve as foundation for future work, and prove that it is feasible to develop models to predict pyrolysis yields based on mineral composition. Extending the study to coals of different rank can make the models universally applicable and deliver a valuable contribution in industry. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Mineral matter affect various coal properties as well as the yield and composition of products released during thermal processes. This necessitates investigation of the effect of the inherent minerals on the products derived during pyrolysis, as pyrolysis forms the basis of most coal utilisation processes. A real challenge in this research has been quantifying the changes seen and attributing these effects to specific minerals. Thus far it has been deemed impossible to predict product yields based on the mineral composition of the parent coal. Limited research regarding these aspects has been done on South African coal and the characterisation of pyrolysis products in previous studies was usually limited to one product phase. A novel approach was followed in this study and the challenges stated were effectively addressed. A vitrinite-rich South African coal from the Highveld coal field, was prepared to an undersize of 75 μm and divided into two fractions. HCl/HF acid washing reduced the ash yield from 14.0 wt% d.b. to 2.0 wt% d.b. (proximate analysis). Pyrolysis was carried out with the North-West University (NWU) Fischer Assay setup at 520, 750 and 900°C under N2 atmosphere and atmospheric pressure. The effect of acid washing and the addition of minerals on the derived pyrolysis products were evaluated. Acid washing led to lower water and tar yields, whilst the gas yields increased, and the char yields were unaffected. The higher gas yield can be related to increased porosity after mineral removal as revealed by Brunauer-Emmett-Teller (BET) CO2 adsorption surface area analysis of the derived chars. Gas chromatography (GC) analyses of the derived pyrolysis gases indicated that the acid washed coal fraction (AW TWD) derived gas contained higher yields of H2, CH4, CO2, C2H4, C2H6, C3H4, C3H6 and C4s when compared to the gas derived from the raw coal fraction (TWD). The CO yield from the TWD coal was higher at all final pyrolysis temperatures. Differences in gas yields were related to increased tar cracking as well as lower hydrogen transfer and de-hydrogenation of the acid washed chars. Analyses of the tar fraction by means of simulated distillation (Simdis), gas chromatography mass spectrometry (GC-MS) –flame ionization detection (–FID) and size exclusion chromatography with ultraviolet (SEC-UV) analyses, indicated that the AW TWD derived tars were more aromatic in nature, containing more heavier boiling point components, which increased with increasing final pyrolysis temperature. The chars were characterised by proximate, ultimate, X-ray diffraction (XRD), X-ray fluorescence (XRF), diffuse reflectance infrared Fourier-transform (DRIFT) and BET CO2 analyses. Addition of either 5 wt% calcite, dolomite, kaolinite, pyrite or quartz to the acid washed fraction (AW TWD) was done in order to determine the effect of these minerals on the pyrolysis products. These minerals were identified as the most prominent mineral phases in the Highveld coal used in this study, by XRD and quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) analyses. It was found that mineral activity decreased in the order calcite/dolomite>pyrite>kaolinite>>>quartz. Calcite and dolomite addition led to a decrease in tar yield, whilst the gas yields were increased. Markedly, increased water yields were also observed with the addition of calcite, dolomite and pyrite. Kaolinite addition led to increased tar, char and gas yields at 520°C, whilst the tar yield decreased at 750°C. Pyrite addition led to decreased tar and gas yields. Quartz addition had no noteworthy effect on pyrolysis yields and composition, except for a decrease in char yield at all final pyrolysis temperatures and an increased gas yield at 520°C. Regarding the composition of the pyrolysis products, the various minerals had adverse effects. Calcite and dolomite affected the composition of the gas, tar and char phases most significantly, showing definite catalytic activity. Tar producers should take note as presence of these minerals in the coal feedstock could have a significant effect on the tar yield and composition. Kaolinite and pyrite showed some catalytic activity under specific conditions. Model coal-mineral mixtures confirmed synergism between coal-mineral and mineral-mineral