@phdthesis{Kopetzki2011,
  author    = {Kopetzki, Daniel},
  title     = {Exploring hydrothermal reactions : from prebiotic synthesis to green chemistry},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-52581},
  school      = {Universit{\"a}t Potsdam},
  year      = {2011},
  abstract  = {In this thesis chemical reactions under hydrothermal conditions were explored, whereby emphasis was put on green chemistry. Water at high temperature and pressure acts as a benign solvent. Motivation to work under hydrothermal conditions was well-founded in the tunability of physicochemical properties with temperature, e.g. of dielectric constant, density or ion product, which often resulted in surprising reactivity. Another cornerstone was the implementation of the principles of green chemistry. Besides the use of water as solvent, this included the employment of a sustainable feedstock and the sensible use of resources by minimizing waste and harmful intermediates and additives. To evaluate the feasibility of hydrothermal conditions for chemical synthesis, exemplary reactions were performed. These were carried out in a continuous flow reactor, allowing for precise control of reaction conditions and kinetics measurements. In most experiments a temperature of 200 °C in combination with a pressure of 100 bar was chosen. In some cases the temperature was even raised to 300 °C. Water in this subcritical range can also be found in nature at hydrothermal vents on the ocean floor. On the primitive earth, environments with such conditions were however present in larger numbers. Therefore we tested whether biologically important carbohydrates could be formed at high temperature from the simple, probably prebiotic precursor formaldehyde. Indeed, this formose reaction could be carried out successfully, although the yield was lower compared to the counterpart reaction under ambient conditions. However, striking differences regarding selectivity and necessary catalysts were observed. At moderate temperatures bases and catalytically active cations like Ca2+ are necessary and the main products are hexoses and pentoses, which accumulate due to their higher stability. In contrast, in high-temperature water no catalyst was necessary but a slightly alkaline solution was sufficient. Hexoses were only formed in negligible amounts, whereas pentoses and the shorter carbohydrates accounted for the major fraction. Amongst the pentoses there was some preference for the formation of ribose. Even deoxy sugars could be detected in traces. The observation that catalysts can be avoided was successfully transferred to another reaction. In a green chemistry approach platform chemicals must be produced from sustainable resources. Carbohydrates can for instance be employed as a basis. They can be transformed to levulinic acid and formic acid, which can both react via a transfer hydrogenation to the green solvent and biofuel gamma-valerolactone. This second reaction usually requires catalysis by Ru or Pd, which are neither sustainable nor low-priced. Under hydrothermal conditions these heavy metals could be avoided and replaced by cheap salts, taking advantage of the temperature dependence of the acid dissociation constant. Simple sulfate was recognized as a temperature switchable base. With this additive high yield could be achieved by simultaneous prevention of waste. In contrast to conventional bases, which create salt upon neutralization, a temperature switchable base becomes neutral again when cooled down and thus can be reused. This adds another sustainable feature to the high atom economy of the presented hydrothermal synthesis. In a last study complex decomposition pathways of biomass were investigated. Gas chromatography in conjunction with mass spectroscopy has proven to be a powerful tool for the identification of unknowns. It was observed that several acids were formed when carbohydrates were treated with bases at high temperature. This procedure was also applied to digest wood. Afterwards it was possible to fermentate the solution and a good yield of methane was obtained. This has to be regarded in the light of the fact that wood practically cannot be used as a feedstock in a biogas factory. Thus the hydrothermal pretreatment is an efficient means to employ such materials as well. Also the reaction network of the hydrothermal decomposition of glycine was investigated using isotope-labeled compounds as comparison for the unambiguous identification of unknowns. This refined analysis allowed the identification of several new molecules and pathways, not yet described in literature. In summary several advantages could be taken from synthesis in high-temperature water. Many catalysts, absolutely necessary under ambient conditions, could either be completely avoided or replaced by cheap, sustainable alternatives. In this respect water is not only a green solvent, but helps to prevent waste and preserves resources.},
  language  = {en}
}
@phdthesis{Kirchhecker2014,
