Die vorliegende Arbeit beschreibt die Ergebnisse der Synthese und Charakterisierung der Hochdruckphase von Aluminiumnitrid mit Kochsalzstruktur (rs-AlN). Die Versuche wurden mittels Schockwellensynthese unter Verwendung der „flyer-plate-Methode“ mit anschließender Probenrückgewinnung durchgeführt. Für verschiedene Aluminiumnitridpulver mit einer Ausgangsporosität k = rho_solid/rho_porous von 1,5 bis 2,5 wurde bei einem Druck von 15 bis 43 GPa die Phasenumwandlung von der Wurtzitstruktur (w-AlN) in die Kochsalzstruktur (rs-AlN) bewirkt. Es ist damit erstmals gelungen, rs-AlN mit dynamischen HP-HT-Methoden herzustellen und damit Probenmengen im Milligramm- bis Grammbereich zu erhalten. Dadurch ist es möglich Untersuchungen durchzuführen, die zur weiteren Erforschung und Charakterisierung des Materials beitragen sollen. Im Fokus liegen dabei insbesondere die Untersuchung der mechanischen, thermischen und chemischen Stabilität, um die Eignung des Materials zur Herstellung ultraharter Komposite zu evaluieren. Die geschockten Pulver bestehen aus einem Phasengemisch aus dem Ausgangsmaterial (w-AlN), der Hochdruckphase (rs-AlN), Aluminiumoxid und -oxynitriden, sowie amorphen Aluminiumhydroxiden. Die höchste Ausbeute an rs-AlN (~41 Ma% bei 2 mm Probenhöhe) kann bei Drücken von 24 GPa und einer Ausgangsporosität k von 2,1 erhalten werden. Anhand dem Auftreten verschiedener Al-O-N Phasen kann die Schocktemperatur für die einzelnen Versuche abgeschätzt werden (<1700 °C bis <2000 °C). Die Phasenumwandlung wird durch die Temperaturerhöhung aufgrund der Schockkompaktion der Pulver aktiviert. Als entgegenwirkender Prozess wurde die thermisch aktivierte Rückwandlung in die Niederdruckphase w-AlN aufgrund einer zu hohen Post-Schocktemperatur und einem zu langsamen Abkühlen der Probe postuliert. Daraus ergibt sich eine optimale Temperatur für den Versuchsaufbau von 1700 bis 1900 °C, bei der die höchsten rs-AlN Anteile beobachtet wurden. Eine Verringerung der Probenhöhe erhöht den Einfluss von Mehrfachreflektionen in der Probe und trägt damit zur Verbesserung der Umsetzung bei. Für drei Nanopulver (Kristallitgröße <25 nm) wurde die teilweise Umwandlung in die Kochsalzstruktur beobachtet, wohingegen für ein gröberes Nanopulver und ein Submikropulver (Kristallitgröße >45 nm) kein rs-AlN in den geschockten Proben nachgewiesen werden konnte. Es wird ein Stabilisierungsmechanismus der Kochsalzstruktur durch Kristallitgrößeneffekte vorhergesagt. Die Verringerung der Kristallitgröße führt zur Herabsetzung des Umwandlungsdrucks w-AlN -> rs-AlN. Es lässt sich daher schlussfolgern, dass für kleinere Partikel die Hochdruckmodifikation aufgrund der geringeren Entfernung vom chemischen Gleichgewicht bei Normalbedingungen stabilisiert werden kann, wohingegen für größere Kristallite die Rückwandlung in die Ausgangsphase geschieht. Weitere Stabilisierungsmechanismen wurden diskutiert. Mithilfe einer Rietveld-Verfeinerung der Röntgendiffraktogramme wurde die Gitterkonstante des rs-AlN mit a = 4,044 ± 0,001 Å und die Kristallitgröße mit 15,3 ± 0,2nm bestimmt. Die mittels hoch-aufgelöster Transmissionselektronenmikroskopie (TEM) bestimmte Kristallitgröße (10 bis 20 nm) ist in guter Übereinstimmung mit den Ergebnissen der Rietveld-Verfeinerung. Mit 27Al Kernspinresonanzspektroskopie (NMR) wurde die oktaedrische Al–N-Umgebung (AlN6) mit einer korrigierten chemischen Verschiebung von 2 ppm nachgewiesen. Anhand der IR-Spektren wird eine Al–N-Schwingungsbande des rs-AlN bei ca. 490 cm−1 vermutet. Dynamisch-thermische Untersuchungen zeigen, dass nanokristallines rs-AlN bei 600 °C beginnt zu Aluminiumoxid zu oxidieren und damit keine größere Beständigkeit im Vergleich zum w-AlN zeigt. Die thermisch aktivierte Rückwandlung des rs-AlN in die Niederdruckphase wurde ab 1200 °C (in Argon) bzw. 1100 °C (im Vakuum) bei einer Heizrate von 10 K/min beobachtet. Eine gute chemische Beständigkeit des Aluminiumnitrid mit Kochsalzstruktur gegenüber Wasser, Natronlauge und Säuren (HCl, H2SO4, H3PO4, HNO3 und Königswasser) wurde in Langzeit-Löslichkeitsversuchen nachgewiesen.:1. Einleitung 2. Grundlagen 3. Methoden und experimentelle Details 4. Ergebnisse 5. Diskussion 6. Schlussfolgerungen und Ausblick / In the present work the results of the synthesis and characterisation of the high-pressure phase of aluminium nitride with rocksalt structure (rs-AlN) are presented. The experiments were carried out with the flyer-plate-method with subsequently sample recovery. For different aluminium nitride powders with starting porosities k = rho_solid/rho_porous of 1.5 to 2.5 the phase transition from wurtzite