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- Institut für Integrierte Naturwissenschaften, Abt. Chemie (22) (remove)
Thousands of chemicals from daily use are being discharged from civilization into the water cycle via different pathways. Ingredients of personal care products, detergents, pharmaceuticals, pesticides, and industrial chemicals thus find their way into the aquatic ecosystems and may cause adverse impacts on the ecology. Pharmaceuticals for instance, represent a central group of anthropogenic chemicals, because of their designed potency to interfere with physiological functions in organisms. Ecotoxicological effects from pharmaceutical burden have been verified in the past. Therapeutic groups with pronounced endocrine disrupting potentials such as steroid hormones gain increasing focus in environmental research as it was reported that they cause endocrine disruption in aquatic organisms even when exposed to environmentally relevant concentrations. This thesis considers the comprehensive investigation of the occurrence of corticosteroids and progestogens in wastewater treatment plant (WWTP) effluents and surface waters as well as the elucidation of the fate and biodegradability of these steroid families during activated sludge treatment. For the first goal of the thesis, a robust and highly sensitive analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed in order to simultaneously determine the occurrence of around 60 mineralocorticoids, glucocorticoids and progestogens in the aquatic environment. A special focus was set to the compound selection due to the diversity of marketed synthetic steroids. Some analytical challenges have been approved by individual approaches regarding sensitivity enhancement and compound stabilities. These results may be important for further research in environmental analysis of steroid hormones. Reliable and low quantification limits are the perquisite for the determination of corticosteroids and progestogens at relevant concentrations due to low consumption volumes and simultaneously low effect-based trigger values. Achieved quantification limits for all target analytes ranged between 0.02 ng/L and 0.5 ng/L in surface water and 0.05 ng/L to 5 ng/L in WWTP effluents. This sensitivity enabled the detection of three mineralocorticoids, 23 glucocorticoids and 10 progestogens within the sampling campaign around Germany. Many of them were detected for the first time in the environment, particularly in Germany and the EU. To the best of our knowledge, this in-depth steroid screening provided a good overview of single steroid burden and allowed for the identification of predominantly steroids of each steroid
type analyzed for the first time. The frequent detection of highly potent synthetic steroids (e.g. triamcinolone acetonide, clobetasol propionate, betamethasone valerate, dienogest, cyproterone acetate) highlighted insufficient removal during conventional Summary wastewater treatment and indicated the need for regulation to control their emission since the steroid concentrations were found to be above the reported effect-based trigger values for biota. Overall, the study revealed reliable environmental data of poorly or even not analyzed steroids. The results complement the existing knowledge in this field but also providednew information which can beused particularly for compound prioritization in ecotoxicological research and environmental analysis. Based on the data obtained from the monitoring campaign, incubation experiments were conducted to enable the comparison of the biodegradability and transformation processes in activated sludge treatment for structure-related steroids under aerobic and standardized experimental conditions. The compounds were accurately selected to cover manifold structural moieties of commonly used glucocorticoids, including non-halogenated and halogenated steroids, their mono- and diesters, and several acetonide-type steroids. This approach allowed for a structure-based interpretation of the results. The obtained biodegradation rate constants suggested large variations in the biodegradability (half-lifes ranged from < 0.5 h to > 14 d). An increasing stability was identified in the order from non-halogenated steroids (e.g. hydrocortisone), over 9α-halogenated steroids (e.g. betamethasone), to C17-monoesters (e.g. betamethasone 17-valerate, clobetasol propionate), and finally to acetonides (e.g. triamcinolone acetonide), thus suggesting a strong relationship of the biodegradability with the glucocorticoid structure. Some explanations for this behavior have been received by identifying the transformation products (TPs) and elucidating individual transformation pathways. The results revealed the identification of the likelihood of transformation reactions depending on the chemical steroid structure for the first time. Among the identified TPs, the carboxylates (e.g. TPs of fluticasone propionate, triamcinolone acetonide) have been shown persistency in the subsequent incubation experiments. The newly identified TPs furthermore were frequently detected in the effluents of full-scale wastewater treatment plants. These findings emphasized i) the transferability of the lab-scale degradation experiments to real world and that ii) insufficient removals may cause adverse effects in the aquatic environment due to the ability of the precursor steroids and TPs to interact with the endocrine system in biota. For the last goal, the conceptual study for glucocorticoids was applied to progestogens.