interactions. Although some correlation between the pyrolysis products derived from the model coal-mineral mixtures and that of TWD coal was observed, it was not possible to entirely mimic the behaviour of the coal prior to acid washing. Linear regression models were developed to predict the gas, tar and char yields (d.m.m.f.) with mineral composition and pyrolysis temperature as variables, resulting in R2 coefficients of 0.837, 0.785 and 0.846, respectively. Models for the prediction of H2, CO, CO2 and CH4 yields with mineral composition and pyrolysis temperature as variables resulting in R2 coefficients of 0.917, 0.702, 0.869 and 0.978, respectively. These models will serve as foundation for future work, and prove that it is feasible to develop models to predict pyrolysis yields based on mineral composition. Extending the study to coals of different rank can make the models universally applicable and deliver a valuable contribution in industry. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Lignite is still one of the most important energy sources in Germany. In 2017, \SI{24.4}{\percent} of the net electricity production was generated by lignite-fired power plants. The operation of lignite-fired boilers faces challenges such as emission control and slagging and fouling issues. Slagging and fouling issues are caused by inorganic constituents in the coal, also referred to as mineral matter. Mineral matter can be associated with the coal in three different ways: A mineral grain within the coal matrix is referred to as included. A mineral grain that is not asscociated with the organic material is referred to as excluded. In addition, there are inorganic elements that are organically associated with the coal matrix. Due to the reaction front in a burning char particle included particles experience temperatures that can be much higher than what excluded particles experience. Included mineral matter particles also have the potential to coalesce or to react with organically bound elements to form new mineral species Two methods were identified to determine the included and excluded mineral matter in a given coal sample: Float-and-sink analysis and computer controlled scanning electron microscopy (CCSEM). The float-and-sink analysis uses the differences in density between minerals and coal to separate excluded mineral particles from coal particles. CCSEM is an automated SEM-EDS process that allows to analyze a large number of coal particles in a given sample. The SEM uses image analysis to identify coal and mineral particles and to determine the mineral association. Both methods are applied to seven coal samples from three major lignite mining areas in Germany. The results show that in the investgated coals the excluded mineral matter fraction consists mainly of quartz, pyrite/marcasite, clay and gypsum, whereas the included mineral matter fraction is dominated by Ca-S rich minerals. The tendency of slagging and fouling is predicted for all coals on the basis of included and excluded mineral matter. Conventional slagging and fouling indices are applied to the bulk ash composition of the included and excluded fraction determined by float-and-sink analysis. In addition, the composition of individual mineral grains determined by CCSEM-analysis is considered. The slagging indices show significant differences between the included and excluded mineral matter, whereas the fouling indices are in the same range for both fractions. The liquid-to-ash ratio is determined for all coal samples with thermochemical equilibrium calculations. The different temperatures for included and excluded mineral matter are taken into account. All investigated coals show significant liquid-to-ash ratios in both included and excluded fractions. Combustion experiments were conducted with all seven coals at a laboratory-scale test rig for pulverized fuels at TU Dresden and/or at large-scale utility boilers. Ash particle samples collected with the particle-wire-mesh method show particles with mixed-phase composition. These particles are the result of coalescence of included mineral particles or the result of reactions between included mineral grains and organically associated elements. / Mineralische Bestandteile im Brennstoff sind mitverantwortlich für Verschmutzung- und Ver\-schlack\-ungsvorgänge in mit Braunkohle gefeuerten Kraftwerken. Sie werden durch den Verbrennungsprozess freigesetzt und können sich je nach Eigenschaft der Mineralien an verschiedenen Stellen eines Feuerungsprozesses ablagern. Es wird zwischen mit dem Kohlekorn verwachsenen (internen) mineralischen Partikeln und als