structure (w-AlN) to the rocksalt structure (rs-AlN) was induced at a pressure of 15 to 43 GPa. This is to our knowledge the first succesful synthesis of rs-AlN with dynamic HP-HT methods. With this advance, samples in the milligram or gram range can be produced. Therefore further investigations to characterise the material are possible, especially the study of the mechanical, thermal and chemical stability to validate the potential for the production of ultrahard composites. The shocked samples consist of a phase mixture from the starting material (w-AlN), the high-pressure phase (rs-AlN), aluminium oxide and oxynitrides, as well as amorphous aluminium hydroxides. The highest yield of rs-AlN (~41 wt% at 2 mm sample height) can be obtained at a pressure of 24 GPa and a starting porosity k of 2.1. The shock temperature can be estimated by the formation of different Al-O-N phases (<1700 °C to <2000 °C). The phase transition is activated by the raise of temperature due to shock compression. A thermal activated reconversion to the low-pressure phase w-AlN caused by a high post-shock temperature and a slow cooling of the sample is postulated as a contrary process. This results in an optimum temperature of 1700 to 1900 °C for this set-up. A decrease of the sample height increases the influence of multiple reflections and therefore causes a better transformation. A partial conversion to rs-AlN was observed for three nanopowders (crystallite size <25 nm), whereas for a more coarse nanopowder and an submicronpowder (crystallite size >45 nm) no rs-AlN could be found in the shocked samples. A stabilisation mechanism of the rocksalt phase by crystallite size effects is predicted. The reduction of the crystallite size causes a decrease of the transition pressure for w-AlN -> rs-AlN. It can be concluded, that for smaller particles the high-pressure phase can be stabilised at ambient conditions on the basis of the smaller distance from equilibrium, whereas for larger particles the reconversion to the low-pressure phase occurs. By a Rietveld refinement of the X-ray diffractograms, the lattice constant of rs-AlN and the crystallite size was determined to be a = 4.044 ± 0.001 Å respectively 15.3 ± 0.2 nm. The crystallite size of rs-AlN (10 to 20 nm) determined with high-resolution transmission electron microscopy (TEM) is in good agreement with the results of the Rietveld refinement. The octahedral Al–Npolyhedral (AlN6) was demonstrated by 27Al nuclear magnetic resonance spectroscopy (NMR) with a corrected chemical shift of 2 ppm. Based on infrared spectroscopy (FTIR) an AlN vibration band at about 490 cm−1 is assumed. Dynamic thermal analysis show, that the rs-AlN starts to oxidise to alumina at 600 °C and thus have no greater resistance in comparison with w-AlN. The thermal activated reconversion of rs-AlN to the low-pressure phase starts at 1200 °C (in argon) respectively 1100 °C (under vacuum) at a heating rate of 10 K/min. The aluminium nitride with rocksalt structure shows a good chemical resistance against water, caustic soda and acids (HCl, H2SO4, H3PO4, HNO3 and aqua regia).:1. Einleitung 2. Grundlagen 3. Methoden und experimentelle Details 4. Ergebnisse 5. Diskussion 6. Schlussfolgerungen und Ausblick

Summary: Raman spectroscopy is a widely used method in geoscience fields. Using a portable Raman spectrometer is possible to identify different materials, Raman spectrometer will participate in the survey the Martian surface. Its use is widely applied in mineralogy. There was measured a set of dark, green and some bright minerals of different mineralogical system groups that have been assessed the applicability of the chosen detector excitation at 785 nm mainly off-road equipment. The obtained spectra were measured off-road equipment ahura at excitation 785 nm and laboratory equipment InVia Renishaw and there were used lasers at excitaion of 785 nm and 514 nm. It was set of these minerals: Prehnite, Sulphur, Tyrkenit (howlit), Pyroxene (diopside), Libethenite, Toutmaline (verdelite), Dioptas, Klinoklas, Langit, Jadeit, Pseudomalachit (ehlit), Actinolite, Epidote, Augite. Results are composed of field measurement device Ahura, with excitation 785 nm and laboratory apparatus Invite Renishaw excitations with 785 nm and 514 nm. Measured values are arranged in tables, where the measurements are compared with each other, including literature and reference graphically demonstrated in the form of spectra. Subsequently evaluated their measurability. Keywords: Raman spektroscopy, portable Raman spectrometer,...