Here, two sub-types of the steroid family frequently used for hormonal contraception were selected (17α-hydroxyprogesterone and 19-norstestosterone type). The progestogens showed a fast and complete degradation within six hours, and thus empathizes pronounced biodegradability. However, cyproterone acetate and dienogest Summary have been found to be more recalcitrant in activated sludge treatment. This was consistent with their ubiquitously occurrence during the previous monitoring campaign. The elucidation of TPs again revealed some crucial information regarding the observed behavior and highlighted furthermore the formation of hazardous TPs. It was shown that 19-nortestosterone type steroids are able to undergo aromatization at ring A in contact with activated sludge, leading to the formation of estrogen-like TPs with a phenolic moiety at ring A. In the case of norethisterone the formation of 17α-ethinylestradiol was confirmed, which is a well-known potent synthetic estrogen with elevated ecotoxicological potency. Thus, the results indicated for the very first time an unknown source of estrogenic compounds, particularly for 17α-ethinylestradiol. In conclusion, some steroids were found to be very stable in activated sludge treatment, others degrade well, and others which do degrade but predominantly to active TPs depending on their chemical structure. Fluorinated acetal steroids such as triamcinolone acetonide and fluocinolone acetonide are poorly biodegradable, which is reflected in high concentrations detected ubiquitously in WWTP effluents. Endogenous steroids and their most related synthetic once such as hydrocortisone, prednisolone or 17α-hydroxyprogesterone are readily biodegradable. Regardless their high influent concentrations, they are almost completely removed in conventional WWTPs. Steroids between this range have been found to form elevated quantities of TPs which are partially still active, which particularly the case for betamethasone, fluticasone propionate, cyproterone acetate or dienogest. The thesis illustrates the need for an extensive evaluation of the environmental risks and carried out that corticosteroids and progestogens merit more attention in environmental regulatory and research than it is currently the case
Bauxite is, among other raw materials, an important material for the production of refractories. However, the availability of refractory raw material grades is limited worldwide. As high iron contents have a negative influence on the temperature resistance of the refractory material produced, a maximum iron oxide content of 2 wt.-% in the bauxite is acceptable. This means that only native raw materials from a few deposits can be used. In order to counteract the problem of too high iron oxide contents in natural bauxites, the possibility of processing bauxite for the refractory industry by using an acid leaching process was to be investigated within the scope of this work. In previous studies on this topic, some investigations on iron leaching have already been carried out on individual bauxites. However, the resulting bauxite composition was mostly neglected in its entirety and only the influences of individual leaching parameters on the leaching result were investigated independently. Moreover, the results and procedures generated are not generally valid and cannot be transferred to bauxites of other chemical or mineralogical compositions.
In order to clarify the open questions in the processing of natural bauxites, leaching tests with hydrochloric acid were carried out on five different bauxites within this work. By using computerized statistical design of experiments, an individual model was generated for each bauxite to predict the optimal factor settings. The factors investigated were acid concentration, solid-acid ratio, leaching temperature, leaching time and grain fraction. The general planning method for bauxite processing developed in this context contains all necessary factors, useful factor settings and the effects to be considered during planning and evaluation. It could be shown that, based on this planning method, a significant, individual model can be created for each of the bauxites investigated, which predicts the optimal leaching settings for the corresponding bauxite. Furthermore, it was found that the transfer of an already created model to another bauxite of similar composition is possible. Based on the results obtained from the leaching tests and model fittings, in combination with further results on the structural analysis of the bauxites, insights into the leachability of various aluminium and iron minerals from bauxite could be gained.
To develop a sustainable acid leaching process, the possibility of regenerating the contaminated acid produced was also tested as an example. It was shown that liquid-liquid extraction can extract more than 99 % of the iron present in the solution and that the regenerated acid can then be reused for the leaching process.
The sediments of surface waters are temporary or final depository of many chemical compounds, including trace metals and metalloids (metal(loid)s) from natural and anthropogenic sources. Whether they act as a source or sink of metal(loid)s depends strongly on the dynamics of the biogeochemical processes that take place at the sediment-water interface (SWI). Important information on biogeochemical processes as well as on the exposure, the fate and the transport of pollutants at the SWI can be obtained by determining chemical concentration profiles in the sediment pore water. A major challenge is to conduct experiments with a spatial resolution, which allows to adequately record existing gradients and to log all the parameters needed, to describe and better understand the complex processes at the SWIs. At the same time, it is from major importance to prevent the formation of any artifacts during sampling, which may occur due to the labile nature of the SWIs and the very steep biogeochemical gradients.