  author    = {Kirchhecker, Sarah},
  title     = {Renewable imidazolium zwitterions as platform molecules for the synthesis of ionic liquids and materials},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-77412},
  school      = {Universit{\"a}t Potsdam},
  pages     = {136},
  year      = {2014},
  abstract  = {Following the principles of green chemistry, a simple and efficient synthesis of functionalised imidazolium zwitterionic compounds from renewable resources was developed based on a modified one-pot Debus-Radziszewski reaction. The combination of different carbohydrate-derived 1,2-dicarbonyl compounds and amino acids is a simple way to modulate the properties and introduce different functionalities. A representative compound was assessed as an acid catalyst, and converted into acidic ionic liquids by reaction with several strong acids. The reactivity of the double carboxylic functionality was explored by esterification with long and short chain alcohols, as well as functionalised amines, which led to the straightforward formation of surfactant-like molecules or bifunctional esters and amides. One of these di-esters is currently being investigated for the synthesis of poly(ionic liquids). The functionalisation of cellulose with one of the bifunctional esters was investigated and preliminary tests employing it for the functionalisation of filter papers were carried out successfully. The imidazolium zwitterions were converted into ionic liquids via hydrothermal decarboxylation in flow, a benign and scalable technique. This method provides access to imidazolium ionic liquids via a simple and sustainable methodology, whilst completely avoiding contamination with halide salts. Different ionic liquids can be generated depending on the functionality contained in the ImZw precursor. Two alanine-derived ionic liquids were assessed for their physicochemical properties and applications as solvents for the dissolution of cellulose and the Heck coupling.},
  language  = {en}
}
@misc{FaireyTimmermanSudoetal.2019,
  author    = {Fairey, Brenton J. and Timmerman, Martin Jan and Sudo, Masafumi and Tsikos, Harilaos},
  title     = {The role of hydrothermal activity in the formation of Karst-hosted manganese deposits of the Postmasburg Mn Field, Northern Cape Province, South Africa},
  series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {966},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-47330},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-473304},
  pages     = {30},
  year      = {2019},
  abstract  = {The Postmasburg Manganese Field (PMF), Northern Cape Province, South Africa, once represented one of the largest sources of manganese ore worldwide. Two belts of manganese ore deposits have been distinguished in the PMF, namely the Western Belt of ferruginous manganese ores and the Eastern Belt of siliceous manganese ores. Prevailing models of ore formation in these two belts invoke karstification of manganese-rich dolomites and residual accumulation of manganese wad which later underwent diagenetic and low-grade metamorphic processes. For the most part, the role of hydrothermal processes and metasomatic alteration towards ore formation has not been adequately discussed. Here we report an abundance of common and some rare Al-, Na-, K- and Ba-bearing minerals, particularly aegirine, albite, microcline, banalsite, s{\´e}randite-pectolite, paragonite and natrolite in Mn ores of the PMF, indicative of hydrothermal influence. Enrichments in Na, K and/or Ba in the ores are generally on a percentage level for most samples analysed through bulk-rock techniques. The presence of As-rich tokyoite also suggests the presence of As and V in the hydrothermal fluid. The fluid was likely oxidized and alkaline in nature, akin to a mature basinal brine. Various replacement textures, particularly of Na- and K- rich minerals by Ba-bearing phases, suggest sequential deposition of gangue as well as ore-minerals from the hydrothermal fluid, with Ba phases being deposited at a later stage. The stratigraphic variability of the studied ores and their deviation from the strict classification of ferruginous and siliceous ores in the literature, suggests that a re-evaluation of genetic models is warranted. New Ar-Ar ages for K-feldspars suggest a late Neoproterozoic timing for hydrothermal activity. This corroborates previous geochronological evidence for regional hydrothermal activity that affected Mn ores at the PMF but also, possibly, the high-grade Mn ores of the Kalahari Manganese Field to the north. A revised, all-encompassing model for the development of the manganese deposits of the PMF is then proposed, whereby the source of metals is attributed to underlying carbonate rocks beyond the Reivilo Formation of the Campbellrand Subgroup. The main process by which metals are primarily accumulated is attributed to karstification of the dolomitic substrate. The overlying Asbestos Hills Subgroup banded iron formation (BIF) is suggested as a potential source of alkali metals, which also provides a mechanism for leaching of these BIFs to form high-grade residual iron ore deposits.},