Im Rahmen einer deutsch-australischen Forschungskooperation erfolgte im Südsommer 2001/2002 eine Expedition in die Amery-Oase (70°50’S, 68°00’E), die im Einzugsgebiet des Lambert-Gletscher/Amery-Schelfeis-Systems, dem größten ostantarktischen Eis-Drainagesystem, liegt. Von deutscher Seite wurden im Zuge der Geländekampagne erstmals lakustrine Sedimentsequenzen gewonnen, um die bislang wenig erforschte spätquartäre Klima- und Umweltgeschichte dieser rund 1800 km² großen eisfreien Region zu rekonstruieren. Die drei untersuchten Glazialseen Beaver, Radok und Terrasovoje unterscheiden sich sowohl deutlich in ihrer Größe, Bathymetrie und den hydrologischen Merkmalen sowie in ihren Sedimentabfolgen. <br><br> Einen Schwerpunkte dieser Doktorarbeit bildet die Rekonstruktion der Sedimentationsprozesse und des Ablagerungsmilieus sowie Untersuchungen zur Herkunft des detritischen Sedimentmaterials in den Seebecken. Der methodische Ansatz verfolgt die Charakterisierung der klastischen Sedimentfazies an Hand lithologisch-granulometrischer Merkmale sowie mineralogisch-geochemischer Analysen der Sedimentherkunft. Ein weiterer Schwerpunkt ist die Rekonstruktion der holozänen biogen gesteuerten Ablagerungsbedingungen im Terrasovoje-See, die Rückschlüsse auf den kurzfristigen postglazialen Klima- und Umweltwandel in der Amery-Oase gestattet. Dabei wurden mikrofazielle Untersuchungsmethoden und hochauflösende Elementscannermessungen angewandt. <br><br> Die klastische Sedimentherkunft in den drei Seen unterscheidet sich räumlich deutlich voneinander und spiegelt den komplexen geologischen Aufbau der Amery-Oase wider. Als Sedimentquellen konnten präkambrische Metamorphite, permotriassische Sedimentgesteine und tertiäre Lockersedimente identifiziert werden. Die Varibilität der Herkunftssignale ist zeitlich weniger deutlich als räumlich ausgeprägt und deutet auf relativ konstante Liefergebiete in den einzelnen Seen hin. <br><br> Das glaziolakustrine Ablagerungsmilieu der drei untersuchten Seen zeigt klare räumliche und zeitliche Unterschiede. In allen drei Seen setzen sich die älteren Sedimente aus grobkörnigem, häufig diamiktischem Material zusammen, während die jüngeren Sedimente aus feinkörnigen Laminiten bestehen. Die lithofazielle Zweiteilung in den Sedimentabfolgen deutet auf einen Rückzug der Gletscher und/oder einen Anstieg der Wassertiefen im Übergang von den grobkörnigen zu den feinkörnigen Ablagerungseinheiten hin. Die oberen feinkörnigen Kernabschnitte spiegeln in allen drei Seen die postglaziale lakustrine Sedimentation wider. Im Beaver-See wird die postglaziale Fazies durch laminierte klastische Stillwassersedimente repräsentiert, im Radok-See durch Turbiditsequenzen und im Terrasovoje-See durch Algenlaminite. <br><br> Abgesehen vom Terrasovoje-See ist die zeitliche Einordnung der Fazieswechsel auf Grund mangelnder Altersinformationen schwer erfassbar. Im Terrasovoje-See setzte die postglaziale Sedimentation um rund 12,4 cal. ka ein. Somit weisen die darunterliegenden glazigenen Klastika mindestens ein spätpleistozänes Alter auf. Die sedimentologischen Eigenschaften, Änderungen der Sedimentationsraten und organogene Zusammensetzung der postglazialen Biogenlaminite des Terrasovoje-Sees deuten auf Variationen der paläolimnologischen Bedingungen hinsichtlich Eisbedeckung, biologischer Produktivität, Wasserstand, Redoxbedingungen und Salinität hin, die mit regionalen holozänen Klimaänderungen in Verbindung gebracht werden können. Weitere Anhaltspunkte ergeben sich aus der Zusammensetzung und den Mächtigkeitsvariationen der Laminae, die generell aus Wechsellagerungen von Cyanobakterienmatten mit feinklastischen Lagen bestehen. Lagenzählungen der Laminae belegen Änderungen des Ablagerungsmilieus auf subdekadischen Zeitskalen, wobei zeitweilige jährliche Signale nicht ausgeschlossen werden können. Unter Berücksichtigung aller faziellen Indikatoren lässt sich aus der Sedimentabfolge des Terrasovoje-Sees ein frühholozänes Klimaoptimum zwischen 9 und 7 cal. ka sowie weitere Wärmephasen zwischen 3,2 und 2,3 cal. ka sowie 1,5 und 1,0 cal. ka ableiten. <br><br> Im Vergleich mit Eiskernarchiven und anderen Seesedimentabfolgen aus ostantarktischen Oasen zeigt sich, dass das Auftreten postglazialer Warmphasen nicht allenorts einem allgemein gültigen räumlich-zeitlichen Muster folgt. Die Ursachen hierfür liegen vermutlich in den lokalen geographischen Gegebenheiten. Es lässt sich daraus schliessen, dass die bisher vorliegenden Klimarekonstruktionen eher das Lokalklima an einem Untersuchungsstandort als das Großklima der Ostantarktis reflektieren. Daraus ergibt sich die Notwendigkeit weiterer Untersuchungen von