In this context, in the first part of this work, a system was developed and tested that enables the automated, minimal invasive sampling of sediment pore water of undisturbed or manipulated sediments while simultaneously recording parameters such as redox potential, oxygen content and pH value. In an incubation experiment the impact of acidification and mechanical disturbance (re-suspension) on the mobility of 13 metal(loid)s was investigated using a triple quadrupole inductively coupled plasma-mass spectrometry (ICP-QQQ-MS) multi-element approach. Most metals were released as consequence of sulfide weathering whereas mechanical disturbance had a major impact on the mobility of the oxide forming elements As, Mo, Sb, U and V. Additionally, options were demonstrated to address with the system the size fractionation of metal(loid)s in pore water samples and the speciation of As(III/V) and Sb(III/V).
In the second part, the focus, with a similar experimental design, was placed on the processes leading to the release of metal(loid)s. For this purpose, two incubation experiments with different oxygen supply were conducted in parallel. For the first time the nonmetals carbon, phosphorus and sulfur were analyzed simultaneous to 13 metal(loid)s in sediment pore water by ICP-QQQ-MS. Throughout the experiment metal(loid) size fractionation was monitored. It was confirmed that resuspension promotes the mobility of metalloids such as As, Sb and V, while the release of most metals was largely attributed to pyrite weathering. The colloidal (0.45-16 μm) contribution in terms of mobilization was only relevant for a few elements.
Finally, the sampling system was used as part of a new approach to sediment risk assessment. Undisturbed sediment cores from differently contaminated positions in the Trave estuary were examined, considering 16 metal(loid)s, the non-metals C, P and S and the ions NH4+, PO43- and SO42-. By the first in-depth comparison with in-situ dialysis-based pore water sampling the ability of the suction-based approach to represent field conditions was proven. The pore water studies together with supplementing resuspension experiments in bio-geochemical microcosms and sequential extraction identified the most “pristine” sediment of the study area as posing the greatest risk of metal(loid) release. However, the potentially released amounts per kg of sediment are only a few parts per thousand of the average daily loads of the Trave river.
Key mechanisms for the release of metal(loid)s from a construction material in hydraulic engineering
(2017)
Hydraulic engineering and thus construction materials are necessary to enable the navigability of water ways. Since, a variety of natural as well as artificial materials are used, this materials are world wide tested on a potential release of dangerous substances to prevent adverse effects on the environment. To determine the potential release, it is important to identify and to understand key mechanisms which are decisive for the release of hazardous substances. A limited correlation between the conditions used in regulatory tests and those found in environmental systems is given and hence, often the significance of results from standardised tests on construction materials is questioned, since they are not designed to mimic environmental conditions.
In Germany industrial by-products are used as armour stones in hydraulic engineering. Especially the by-product copper slag is used during the last 40 years for the construction of embankments, groynes and coastal protection. On the one hand, this material has a high density and natural resources (landscape) are protected. One the other hand, the material contains high quantities of metal(loid)s. Therefore the copper slag (product name: iron silicate stones) is very suitable as test material. Metal(loid)s examined were As, Sb and Mo as representatives for (hydr)oxide forming elements and Cd, Co, Cu, Fe, Ni, Pb and Zn were studied as representatives for elements forming cations during the release.
Questions addressed in this Thesis were: (i) can we transfer the results from batch experiments to construction scenarios under the prevalent environmental conditions, (ii) which long-term trends exist for the release of metal(loid)s from copper slags and (iii) how environmental conditions influence the leaching of metal(loid)s from water construction materials?
To answer the first question the surface depending release of the metal(loid)s from the construction materials was examined. Therefore, batch leaching experiments with different particle sizes and a constant liquid/solid ratio were performed. In a second step a comparison between different methods for the determination of the specific surface area of armour stones with a 3D laser scanning method as a reference were performed. In a last step it was possible to show that via a roughness factor the results of the specific surface area from small stones, measured with gas adsorption, can be connected with the results from armour stones, determined with an aluminium foil method. Based on calculations of the specific surface area, it was possible to significantly improve catchment scale calculation about the release of metal(loid)s and to evaluate a potential impact of construction materials in hydraulic engineering on the water chemistry of rivers and streams.