eigenständige Partikel vorliegenden (externen) mineralischen Partikeln unterschieden. Weiterhin können anorganische Elemente organisch an die Kohlematrix gebunden sein. Mit der Kohlestruktur verwachsene, interne Partikel sind der Reaktionsfront des brennenden Kohlepartikels direkt ausgesetzt. Sie erfahren höhere Temperaturen als externe Partikel. Höhere Temperaturen fördern das Aufschmelzen der Partikel und beeinflussen so das Ablagerungspotential. Mehrere im Kohlekorn vorliegende mineralische Partikel können beim Abbrennen des Restkokses zu einem Partikel mit neuer chemischer Zusammensetzung verschmelzen. Auch Reaktionen mit den organisch gebundenen mineralischen Elementen sind möglich. Es gibt verschiedene Methoden zur Bestimmung der Bindungsart der Mineralien in der Kohle. Die Schwimm- und Sinkanalyse nutzt die unterschiedlich großen Dichten von externen mineralischen Partikeln, Kohlekörnern mit mineralischen Einschlüssen und reinen Kohlekörnern zur Trennung in einzelne Fraktionen. Eine weitere Methode ist die computergesteuerte Rasterelektronenmikroskopie (CCSEM), mit der die Verteilung mineralischer Partikel im Kohlekorn sowie deren Zusammensetzung bestimmt werden kann. Im Rahmen dieser Dissertation werden beide Methoden auf sieben Kohleproben aus den drei größten deutschen Braunkohleabbaugebieten angewendet. Die Anwendung der Schwimm- und Sinkanalyse und von CCSEM auf die ausgewählten Kohleproben zeigen, dass die externen mineralischen Partikel in den untersuchten deutschen Braunkohlen von Quarz dominiert werden. Weitere signifikante Bestandteile sind Pyrit/Markasit, Tone und Gips. Die internen Minerale werden von Ca-S-haltigen Mineralien dominiert. Das Verschmutzungs- und Verschlackungspotential der untersuchten Kohlen wird u.a. mit Hilfe von Kennzahlen bewertet. Die Kennzahlen zur Bewertung des Verschlackungspotentials zeigten deutliche Unterschiede zwischen der internen und externen mineralischen Fraktion. Die Verschmutzungskennzahlen liegen in ähnlichen Größenordnungen für beide Fraktionen. Ein weiteres Bewertungskriterium ist der Flüssigphasenanteil bei der maximalen Partikeltemperatur. Dieser wird auf der Basis des thermochemischen Gleichgewichts berechnet. Dabei wird berücksichtigt, dass interne und externe mineralische Partikel unterschiedliche maximale Temperaturen erfahren. Sowohl der interne mineralische Anteil, als auch der externen Anteil aller untersuchten Kohlen zeigt signifikante Flüssigphasenanteile. Mit allen in der Arbeit untersuchten Kohlen wurden Verbrennungsexperimente in einer Technikumsanlage zur Verbrennung staubförmiger Brennstoffe sowie in Großkraftwerken durchgeführt. Mit der Methode der Partikelgitternetzsonde gesammelte Aschepartikelproben zeigen, dass beim Verbrennungsvorgang Partikel mit einer Mischphasenzusammensetzung entstehen. Diese Partikel sind durch das Verschmelzen verschiedener interner Mineralien bzw. aufgrund von Reaktionen von internen Mineralien mit organisch gebundenen anorganischen Elementen entstanden.

Composted biosolids have been shown to enhance turfgrass establishment and growth more than fertilizer alone, but few studies have investigated the production of turfgrass using uncomposted biosolids. Increasingly employed treatment methods that generate pathogen-free, low pollutant-containing biosolids are creating alternative products for use in urban settings.  Understanding the effects of these uncomposted and alternative biosolids products on turfgrass culture and soil chemical and physical properties is essential to understanding the benefits these products may provide in sod production systems. The objectives of this study were to compare processing methods, application and N mineralization rates of two biosolids products and an inorganic fertilizer control for sod fertilization on 1) agronomic parameters related to turfgrass quality, 2) the amount of soil, C and P exported at harvest, and 3) chemical and physical properties of the soil following sod harvest as an indicator of the benefits of biosolids use. The study was conducted on a sod farm in Remington, Virginia on a silt loam Ashburn-Dulles complex from 2009 to 2012. The biosolids products were applied at estimated plant available nitrogen (PAN) rates of 98 kg N ha-1  (0.5X), 196 kg N ha-1 (1.0X) and 294 kg N ha-1  (1.5X) for a tall fescue (Festuca arundinacea Schreb. \'Rebel Exeda\' \'Rebel IV\' and \'Justice\')/ Kentucky bluegrass (Poa pratensis L. \'Midnight\') mixture. One biosolids product was an anaerobically digested dewatered cake applied at 15, 30.5 and 46 wet Mg ha-1. The second biosolids product was the same cake blended with wood