antarktischen Klimaarchiven und Untersuchungsstandorten, um örtliche von überregionalen Klimasignalen besser unterscheiden zu können. / In the scope of a German-Australian research cooperation field work was conducted in the Amery Oasis (70°50’S, 68°00’E), situated in the Lambert Glacier/Amery Ice Shelf region, the largest East Antarctic ice drainage system. The German part comprised the retrieval of lacustrine sediment cores for the reconstruction of the late Quaternary development of the palaeoenvironment in the 1800 km² large ice-free region. The three studied glacial lakes Beaver, Radok, and Terrasovoje reveal marked differences in size, hydrology and their sedimentary inventory. The goals of this thesis were to infer the onset of depostion in the lacustrine basins and to characterize changes in the depositional environment in the course of glacial retreat and the postglacial climate development. The methodic approach followed the recognition of sedimentary facies variability and sediment sources by means of facies analysis and mineralogical-geochemical provenance analysis. Another aspect was the high-resolution reconstruction of postglacial biogenic sedimentary modes in Lake Terrasovoje that provide insights into the short-term Holocene palaeo-climatic and palaeoenvironmental development. <br><br> The origin of siliciclastics shows marked spatial differences between the lakes, reflecting the complex geological setting of the Amery Oasis. The main detrital sources comprise crystalline rocks of the East Antarctic craton, Permotriassic and Tertiary sedimentary rocks. The temporal variability of sediment provenance is less developed than the spatial pattern, pointing to relatively constant sediment sources through time in the respective lakes. <br><br> The glaciolacustrine depositional environment of the three lakes shows clear spatial and temporal contrasts. In all lakes, the older sediments are composed of coarse, partly diamictic lithologies, while the younger materials consist of fine-grained laminites. The twofold lithofacial pattern is related to regional glacial retreat at the boundary between both sedimentary units that reduced direct glacigenic sediment input. In the epishelf Lake Beaver, in addition, the effect of postglacial sea-level rise led also to the rise of lake level and shifted the study site towards a more distal position from the shore, away from the influence of coarse clastic sediment input. The upper sedimentary units of the three lakes are dominated by fine-grained sediments, which only occasionally include ice-rafted dropstones. The postglacial sediments comprise clastic stillwater laminites at Lake Beaver, finely laminated turbidites in Lake Radok, and algal laminites in Lake Terrasovoje. <br><br> Apart from Lake Terrasovoje the timing of the lithological change is hard to determine, because of missing age constraints. At Lake Terrasovoje, the postglacial sequence started at approximately 12.4 cal. ka BP, suggesting an late Pleistocene age for the underlying glacial sediments. Sedimentological features, changes in sedimentation rates, and the compositional variability of the organic-rich postglacial laminites in Lake Terrasovoje point to variations in the palaeolimnic environment in terms of ice cover, biological productivity, lake level, redox conditions, and salinity that can be related to the regional Holocene climate history. Further evidence arises from the structure, composition, and thickness variations of the laminae, which basically consist of alternations of algal mats (cyanobacteria) and fine-clastic layers. The counting of laminae couplets reveal changes in the depositional enviroment at sub-decadal time scales that partly might include annual layering. Under the consideration of all sedimentological facies indicators, the postglacial laminite sequence of Lake Terrasovoje documents an early Holocene climate optimum between 9 and 7 cal. ka as well as two warm spells between 3.2 and 2.3 cal. ka and 1.5 and 1.0 cal. ka, respectively. <br><br> In comparison with ice-core records and lake records from other East Antarctic ice-free regions, it becomes evident that the appearence of warm episodes does not follow a consistent spatial-temporal pattern. Common trends comprise the existence of an early Holocene climate optimum, as seen in the ice-core records and in the Amery Oasis, and several warm episodes in the middle to late Holocene that are often time-transgressive. The cause of this inconsistent pattern probably can be explained by local boundary conditions that affect the study sites, such as topography, maritime influences and the distance to glacial ice. Therefore, many climate reconstructions basically document local climate rather than overregional Antarctic climate. In conclusion, there is need for ongoing palaeoclimatic studies in East Antarctica and the establishment of a dense network of study sites to distinguish and validate local from overregional palaeoclimatic fingerprints.