To answer the second question long-term leaching diffuse gradient in thin films supported experiments were performed for half a year. Diffuse gradients in thin films (DGT) is an in situ method to passive sample metal(loid)s in water, sediments and soils. They were used as a sink for metal(loid)s in the eluate to provide solution equilibriums. Thus the exchange of the eluent, which is performed normally in long-term experiments, was superfluous and long-term effects under undisturbed conditions were studied. The long-term leaching experiments with DGT have proven to be capable (i) to differentiate between the depletion of the material surface and the solution equilibriums and (ii) to study sorption processes with or without a further release of the analytes. This means for the practically relevant test material copper slag that: (i) the cations Cd, Co, Cu, Ni and Pb are confirmed to be released from the slag over the whole time period of six months, (ii) a surface depletion of Zn was detected, and (iii) that the (hydr)oxide forming elements As, Mo and Sb were released from the slag over the hole periods of six months but the release was masked by adsorption to Fe-oxide colloids, which were formed during the leaching experiments. It was confirmed, that sulphide minerals are the main source for long-term release of Cd, Cu, Ni, Pb and Mo.
To answer the third question short-term leaching experiments simulating environmental conditions in hydraulic engineering were performed. One factor is the salinity. The influence of this parameter was tested in batch experiments with sea salt solution (30 g/l), river Rhine water, ultra pure water and in addition with different NaCl concentration (5, 10, 20 and 30 g/l). In general, the ionic strength is an important factor for the metal(loid) release but the composition of the water (e.g. the HCO3- content) may superimpose this effect. Therefore, the concentrations of the metal(loid)s in the experiments with ultra-pure water spiked with sea salt or native river water and the ultra-pure water spiked with NaCl were significantly different. In a second experiment the influence of the environmental parameters and the interactions between the environmental parameters pH (4–10), sediment content (0 g–3.75 g), temperature (4 °C–36 °C) and ionic strength (0 g/l–30 g/l NaCl) on the release of metal(loid)s from the test material was examined. The statistical Design of Experiments (DoE) was used to study the influence of these factors as well as their interactions. All studied factors may impact the release of metal(loid)s from the test material to the eluent, whereas the release and the partitioning between sediment and eluate of metal(loid)s was impacted by interactions between the studied factors. The main processes were sorption, complexation, solubility, buffering and ion exchange. In addition, by separating the sediment from the slag after the experiments by magnetic separation, the enrichment of metal(loid)s in the sediment was visible. Thus, the sediment was the most important factor for the release of the metal(loid)s, via pH, temperature and ionic strength, because the sediment acted as a sink.
Die Biopolyester Cutin und Suberin stellen hydrophobe Grenzbarrieren dar, die sich im Laufe der Evolution der Landpflanzen entwickelt haben. Cutin bildet den Hauptbestandteil der Cuticula, die den Pflanzen Schutz vor unkontrollierter Transpiration bietet. Die Einlagerung von Suberin in die Zellwände definierter Zellen des Wurzelgewebes ermöglicht eine kontrollierte Aufnahme von Wasser und Nährstoffen. Zu den wichtigsten monomeren Bestandteilen dieser biologischen Polyester gehören langkettige α,ω-Dicarbonsäuren und ω-Hydroxycarbonsäuren. Bisher wurde der mikrobielle Abbau der Makromoleküle unzureichend erforscht. Zur Entschlüsselung der Zersetzung ist es notwendig, den Kreislauf der monomeren Bestandteile im Boden zu betrachten. Hierzu eignen sich vor allem