fines applied at 17, 34 and 51 wet Mg ha-1. The biosolids treatments were compared to an inorganic fertilizer control that supplied 196 kg N ha-1 through three applications over the production cycle. There were no differences in establishment between the cake biosolids treatments and the inorganic fertilizer control, but all of the blended biosolids were slower to establish. Only the 1.0X and 1.5X PAN rates from the cake biosolids matched the inorganic fertilizer control in producing an acceptable quality sod in ten months. Lower nitrogen uptake between the blended biosolids treatments compared to the inorganic fertilizer control and lower although acceptable sod quality ratings at harvest of the 1.0X cake biosolids indicate our PAN estimates of 30% organic nitrogen mineralization overestimated the PAN for both materials. There were no differences in sod tensile strength between the 1.5X cake biosolids and inorganic fertilizer control. There were no differences in transplant rooting strength among all treatments. After repeat applications of biosolids, the 0.5X rates did not increase soil extractable phosphorus, while the 1.0X rates steadily increased soil extractable phosphorus at. The 1.0X and 1.5X biosolids rates increased soil organic matter content, but only the 1.5X rate of cake biosolids reduced soil bulk density and mineral matter export at harvest. Overall results indicate that the cake biosolids are an acceptable fertility alternative to inorganic fertilizer, and applications of biosolids for sod production can improve soil quality. Sod growers should consider using biosolids in a rotational system to offset rising production costs and improve production field soil quality. / Master of Science

The present study mainly focus on two parts: one was the optimization of FactSage calculation, compared with HT-XRD measurements on mineral matter behaviors during the heating of coal and blend ashes from 500 °C to 1000 °C in reducing atmosphere. The aim was to obtain the optimized input parameters and options for FactSage calculation, and the outputs should be as close as possible to HT-XRD results. The other was the application of FactSage on ash melting behaviors. Since the maximum temperature of HT-XRD measurement in laboratory was 1000 °C in reducing atmosphere, the optimized FactSage was applied to investigate the ash melting behaviors in temperature range between 600 °C and 1600 °C for coal, biomass and their blends. The FactSage calculation was optimized by investigations of several input parameters and options including the mass ratio of reactant gas amount to ash sample, solution species and compound solid species. The results obtained from the optimized calculation were much better to fit the mineral transformations measured by HT-XRD. However, there were still some differences between the results from optimized FactSage calculations and HT-XRD measurements. This is mainly due to the amorphous substances which occurred as solid phases and liquid slag in FactSage outputs but cannot be detected by HT-XRD. Besides, several factors, such as the diffusion, particle size distribution and so on, affect the actual measurements greatly but been neglected in thermodynamic calculations, which enhance the distinctions. In addition, the effects of atmosphere were investigated and the differences of mineral matter behaviors were mainly embodied in sulphur-rich minerals, iron-rich minerals and amorphous substance. For application of FactSage on ash melting behaviors, AFTs tests for coal, biomass and their blends were adopted, and the results were well investigated by ash chemical components analyzed by XRF and also equilibrium phases calculated by FactSage. Hemispheric temperature and flowing temperature were mainly dependent on the high melting point substances at high temperature, such as free CaO in HKN and SWC, SiO2 in WS and KOL. The sintering temperature was largely affected by alkali oxides, which could combine with other oxides to form low melting point substances. For blended ashes, AFTs of the blended ash of HKN and WS shown a V shape with WS addition mass ratio rising, and the minimum values of AFTs appeared at 50 wt.% WS addition. AFTs of KOL changed in a small scale when mixed with WS, due to their similar ash composition (high in SiO2). As the SWC ash contents is much less than HKN and KOL, it did not affect the AFTs much when blended with coals. Moreover, the biomass addition affection on the blended ashes AFTs were also well illustrated by the liquid phases mass fraction and also the mineral matter transformations calculated by FactSage.