No description available.

Thesis.

Techn. University, Diss., 2002--Berlin.

Clay minerals and pedogenic metal (oxyhydr)oxides (hereafter termed ‛oxides’) significantly affect organic carbon (OC) storage and persistence in soils. Although it is known from laboratory experiments that minerals have a high variability in their reactivity, there is still a lack of fundamental knowledge how changing mineral composition under natural soil conditions works. The frequently used clay content (soil particles < 2-μm) or the dithionite-citrate-bicarbonate extractable Fe (Fed) content do not allow a mechanistic explanation of the function of clay minerals and pedogenic metal oxides. This is due to the fact that a similar relative mineral composition cannot necessarily be derived from the clay content. Therefore, the overall objective of the thesis was to identify the influence of defined mineralogical combinations on OC content, stock, and persistence under forest and cropland. The study examined highly weathered acidic soils (mainly Acrisols) from the East Usambara Mountains in NE Tanzania. The long-term weathering of geologically similar crystalline material under a humid tropical climate has produced a uniform spectrum of pedogenic minerals. Nonetheless, differences in the relative compositions of kaolinite (Al2Si2O5(OH)4), gibbsite (γ-Al(OH)3), goethite (α-FeOOH) and hematite (α-Fe2O3) were identified for the investigated soils. The soils were classified according to their mineralogical composition, based on the content of aluminous clay (kaolinite and gibbsite) and pedogenic Fe oxides (goethite and hematite). The applied approach generated a range of 149–434 g kg–1 for aluminous clay, and a range of 21–101 g kg–1 for Fed. A significant loss of 1.3 kg C m–2 was observed for the top 0–10 cm under cropland in comparison to the near-natural forests. Both the OC content and its persistence were significantly affected by the mineralogical composition in the soils. The ‛low clay‒high Fe’ combination had a similar or significantly higher OC content under both land uses, whereas significantly lower OC contents were measured for the other combinations under cropland. A more distinct effect of the mineral composition was measured for the mineral-associated OC (MAOC) content, which was determined by density fractionation and defined as OC associated with the heavy fraction (HF). A MAOC content of 37.4 g C kg–1 was measured for the ‛low clay‒high Fe’ combination, while only 19.4 g C kg–1 was found for the ‛high clay‒high Fe’ combination under cropland in the 0–10 cm depth. The lower OC and MAOC contents were accompanied by a significantly higher content of soil particles < 2-μm for the latter combination. This clearly reveals that no causal relationship between the OC and MAOC contents with the clay content can be established unless the dominant mineral phases and their composition for the soil sample are known. Analysis of the soils in the mineralogical combinations showed that with similar mineralogy, the Fed / aluminous clay ratio can be used as a metric to evaluate OC and MAOC contents and the persistence against land-use change. No significant changes were measured in the investigated soils under land-use change from forest to cropland for ratio values between 0.44 and 0.56. Results from a conducted incubation experiment and chemical oxidation of mineral-bound OC supported this result. The separation of the HF material in defined grain-size fractions along the respective mineralogical combinations revealed that the siltHF and clayHF fractions make an almost identical contribution to the total MAOC storage under undisturbed soil conditions. Thus, the MAOC content of the entire HF is mainly explained by the different mass of the grain-sizes fractions. Of particular note is the variable effect of land-use change on MAOC contents in the siltHF and clayHF fractions. While the MAOC content of the clayHF fraction showed little variation between land uses, the MAOC content of the siltHF fraction tracked the contents of the entire HF fraction along the mineralogical combinations. This result implies that small microaggregates / mineral-clusters (< 63-μm) are modified in their properties