Experimente mit positionsspezifisch ¹³C -markierten α,ω-Dicarbonsäuren und ω-Hydroxycarbonsäuren, die in der vorliegenden Arbeit erstmals synthetisch zugänglich gemacht wurden. Die Synthesen umfassten Dicarbonsäuren der geradzahligen Kettenlängen C12 bis C30, deren Carboxygruppen ¹³C -markiert sind. Ebenfalls wurde die Synthese von ω-Hydroxycarbonsäuren der Kettenlängen C14, C18, C22 und C30 mit ¹³C-Markierung an der Carboxygruppe realisiert. Weitere Zielverbindungen waren ω-Hydroxycarbonsäuren der Kettenlängen C14, C15, C18, C22 und C30, deren terminales hydroxyliertes Kohlenstoffatom mit ¹³C markiert ist. Im Rahmen der durchgeführten Arbeit gelang es, alle 19 Zielcarbonsäuren erfolgreich in hohen Ausbeuten und Reinheiten darzustellen. Die Synthese der isotopenmarkierten Verbindungen erforderte die Entwicklung spezieller auf die jeweiligen Zielsubstanzen individuell angepasster Syntheserouten, die den Einbau des Kohlenstoffisotops ¹³C ermöglichten. Für alle Zielverbindungen erfolgte die Einführung des ¹³C durch die Verwendung von ¹³C -markiertem Kaliumcyanid (99 at%). Wegen der hohen Kosten des ¹³C -markierten Ausgangsstoffes wurden alle Reaktionen zunächst unter der Verwendung analoger unmarkierter Edukte optimiert. Der letzte Teil der Arbeit bestand in der Ausführung eines Inkubationsexperimentes mit den ¹³C -markierten α,ω-Dicarbonsäuren der Kettenlängen C12, C18, C22 und C30. Mittels Phospholipidfettsäure-Analyse konnte gezeigt werden, dass die ¹³C -Dicarbonsäuren zu unterschiedlichen Anteilen von verschiedenen Mikroorganismengruppen zum Aufbau von Phospholipidfettsäuren verwendet wurden. Außerdem konnte durch die Anreicherung des CO2 mit dem Isotop ¹³C nachgewiesen werden, dass die ¹³C -markierten Fettsäuren von den Mikroorganismen zur Energiegewinnung abgebaut wurden. Für zukünftige Arbeiten wäre es interessant, Ausschnitte der Cutin- und Suberinstruktur nachzubilden. Durch die Veresterung der ¹³C -markierten α,ω-Dicarbonsäuren und der ¹³C -markierten ω-Hydroxycarbonsäuren untereinander oder mit Alkoholen könnten Dimere und Oligomere hergestellt werden.
In der vorliegenden Arbeit wird das thermochemische Wechselwirkungsverhalten verschiedener Magnesiakohlenstoffmaterialen in Abhängigkeit verschiedener Einflussgrößen wissenschaftlich untersucht. Schwerpunkte der experimentellen Arbeiten bilden thermoanalytische Experimente, Gefügeuntersuchungen der Magnesiakohlenstoff-Proben sowie thermodyna-mische Berechnungen und Auswertungen durch CAT (Computer Aided Thermochemistry) mittels des Softwarepakets FactSage.
Erster Themenbereich dieser Arbeit ist die Untersuchung des Einflusses der in dem Rohstoff Magnesia enthaltenen mineralogischen Nebenphasen Merwinit (C3MS2), Monticellit (CMS) und Belit (C2S) auf den carbothermisch induzierten Verschleiß im MgO-C-Material. Für die Messreihen wurden die Nebenphasen eigens synthetisiert und hiermit MgO-C-Nebenphase-Modellwerkstoffe hergestellt. Die Nebenphase Monticellit ist unbeständig gegenüber der carbothermischen Reduktion. Monticellit wird im MgO-C-Gefüge durch Kohlenstoff reduziert und hieraus ergibt sich ein erhöhter Gewichtsverlust des Probenmaterials. Auch Merwinit wird bei T = 1600°C reduziert, der Gewichtsverlust wird dadurch allerdings nicht erhöht. Belit ist im MgO-C-Gefüge stabil gegenüber carbothermischer Reduktion.
Ein weiterer Schwerpunkt der Arbeit lag auf der Untersuchung des Einflusses des klassischen Antioxidans Aluminium auf die thermochemische Stabilität von MgO-C. Bei geringen Sauerstoffpartialdrücken ist die Reaktion des Aluminium-Metalls bzw. des bereits zu Al4C3 carbidisierten Aluminiums mit dem steineigenen Periklas unter Mg(g)-Bildung möglich, was einen erhöhten Gewichtsverlust zur Folge hat. Aber auch nach der Oxidation zu Al2O3 bzw. Spinell liegt Aluminium in signifikanten Mengen als Al(g) und Al2O(g) in der Gasphase vor und greift des Weiteren die Nebenphasen an, was ebenfalls zu einem messbaren Gewichtsverlust führt.