  language  = {en}
}
@article{FaireyTimmermanSudoetal.2019,
  author    = {Fairey, Brenton J. and Timmerman, Martin Jan and Sudo, Masafumi and Tsikos, Harilaos},
  title     = {The role of hydrothermal activity in the formation of Karst-hosted manganese deposits of the Postmasburg Mn Field, Northern Cape Province, South Africa},
  series = {Minerals},
  volume    = {9},
  journal   = {Minerals},
  number    = {7},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2075-163X},
  doi       = {10.3390/min9070408},
  pages     = {28},
  year      = {2019},
  abstract  = {The Postmasburg Manganese Field (PMF), Northern Cape Province, South Africa, once represented one of the largest sources of manganese ore worldwide. Two belts of manganese ore deposits have been distinguished in the PMF, namely the Western Belt of ferruginous manganese ores and the Eastern Belt of siliceous manganese ores. Prevailing models of ore formation in these two belts invoke karstification of manganese-rich dolomites and residual accumulation of manganese wad which later underwent diagenetic and low-grade metamorphic processes. For the most part, the role of hydrothermal processes and metasomatic alteration towards ore formation has not been adequately discussed. Here we report an abundance of common and some rare Al-, Na-, K- and Ba-bearing minerals, particularly aegirine, albite, microcline, banalsite, serandite-pectolite, paragonite and natrolite in Mn ores of the PMF, indicative of hydrothermal influence. Enrichments in Na, K and/or Ba in the ores are generally on a percentage level for most samples analysed through bulk-rock techniques. The presence of As-rich tokyoite also suggests the presence of As and V in the hydrothermal fluid. The fluid was likely oxidized and alkaline in nature, akin to a mature basinal brine. Various replacement textures, particularly of Na- and K- rich minerals by Ba-bearing phases, suggest sequential deposition of gangue as well as ore-minerals from the hydrothermal fluid, with Ba phases being deposited at a later stage. The stratigraphic variability of the studied ores and their deviation from the strict classification of ferruginous and siliceous ores in the literature, suggests that a re-evaluation of genetic models is warranted. New Ar-Ar ages for K-feldspars suggest a late Neoproterozoic timing for hydrothermal activity. This corroborates previous geochronological evidence for regional hydrothermal activity that affected Mn ores at the PMF but also, possibly, the high-grade Mn ores of the Kalahari Manganese Field to the north. A revised, all-encompassing model for the development of the manganese deposits of the PMF is then proposed, whereby the source of metals is attributed to underlying carbonate rocks beyond the Reivilo Formation of the Campbellrand Subgroup. The main process by which metals are primarily accumulated is attributed to karstification of the dolomitic substrate. The overlying Asbestos Hills Subgroup banded iron formation (BIF) is suggested as a potential source of alkali metals, which also provides a mechanism for leaching of these BIFs to form high-grade residual iron ore deposits.},
  language  = {en}
}
@phdthesis{Stoltnow2023,
  author    = {Stoltnow, Malte},
  title     = {Magmatic-hydrothermal processes along the porphyry to epithermal transition},
  doi       = {10.25932/publishup-61140},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-611402},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xxviii, 132},
  year      = {2023},
  abstract  = {Magmatic-hydrothermal systems form a variety of ore deposits at different proximities to upper-crustal hydrous magma chambers, ranging from greisenization in the roof zone of the intrusion, porphyry mineralization at intermediate depths to epithermal vein deposits near the surface. The physical transport processes and chemical precipitation mechanisms vary between deposit types and are often still debated. The majority of magmatic-hydrothermal ore deposits are located along the Pacific Ring of Fire, whose eastern part is characterized by the Mesozoic to Cenozoic orogenic belts of the western North and South Americas, namely the American Cordillera. Major magmatic-hydrothermal ore deposits along the American Cordillera include (i) porphyry Cu(-Mo-Au) deposits (along the western cordilleras of Mexico, the western U.S., Canada, Chile, Peru, and Argentina); (ii) Climax- (and sub-) type Mo deposits (Colorado Mineral Belt and northern New Mexico); and (iii) porphyry and IS-type epithermal Sn(-W-Ag) deposits of the Central Andean Tin Belt (Bolivia, Peru and northern Argentina). The individual studies presented in this thesis primarily focus on the formation of different styles of mineralization located at different proximities to the intrusion in magmatic-hydrothermal systems along the American Cordillera. This includes (i) two individual geochemical studies on the Sweet Home Mine in the Colorado Mineral Belt (potential endmember of peripheral Climax-type mineralization); (ii) one numerical modeling study setup in a generic porphyry Cu-environment; and (iii) a numerical modeling study on the Central Andean Tin Belt-type Pirquitas Mine in NW Argentina. Microthermometric data of fluid inclusions trapped in greisen quartz and fluorite from the Sweet Home Mine (Detroit City Portal) suggest that the early-stage mineralization precipitated from low- to medium-salinity (1.5-11.5 wt.