by changing mineral composition, which has a direct impact on the persistence of MAOC. Soil structure analysis revealed a high amount of very stable macroaggregates of the soils along the mineralogical combinations with small, but significant differences under both land uses. The results showed that an aluminous clay content of > 250 g kg–1 combined with Fed content of < 60 g kg–1 (‛high clay‒low Fe’) had a significantly positive effect on macroaggregation. The opposite combination (‛low clay‒high Fe’) caused a significant decrease in aggregates > 4 mm under cropland, which, however, was not associated with a significant decrease of the aggregate related OC content. Thus, the macroaggregation was influenced by the mineralogical combinations, but this had no significant effect on the related OC content. Rather, it becomes clear that interactions between minerals were particularly important in mineral clusters > 2-μm and < 63-μm, which determined the significant impact on the total (MA)OC content along the mineralogical combinations. Further studies can follow this trajectory to extend the mechanistic understanding of OC and MAOC content and persistence for highly weathered soils in the humid tropics.:1. General introduction 1.1 Soils of the humid tropics and their dominant mineral phases 1.2 Influence of mineralogy on the formation of mineral-associated OM in highly weathered soils of the humid tropics 1.3 Aggregation in weathered soils of the humid tropics: formation and associated organic carbon content 1.5 Scientific goals, main objectives, and hypotheses 2. Methodology 2.1 Characterization of the study area and the sampling strategy 2.2 Analyses to characterize mineral phases, MAOC and aggregation of the selected mineralogical combinations 2.3 Data set and applied statistical methods 3. General results and discussion 3.1 Soil mineralogical properties of the selected aluminous clay and pedogenic Fe oxide combinations 3.2 Basic considerations on bulk OC stocks and effect of mineralogical combinations on bulk OC and MAOC content and persistence 3.3 Effect of mineralogy on aggregation and aggregate-related OC contents 4. Conclusion 5. References Part II – Scientific publications 1. Impact of land use on soil organic carbon stocks in the humid tropics of NE Tanzania 1.0 Abstract 1.1 Introduction 1.2 Material and Methods 1.2.1 Study area 1.2.2 Description of the investigated land uses 1.2.3 Sampling, processing and analysis of soil 1.3 Results 1.3.1 Soil characterization 1.3.2 Content and stocks of SOC to 100 cm depth (soil profile approach) 1.3.3 SOC stocks of diagnostic soil horizons compared to fixed depth increments (satellite approach) 1.3.4 Content of clay, dithionite- and oxalate-extractable Fe and Al, and relationships to SOC content 1.4. Discussion 1.4.1 Impacts of land use on SOC stocks and potential controls of SOC stabilization 1.4.2 Effects of sampling schemes on the analysis of SOC stocks 1.5 Conclusions 1.6 References 2. Iron oxides and aluminous clays selectively control soil carbon contents and stability in the humid tropics 2.0 Abstract 2.1 Introduction 2.2 Results and Discussion 2.2.1 Mineralogical and geochemical properties of soil mineralogical combinations 2.2.2 Dependence of bulk soil carbon on aluminous clay and pedogenic Fe oxides 2.2.3 Effects of aluminous clay and pedogenic Fe oxides on mineral-associated carbon 2.2.5 Chemical and biological resistance of bulk and mineral-associated carbon 2.3 Implications 2.4. Methods 2.4.1 Study area and soil sampling 2.4.2 Basic soil properties 2.4.3 Density fractionation 2.4.4 Aluminous clay and pedogenic Fe oxide contents 2.4.5 Total element contents and weathering indicators 2.4.6 X-ray diffraction (XRD) 2.4.7 Mössbauer spectroscopy 2.4.8 Specific surface area (SSA) 2.4.9 13C Nuclear Magnetic Resonance Spectroscopy 2.4.10 Wet chemical oxidation and soil respiration 2.4.11 Statistics and calculations 2.5 References 2.6 Supplementary material 3. Aluminous clay and pedogenic Fe oxides modulate aggregation and related carbon contents in soils of the humid tropics 3.0 Abstract 3.1 Introduction 3.2 Material and methods 3.2.1 Study area and soil sampling 3.2.2 Soil analyses 3.2.2.1 Basic soil properties and terminology of selected mineralogical combinations 3.2.2.2 Aggregate size distribution and aggregate stability 3.2.2.3 Statistics and calculations 3.3 Results 3.3.1 Mineralogical composition and general soil properties 3.3.2 Aggregate size distribution 3.3.3 Aggregate stability 3.3.4 Organic carbon in soils and aggregate size fractions 3.4 Discussion 3.4.1 Aggregation and aggregate stability as controlled by aluminous clay and pedogenic Fe oxides 3.4.2 Importance of aggregation for OC persistence – effects of aluminous clay and pedogenic Fe oxides 3.5 Conclusions 3.6 References 3.7 Supplementary material 4. Appendix Erklärung zur Eröffnung des Promotionsverfahrens