Dritter Arbeitsschwerpunkt war die Untersuchung des Einflusses des Umgebungsdruckes auf die carbothermische Reduktion von MgO. Die Ergebnisse zeigen, dass der Druck sich in zweierlei Hinsicht auf die carbothermische Reduktion von MgO auswirkt. Zum einen bewirkt ein sinkender Umgebungsdruck eine Beschleunigung der carbothermischen Reduktion durch die Verschiebung des thermodynamischen Gleichgewichts auf die Produktseite. Des Weiteren sorgt er für einen schnelleren Abtransport der Produktgase vom Reaktionsort und ver-hindert somit die Einstellung eines lokalen Gleichgewichts im Gefüge. Dritter Effekt ist die mit steigendem Druck verstärkt ablaufende Kohlenstoffoxidation durch Umgebungssauerstoff, da die Sauerstoffmenge in der Umgebung des MgO-C-Materials vom Umgebungsdruck bestimmt wird. Für die Geschwindigkeit des thermochemischen Verschleißes von Magnesiakohlenstoffmaterialien, der immer eine Kombination aus Kohlenstoffoxidation und carbothermischer Reduktion darstellt, bedeutet dies, dass sie in Abhängigkeit vom Umgebungsdruck in unterschiedlichem Ausmaß von diesen beiden Reaktionen beeinflusst wird.
Identifizierung und Quantifizierung von Mikroplastik mittels quantitativer ¹H-NMR Spektroskopie
(2021)
Plastic, and so microplastics (MP), are globally present and represent an increasingly significant problem for the environment. In order to understand the distribution and impact of MP it is important to identify and quantify MP over a wide range of sizes and to ensure comparability of studies. However, comparability of studies is made difficult or even impossible by different MP concentration data. There still is a great need for research in the field of size-independent, quantitative analysis of MP in environmental samples, especially with regard to mass-based MP concentration information. Therefore, this thesis aims to utilize quantitative ¹H-NMR spectroscopy (qNMR) as an alternative method in MP analysis. The qNMR method is a size-independent, mass-based method which can be used as an alternative for MP analysis and has potential for routine analysis. The proof-of-concept was demonstrated for LDPE, PET and PS particles (Chapter 2). Additionally, PVC, PA, and ABS particles were tested to cover the most important polymer types for MP-analysis (Chapter 3). Moreover, using PET, PVC and PS as examples it was examined whether the qNMR method can also be transferred to the more cost-effective NoD method (Chapter 4). Results of method validation of both methods (1D and NoD) show that quantification using the qNMR method is not only possible in principle, but also shows high accuracy (88.0-110 %) and detection limits (1 – 84 µg) that lie within the environmentally relevant range. Furthermore, it was examined whether not only high-field instruments are suitable for MP analysis, but also benchtop devices (low-field instruments), which are much more cost-effective in purchase and maintenance. Increasing measurement times for PET and PS to 30 min and for PVC to 140 min, the lower measuring frequency especially concerning resolving capacity could be compensated (Chapter 4). To address the question of potential matrix effects of environmental samples, matrix effects and recovery rates of sample preparation procedures, which have been developed specifically for the application of the qNMR method were investigated using PET fibers as an example (Chapter 5). It could be shown that environmental matrices do not interfere with the quantitative analysis of MP using qNMR methods. Specific sample preparation methods developed for qNMR analysis can be used with recovery rates > 80 % for different environmental matrices (Chapter 5). Finally, first orienting investigations for the simultaneous determination of several polymer types in one sample are reported (Chapter 6).