Στην παρούσα διατριβή διερευνώνται οι διεργασίες που λαμβάνουν χώρα στο τυρφογενές στρώμα, έτσι ώστε να ανιχνευθούν οι μεταβολές των φυσικών, πετρογραφικών και χημικών χαρακτηριστικών των οργανικών ιζημάτων συναρτήσει των παραμέτρων τυρφογένεσης, όπως το κλίμα και οι τοπικές γεωλογικές συνθήκες. Απώτερο στόχο συνιστά η μοντελοποίηση παλαιοπεριβαλλόντων γένεσης των γαιανθράκων. Τέλος αξιολογείται η συμπεριφορά των ορυκτών, η γεωχημική συγγένεια και η κινητικότητα των ιχνοστοιχείων σε ενδεχόμενη αξιοποίηση της τύρφης για ενεργειακούς σκοπούς. Η έρευνα εστιάστηκε στους τυρφώνες Φιλίππων (Ν. Καβάλας) και Νησιού (Ν. Πέλλας) στη Βόρεια Ελλάδα και στον παράκτιο τυρφώνα του Κεριού (Ν. Ζακύνθου). Εξετάστηκαν τα ποιοτικά και ποσοτικά χαρακτηριστικά των οργανικών και ανοργάνων ιζημάτων που πληρούν τους τυρφώνες, αλλά και τα αντίστοιχα τυρφογενετικά φυτικά είδη, που αναπτύσσονται στους ενεργούς τυρφώνες Νησιού και Κεριού. Συγκεκριμένα πραγματοποιήθηκαν προσεγγιστική και στοιχειακή ανάλυση, ορυκτολογικοί προσδιορισμοί, εξέταση στιλπνών τομών με ηλεκτρονική μικροσκοπία σάρωσης, αναλύσεις τόσο της ανόργανης χημικής σύστασης (XRF, ICP/OES, ICP/MS), όσο και της οργανικής χημικής σύστασης (13C CP/MAS NMR, FTIR, py-GC/MS), όπως επίσης και ανθρακοπετρογραφικοί προσδιορισμοί. Αναφορικά με τους ορυκτολογικούς προσδιορισμούς εφαρμόστηκε μέθοδος πλήρους ποσοτικοποίησης των ορυκτών φάσεων με εφαρμογή περιθλασιμετρίας ακτίνων Χ σε ξηρό δείγμα, συνυπολογίζοντας την επίδραση του οργανικού υλικού. Αξιολογήθηκε επίσης η εφαρμογή περιθλασιμετρίας ακτίνων Χ σε υπολείμματα οξείδωσης της τύρφης. Οι τυρφώνες Φιλίππων και Νησιού συνιστούν παρόμοια περιβάλλοντα τυρφογένεσης, καθώς και οι δύο αναπτύσσονται σε ενδοηπειρωτικές λεκάνες, των οποίων η βύθιση ελέγχεται κυρίως από τεκτονικούς παράγοντες, με την ανάπτυξη παρόμοιων τυρφογενετικών φυτικών ειδών, όπως Cyperaceae και ειδικότερα το ασβεστόφιλο Cladium mariscus και διάφορα Carex spp., ενώ επηρεάζονται στη σύγχρονη εξέλιξή τους τουλάχιστον και οι δύο από καρστικούς υδροφόρους, συνιστώντας τοπογενείς ποωτυρφώνες, με κύριο μορφολογικό χαρακτηριστικό την παρουσία εξάρσεων (hummocks). Αντίθετα στο Κερί η τυρφογένεση αναπτύχθηκε σε παράκτιο περιβάλλον με τη βύθιση (δηλ. το πλημμύρισμα) να ελέγχεται τόσο από τεκτονικούς παράγοντες, όσο και από τις ευστατικές κινήσεις της θάλασσας, και το πεδίο χαρακτηρίζεται ως υφάλμυρος ποωτυρφώνας. Στο Κερί πέρα από ελόφυτα γλυκών νερών, αναπτύσσονται και είδη υφάλμυρων οικολογικών συνθηκών, όπως Scirpus maritimus και Juncus maritimus, λόγω της υφαλμύρινσης του υδροφόρου ορίζοντα. Με βάση τα χαρακτηριστικά τυρφογένεσης στους τρεις τυρφώνες τροποποιήθηκαν οι δείκτες φάσεων, που χρησιμοποιούνται στη γεωλογία γαιανθράκων, έτσι ώστε να αντανακλούν καλύτερα τις συγγενετικές διεργασίες στο ακρότελμα. Επιπρόσθετα περιγράφονται τόσο ποιοτικά, όσο και ποσοτικά τα χαρακτηριστικά των ιζημάτων στο τελματικό και το λιμνοτελματικό πεδίο, ενώ εκτιμάται επίσης και η πορεία της ενανθράκωσης των υπό μελέτη οργανογενών ιζημάτων, έτσι ώστε να εξαχθούν διαγνωστικές παράμετροι εφαρμογής στα παλαιοπεριβάλλοντα τυρφογένεσης. / The present study focuses on the processes taking place in the peatigenic layer (acrotelma), in order to trace the alteration of physical, chemical and petrographical features of the organic sediments in connection with the peat-forming factors. The ulterior aim is to propose a model for interpreting the coal-forming palaeoenvorinmental conditions. Finally, the mobility of the toxic trace elements is evaluated, in case of peat utilization for power generation in the future. Cores from the peatlands of Philippi (Prefecture of Kavala) and Nissi (Prefecture of Pella) in Northern Greece and of Keri (Zakynthos Island) in Southern Greece, were examined. The objective was to determine the qualitative and quantitative characteristics of the organogenic sediments hosted in the peatlands and additionally, of the peat-forming plants that grow on the surface of the Nissi and Keri mires. A series of laboratory examinations were performed on the collected samples, including proximate and ultimate analyses, mineralogical determinations by applying X-ray diffraction and SEM, inorganic geochemical analyses using XRF, ICP-OES and ICP-MS, organic geochemical analyses using 13C CP/MAS NMR, FTIR and py-GC/MS techniques and organic petrographical examinations on intact samples. Regarding the mineralogical determinations a method for full quantification of the mineral phases has been developed taking into account the pattern of the organic phases. Additionally the application of X-ray diffraction in oxidized peat residues has been evaluated. The Philippi and Nissi peatlands comprise similar peat-forming environments, since: (a) both developed in intermontane basins, the subsidence of