No description available.

Mining will remain indispensable for the foreseeable future. For millennia, our society has been exploring and exploiting mineral deposits. Consequently, most of the easily exploitable high-grade deposits, which were of primary interest given their obvious technical and economic advantages, have already been depleted. For the future, the mining sector will have to efficiently produce metals and minerals from low-grade orebodies with complex mineralogical and microstructural properties -- these are generally referred to as complex orebodies. The exploitation of such complex orebodies carries significant technical risks. However, these risks may be reduced by applying modelling tools that are reliable and robust. In a broad sense, modelling techniques are already applied to estimate the resources and reserves contained in a deposit, and to evaluate the potential recovery (i.e., behaviour in comminution and separation processes) of these materials. This thesis focusses on the modelling of recovery processes, more specifically mineral separation processes, suited to complex ores. Despite recent developments in the fields of process mineralogy and geometallurgy, current mineral separation modelling methods do not fully incorporate the available information on ore complexity. While it is well known that the mineralogical and microstructural properties of individual particles control their process behaviour, currently widely applied modelling methods consider only distributions of bulk particle properties, which oftentimes require much simplification of the particle data available. Moreover, many of the methods used in industrial plant design and process modelling are based on the chemical composition of the samples, which is only a proxy for the mineralogical composition of the ores. A modelling method for mineral separation processes suited to complex ores should be particle-based, taking into consideration all quantifiable particle properties, and capable of estimating uncertainties. Moreover, to achieve a method generalizable to diverse mineral separation units (e.g., magnetic separation or flotation) with minimal human bias, strategies to independently weight the importance of different particle properties for the process(es) under investigation should be incorporated. This dissertation introduces a novel particle-based separation modelling method which fulfills these requirements. The core of the method consists of a least absolute shrinkage and selection operator-regularized (multinomial) logistic regression model trained with a balanced particle dataset. The required particle data are collected with scanning electron microscopy-based automated mineralogy systems. Ultimately, the method can quantify the recovery probability of individual particles, with minimal human input, considering the joint influence of particle shape, size, and modal and surface compositions, for any separation process. Three different case studies were modelled successfully using this new method, without the need for case-specific modifications: 1) the industrial recovery of pyrochlore from a carbonatite deposit with three froth flotation and one magnetic separation units, 2) the laboratory-scale magnetic separation of a complex skarn ore, and 3) the laboratory-scale separation of apatite from a sedimentary ore rich in carbonate minerals by flotation. Moreover, the generalization potential of the method was tested by predicting the process outcome of samples which had not been used in the model training phase, but came from the same geometallurgical domain of a specific ore deposit. In each of these cases, the method obtained high predictive accuracy. In addition to its predictive power, the new particle-based separation modelling method provides detailed insights into the influence of specific particle properties on processing behaviour. To name a couple, the influence of size on the recovery of different carbonate minerals by flotation in an industrial operation; and a comparison to traditional methodologies demonstrated the limitation of only considering particle liberation in process mineralogy studies -- the associated minerals should be evaluated, too. Finally, the potential application of the method to minimize the volume of test work required in metallurgical tests was showcased with a complex ore. The approach developed here provides a foundation for future developments, which can be used to optimize mineral separation processes based on particle properties. The opportunity exists to develop a similar approach to model the comminution of single particles and ultimately allow for the full prediction of the recovery potential of complex ores.:1 Introduction 1 1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.2 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.3 State-of-the-art in particle-based separation models . . . . . . . . . . . 