In the present dissertation, the structural interaction between potassium waterglass and aluminium metaphosphates (aluminium tetrametaphosphate and aluminium hexametaphosphate) were investigated in terms of the resettlement behaviour of the metaphosphates as hardening agents. The crystalline phase composition was described qualitatively and quantitatively in terms of powder diffraction patterns combined with Rietveld refinement. The amorphous phase content was determined by different spectroscopic methods (e.g. solid-state NMR, ATR-IR, and Raman spectroscopy). The solubility behaviour of the chemical hardening agents was investigated by optical emission spectroscopy and electron absorption spectroscopy. The mechanical properties of the samples were measured by three-point bending tests, resonance damping frequency analysis, and acid test. The structural framework of the chemically hardened waterglasses was explored by scanning electron microscopy method. It could be proven, that the reaction mechanism of the resettlement is strongly dependent on the structure of the aluminium metaphosphate. After the dissolution of the aluminium ions of aluminium tetrametaphosphate through the alkalic environment of the potassium waterglass, a potassium tetrametaphosphate is developed through an ion-exchange reaction with the waterglass` potassium ions. In the hexametaphosphate system, no analogous structure could be proven. Parallel to the ion-exchange reaction an incremental depolymerization of the cyclic metaphosphate structure to the final crystalline product potassium dihydrogen phosphate occurs. The drop in pH value due to the addition of the respective aluminium metaphosphate initiates a polycondensation of the potassium waterglass due to the decreasing stabilization of the waterglass. This process is increased by the depolymerization products of the metaphosphate, that remove further quantities of the alkali ions, which accelerates the polycondensation reaction due to a further decrease in pH value. The dissolved aluminium ions from the aluminium metaphosphate penetrate into the amorphous, hardening silica network and develops an alumosilicate binder matrix. Furthermore, amorphous hydrated aluminium phosphate phases develop in separate domains beside silicate, alumosilicate phases, and the crystalline phase contents e.g. potassium dihydrogenphosphate and the incomplete reacted aluminium metaphosphate. Consequently, the chemically hardened potassium waterglass binder is not necessarily homogenous. Regarding the mechanical and chemical properties, in summary with increasing alkali modulus the mechanical flexural strength, and the young modulus drop, while the chemical resistance towards acid attack, and the porosity of the samples increase. The change in the cyclic structure from aluminium tetrametaphosphate to aluminium hexametaphosphate leads to a drop in the acid resistance, the porosity of the samples, the flexural strength, and the young modulus.
The present study deals with the synthesis of N-phenacylpyridinium salts and their use as photoinitiators for epoxy resins. The use and suitability of phenacyl salts as photoinitiators for epoxy resins has already been described in previous studies. The individual impact of the specific components on the rate constants of epoxy reaction has not been investigated in detail. Based on the structure of N-phenacylpyridinium salt the substances described in the present study were varied due to the exchange of counter ion and different substituents. Investigating the impact of the specific substituent with focus on the reaction of epoxy groups there is a dependence found for three main factors. First, depending on whether to use a phenyl or methyl group as substituent there was found an impact on the process of photolysis. Furthermore, concerning the dependences on the pyridine derivative and the counter ion, it was found that pyridine derivatives with electron withdrawing groups and counter ions, which can build strong acids, accelerate the rate constants of the epoxy reaction. Vice versa, pyridine derivatives with electron donating groups and counter ions, which can form weaker acids, decrease the rate constants.
The determined rate constants and the formulation of substances discussed in the present thesis in an adhesive formulation show the suitability of selected substances as photoinitiators for the polymerization of epoxy resins.
Investigating the environmental fate of iodinated X-ray contrast media in the urban water cycle
(2010)
Iodinated X-ray contrast media (ICM) are a group of emerging contaminants which have been detected at elevated concentrations in the aquatic environment. These compounds are excreted unmetabolized into hospital wastewater, and eventually treated at wastewater treatment plants (WWTPs). The removal of ICM in WWTPs has not been very effective and therefore the ICM enter the aquatic environment via WWTP effluent discharges. Research has investigated the removal of selected ICM via abiotic and biotic processes, however limited work has attempted to determine the fate of these compounds once released into the environment. This thesis investigates the biotransformation of four selected ICM (diatrizoate, iohexol, iomeprol, and iopamidol) in aerobic soil-water and sediment-water systems as well as in different environmental matrices. Iohexol, iomeprol and iopamidol were biotransformed to several TPs in the aerobic batch systems, while no biotransformation was observed for the ionic ICM, diatrizoate. In total 34 biotransformation products (TPs) of the three non-ionic ICM were identified. The combination of semi-preparative HPLC-UV, hybrid triple quadrupole-linear ion trap mass spectrometry (Qq-LIT-MS) was found to be an accurate approach for the structural elucidation of ICM TPs. The ICM TPs resulted in microbial transformation occurring at the side chains of the parent ICM, with the iodinated aromatic ring unmodified.