which is controlled mainly by the tectonic activity, (b) Cyperaceae, mainly Cladium mariscus and various Carex spp., constitutes the main peat-forming plants, (c) whereas both are affected by karstic waters. They are fens for most of the peat accumulation period. On the contrary, in Keri the peat accumulation developed in a coastal environment due to paludification controlled both by the tectonic activity and the eustatic sea level changes, and the environment is characterized as a brackish mire, where additionally Scirpus maritimus και Juncus maritimus thrive. Taking in consideration the peat-forming features in the three studied peatlands the coal facies indices were modified in order to reflect more precisely the syngenetic processes in the acrotelma. Additionally a model is provided that describes both qualitatively and quantitatively the characteristics of the organogenic sediments deposited in the telmatic and the limnotelmatic fields. Furthermore, the coalification pathways of the studied sediments are interpreted, in order to obtain diagnostic parameters that can be applied to coal palaeoenvironmental studies.

The intermontane Ipswich Basin, which is situated 30km south-west of Brisbane, contains coal measures formed in the Late Triassic Epoch following a barren non-depositional period. Coal, tuff, and basalt were deposited along with fluvial dominated sediments. The Ipswich Coal Measures mark the resumption of deposition in eastern Australia after the coal hiatus associated with a series of intense tectonic activity in Gondwanaland during the Permo-Triassic interval. A transtensional tectonic movement at the end of the Middle Triassic deformed the Toogalawah Group before extension led to the formation of the Carnian Ipswich Coal Measures in the east. The Ipswich Coal Measures comprise the Brassall and Kholo Subgroups. The Blackstone Formation, which forms the upper unit of the Brassall Subgroup, contains seven major coal seams. The lower unit of the Brassall Subgroup, the Tivoli Formation, consists of sixteen stratigraphically significant coal seams. The typical thickness of the Blackstone Formation is 240m and the Tivoli Formation is about 500m. The coal seams of the Ipswich Basin differ considerably from those of other continental Triassic basins. However, the coal geology has previously attracted little academic attention and the remaining exposures of the Ipswich coalfield are rapidly disappearing now that mining has ceased. The primary aim of this project was to study the patterns of coal sedimentation and the response of coal seam characteristics to changing depositional environments. The coal accumulated as a peat-mire in an alluvial plain with meandering channel systems. Two types of peat-mire expansion occurred in the basin. Peat-mire aggradation, which is a replacement of water body by the peatmire, was initiated by tectonic subsidence. This type of peat-mire expansion is known as terrestrialisation. It formed thick but laterally limited coal seams in the basin. Whereas, peat-mire progradation was related to paludification and produced widespread coal accumulation in the basin. The coal seams were separated into three main groups based on the mean seam thickness and aerial distribution of one-meter and four-meter thickness contour intervals. Group 1 seams within the one-meter thickness interval are up to 15,000m2 in area, and seams within the four-meter interval have an aerial extent of up to 10,000m2. Group 1A contains the oldest seam with numerous intraseam clastic bands and shows a very high thickness to area ratio, which indicates high subsidence rates. Group 1B seams have moderately high thickness to area ratios. The lower clastic influx and slower subsidence rates favoured peat-mire aggradation. The Group 1A seam is relatively more widespread in aerial extent than seams from Group 1B. Group 1C seams have low mean thicknesses and small areas, suggesting short-lived peat-mires as a result of high clastic influx. Group 2 seams arebetween 15,000 and 35,000m2 in area within the one-meter interval, and between 5,000 and 10,000m2 within the four-meter interval. They have moderately high area to thickness ratios, indicating that peat-mire expansion occurred due to progressively shallower accommodation and a rising groundwater table. Group 3 seams, which have aerial extents from 35,000 to 45,000m2 within the one-meter thickness contour interval and from 10,000 to 25,000m2 within the four-meter interval, show high aerial extent to thickness ratios. They were deposited in quiet depositional environments that favoured prolonged existence of peat-mires. Group 3 seams are all relatively young whereas most Group 1 seams are relatively old seams. All the major fault systems, F1, F2 and F3, trend