11 1.4 Moving forward . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 1.4.1 Particle data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 1.4.2 Mathematical tools required for the particle-based separation model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 1.4.3 Workflow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 1.5 Structure of the thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2 The method and its application to industrial operations 23 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.2 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.2.1 Assumptions and limitations . . . . . . . . . . . . . . . . . . . . 26 2.2.2 Data structure and required pre-treatment . . . . . . . . . . . . 27 2.2.3 Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 2.3 Demonstration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 2.3.1 Artificial test cases . . . . . . . . . . . . . . . . . . . . . . . . . 31 2.3.2 Real case study . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 2.4 Discussion and final considerations . . . . . . . . . . . . . . . . . . . . 39 3 The robustness of the method towards compositional variations of new feed samples 45 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 3.2 Generalization potential of current Particle-based Separation Model (PSM) methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 3.3 Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 3.3.1 Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 3.3.2 Dry magnetic separation tests . . . . . . . . . . . . . . . . . . . 53 3.3.3 Sample characterization . . . . . . . . . . . . . . . . . . . . . . 53 3.3.4 Particle-based separation models . . . . . . . . . . . . . . . . . 54 3.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 3.5 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 4 Flotation kinetics of individual particles 67 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68 4.2 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 4.2.1 Data collection . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 4.2.2 Cumulative recovery probability . . . . . . . . . . . . . . . . . . 72 4.2.3 Particle-based kinetic flotation model . . . . . . . . . . . . . . . 74 4.3 Demonstration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 4.3.1 Materials and methods . . . . . . . . . . . . . . . . . . . . . . . 75 4.3.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 4.4 Discussion and final thoughts . . . . . . . . . . . . . . . . . . . . . . . 80 5 Conclusions and outlook 85 5.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 5.2 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 Bibliography 89

Use of greisen - a rock mined primarily for (Sn-W) ore components - in sculpture and construction industry is typical for the Slavkovský les area and its surroundings. Material mined in the greisenized granite stock near Prameny for construction purposes was the source of stone used for a valuable Baroque sight - the Holy Trinity column in a nearby town of Teplá. Samples collected in the abandoned construction stone quarry were analysed for the study of properties of the original material mined in the locality Prameny. These samples were compared with the material collected from the monument in the pre-restoration research to prove the source locality of the original material. Provenance of the original material was determined on the basis of qualitative and quantitative petrographic and micro-structural characteristics. Micro-structural petrographic parameters of the studied samples were determined by the microscopic study using the Petrographic Image Analysis (PIA). Distribution of accessories and micro-structural characteristics were observed using the cathode-luminescence. Conventional index and mechanical parameters with respect to the use of the material in construction industry and sculpture were determined for the material collected in the abandoned quarry. Studied material collected in the...