\% equiv. NaCl), CO2-bearing fluids at temperatures between 360 and 415°C and at depths of at least 3.5 km. Stable isotope and noble gas isotope data indicate that greisen formation and base metal mineralization at the Sweet Home Mine was related to fluids of different origins. Early magmatic fluids were the principal source for mantle-derived volatiles (CO2, H2S/SO2, noble gases), which subsequently mixed with significant amounts of heated meteoric water. Mixing of magmatic fluids with meteoric water is constrained by δ2Hw-δ18Ow relationships of fluid inclusions. The deep hydrothermal mineralization at the Sweet Home Mine shows features similar to deep hydrothermal vein mineralization at Climax-type Mo deposits or on their periphery. This suggests that fluid migration and the deposition of ore and gangue minerals in the Sweet Home Mine was triggered by a deep-seated magmatic intrusion. The second study on the Sweet Home Mine presents Re-Os molybdenite ages of 65.86±0.30 Ma from a Mo-mineralized major normal fault, namely the Contact Structure, and multimineral Rb-Sr isochron ages of 26.26±0.38 Ma and 25.3±3.0 Ma from gangue minerals in greisen assemblages. The age data imply that mineralization at the Sweet Home Mine formed in two separate events: Late Cretaceous (Laramide-related) and Oligocene (Rio Grande Rift-related). Thus, the age of Mo mineralization at the Sweet Home Mine clearly predates that of the Oligocene Climax-type deposits elsewhere in the Colorado Mineral Belt. The Re-Os and Rb-Sr ages also constrain the age of the latest deformation along the Contact Structure to between 62.77±0.50 Ma and 26.26±0.38 Ma, which was employed and/or crosscut by Late Cretaceous and Oligocene fluids. Along the Contact Structure Late Cretaceous molybdenite is spatially associated with Oligocene minerals in the same vein system, a feature that precludes molybdenite recrystallization or reprecipitation by Oligocene ore fluids. Ore precipitation in porphyry copper systems is generally characterized by metal zoning (Cu-Mo to Zn-Pb-Ag), which is suggested to be variably related to solubility decreases during fluid cooling, fluid-rock interactions, partitioning during fluid phase separation and mixing with external fluids. The numerical modeling study setup in a generic porphyry Cu-environment presents new advances of a numerical process model by considering published constraints on the temperature- and salinity-dependent solubility of Cu, Pb and Zn in the ore fluid. This study investigates the roles of vapor-brine separation, halite saturation, initial metal contents, fluid mixing, and remobilization as first-order controls of the physical hydrology on ore formation. The results show that the magmatic vapor and brine phases ascend with different residence times but as miscible fluid mixtures, with salinity increases generating metal-undersaturated bulk fluids. The release rates of magmatic fluids affect the location of the thermohaline fronts, leading to contrasting mechanisms for ore precipitation: higher rates result in halite saturation without significant metal zoning, lower rates produce zoned ore shells due to mixing with meteoric water. Varying metal contents can affect the order of the final metal precipitation sequence. Redissolution of precipitated metals results in zoned ore shell patterns in more peripheral locations and also decouples halite saturation from ore precipitation. The epithermal Pirquitas Sn-Ag-Pb-Zn mine in NW Argentina is hosted in a domain of metamorphosed sediments without geological evidence for volcanic activity within a distance of about 10 km from the deposit. However, recent geochemical studies of ore-stage fluid inclusions indicate a significant contribution of magmatic volatiles. This study tested different formation models by applying an existing numerical process model for porphyry-epithermal systems with a magmatic intrusion located either at a distance of about 10 km underneath the nearest active volcano or hidden underneath the deposit. The results show that the migration of the ore fluid over a 10-km distance results in metal precipitation by cooling before the deposit site is reached. In contrast, simulations with a hidden magmatic intrusion beneath the Pirquitas deposit are in line with field observations, which include mineralized hydrothermal breccias in the deposit area.},
  language  = {en}
}