northwest-southeast. Apart from the West Ipswich Fault (F3), the F1 and F2 systems are broad Palaeozoic basement structures and thus they may not have had a direct influence on the formation of the much younger coal measures. However, the sedimentation patterns appear to relate to these major fault systems. Depocentres of earlier seams in the Tivoli Formation were restricted to the northern part of the basin, marked by the F1 system. A major depocentre shift occurred before the end of the deposition of the Tivoli Formation as a result of subsidence in the south that conformed to the F2 system configuration. The Blackstone Formation depocentres shifted to the east (Depocentre 1) and west (Depocentre 2) simultaneously. This depocentre shift was associated with the flexural subsidence produced by the rejuvenation of the West Ipswich Fault. Coal accumulation mainly occurred in Depocentre 1. Two types of seam splitting occurred in the Ipswich Basin. Sedimentary splitting or autosedimentation was produced by frequent influx of clastic sediments. The fluvial dominant depositional environments created the random distribution of small seam splits. However, the coincidence of seam splits and depocentres found in some of the seams suggests tectonic splitting. Furthermore, the progressive splitting pattern, which displays seam splits overlapping, was associated with continued basin subsidence. The tectonic splitting pattern is more dominant in the Ipswich Basin. Alternating bright bands shown in the brightness profiles are a result of oscillating water cover in the peat-mire. Moderate groundwater level, which was maintained during the development of the peat, reduced the possibility of salinisation and drowning of the peat swamp. On the other hand, a slow continuous rise of the groundwater table, that kept pace with the vertical growth of peat, prevented excessive oxidation of peat. Ipswich coal is bright due to its high vitrinite content. The cutinite content is also high because the dominant flora was pteridosperms of Dicroidium assemblage containing waxy and thick cuticles. Petrographic study revealed that the depositional environment was telmatic with bog forest formed under ombrotrophic to mesotrophic hydrological conditions. The high preservation of woody or structured macerals such as telovitrinite and semifusinite indicates that coal is autochthonous. The high mineral matter content in coal is possibly due to the frequent influx of clastic and volcanic sediments. The Ipswich Basin is part of a much larger Triassic basin extending to Nymboida in New South Wales. Little is known of the coal as it lacks exposures. It is apparently thin to absent except in places like Ipswich and Nymboida. This study suggests that the dominant control on depocentres of thick coal at Ipswich has been the tectonism. Fluvial incursions and volcanism were superimposed on this.

Coals, from mines in the Highveld coalfield, as well as gasification ash samples were characterised, in order to understand the mineralogical and chemical properties of the individual components in the gasification feedstocks. X-ray diffraction of low temperature oxygen-plasma ash indicates that the coals contain significant proportions of kaolinite, quartz and a fluxing elements-bearing mineral (dolomite), plus minor concentrations of illite and other fluxing elements-bearing minerals namely calcite, pyrite and siderite. Of the feed coal, the -75+53 mm size fraction has a high pyrite, and to a lesser extent a high calcite and dolomite content. However, the small proportion of iron-bearing phases (from the reaction between kaolinite and pyrite) in samples taken from the gasifier implies that pyrite contributes minimally to sintering or slagging in this case. Calcite is mainly present in the >1.8 g/cm3 density fraction of the feed coal, whereas dolomite is mainly present in the 1.5-1.8 g/cm3 density fraction, as inclusions or fine cleats in the coal matrix. Electron microprobe analyses of coals from the six different South African mines confirmed that some Ca, Mg, Al, Si, Na, K, Ti and Fe are present in the organic matrix in the coal samples tested in this study, but the amounts of these are small compared with the fluxing elements in minerals. XRD and microprobe analyses indicate that the ash clinker samples taken from the gasifiers contain a number of crystalline high temperature phases, including anorthite, mullite, cristobalite, quartz and diopside. FactSage confirmed that anorthite and mullite are equilibrium phases at elevated temperatures in the ash clinkers and heated rock fragments. Limited reaction takes place between the included coal minerals and the extraneous rock fragments. / Thesis (PhD)--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / unrestricted