Doctoral Thesis
Refine
Year of publication
Document Type
- Doctoral Thesis (22) (remove)
Keywords
- Aluminiumorthophosphat (1)
- Arzneimittel (1)
- Bauxit (1)
- Biotransformation (1)
- Bororthophosphat (1)
- Cloud Point Extraction (1)
- Depth Profile (1)
- Ecotoxicity (1)
- Environmental organic chemistry (1)
- Environmental samples (1)
Institute
- 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
Modellbildung zum Abbindeverhalten von PCE-verflüssigten und CA-Zement-gebundenen Feuerbetonen
(2021)
Feuerbetone werden als Auskleidung in industriellen Hochtemperaturaggregaten, wie beispielsweise in der Eisen- und Stahlindustrie, eingesetzt. Nach dem Mischen und dem Gießen eines Feuerbetons in Formen bzw. Schalungen, muss dieser abbinden und eine ausreichende Festigkeit ausbilden. Die Kinetik der Abbindevorgänge und somit auch das Erhärtungsverhalten variiert dabei stark in Abhängigkeit der Zusammensetzung, vor allem hinsichtlich des Bindemittels und der Additive, des Feuerbetons. In der Praxis der Herstellung von Feuerbetonen kommt es häufig zu Beschädigungen der hergestellten Bauteile oder Auskleidungen durch das Fließen noch nicht ausreichend abgebundener Feuerbetone bzw. die Beschädigung von Ecken und Kanten während des Ausschalens oder Bauteilen reißen durch mechanische Belastung beim Umsetzen oder beim Transport. Diese Beschädigungen basieren auf Fehleinschätzungen zum Abbindefortschritt und der korrespondierenden Festigkeitsausprägung der Feuerbetone. Diese wiederum sind auf Lücken im Stand der Technik zurück zu führen.
Für PCE-verflüssigte und CA-Zement-gebundene Korund-Feuerbetonen mit einer Al₂O₃- und Al₂O₃-SiO₂-Matrix, werden die Defizite des Stands der Technik für diese Feuerbetonklasse identifiziert: Diese liegen im Bereich der Verflüssigungswirkung und des ersten Ansteifens der Feuerbetone, der Hydratation des CA-Zements in den Feuerbetonen und der Festigkeitsausprägung der Feuerbetone. Hieraus leitet sich ein entsprechender Forschungsbedarf ab.
Am Beispiel von zwei PCE-verflüssigten (PCE mit kurzer Hauptkette und langen Seitenketten sowie PCE mit langer Hauptkette und kurzen Seitenketten) und CA-Zement-gebundenen (70 % Al₂O₃) Feuerbetonen mit einer reaktivtonerde-basierten und einer reaktivtonerde-mikrosilika-basierten Matrix werden abbindekinetische Untersuchungen durchgeführt. Anhand verschiedener abbindekinetischer Messmethoden, wie Schallgeschwindigkeit oder elektrischer Leitfähigkeit, und einigen ergänzenden Messung, wie beispielsweise das ζ-Potential, wird der Abbindeverlauf der Feuerbetone untersucht und die Defizite aus dem Stand der Technik aufgeklärt.
Im Detail wurde der Stand der Technik um folgende Erkenntnisse ergänzt:
• Verflüssigung von Feuerbetonen mit PCE-Molekülen: Es wurde festgestellt, dass die Verflüssigungswirkung und das erste Ansteifen maßgeblich durch die Struktur der Verflüssigermoleküle hervorgerufen werden.
PCE-Moleküle mit langen Seitenketten verflüssigen eher sterisch. Durch die Vermittlung von Ca²⁺ aus dem CA-Zement wird die Adsorption der PCE-Moleküle verstärkt. Freie PCE-Moleküle können auf CAH-Phasen (Hydratationsprodukte) adsorbieren und somit die Fließfähigkeit des Feuerbetons für eine gewisse Zeit aufrechterhalten.
PCE-Moleküle mit kurzen Seitenketten verflüssigen elektrosterisch. Bei Lösung von Ca²⁺ aus dem CA-Zement kommt es zu einer Ca-PCE Gel-Bildung und einer korrespondierenden Koagulation der Feuerbetonmatrix und der Feuerbeton steift zeitnah nach dem Mischen an.
• Hydratation von CA-Zement: Die Hydratation von CA-Zement in den Feuerbetonen wird wesentlich durch die Länge der Seitenketten der PCE-Moleküle bzw. der Anwesenheit von Zitronensäure beeinflusst.
In Feuerbetonen die mit PCE-Molekülen mit langen Seitenketten verflüssigt wurden, kann der CA-Zement weitestgehend frei hydratisieren. Der CAH-Phasenanteil steigt in zwei Abschnitten, getrennt von einer dormanten Phase. Die dormante Phase der CA Zementhydratation wurde auf eine Lösungshemmung der Al-O-H-Passivierungsschicht auf dem CA-Zement bei mäßigem pH-Wert (pH = 12,3) zurückgeführt.
In Feuerbetonen die mit PCE-Molekülen mit kurze Seitenketten und Zitronensäure verflüssigt werden, wird die Hydratationsreaktion durch eine Ca-Citrat-PCE-Al(OH)₄-Gelbildung stark gehemmt. Es besteht die Vermutung, dass die Bindung von Ca²⁺ in dem Gel zum einen eine sehr ausgeprägte dormante Phase (pH < 12,3), mit einer schlechten Löslichkeit der Passivierungsschicht, bewirkt und zum anderen auch die Fällung von CAH-Phasen unterdrückt.
• Festigkeitsausprägung von CA-Zement-gebundenen Feuerbetonen:
Eine Koagulation bewirkt die erste Festigkeitssteigerung der Feuerbetone auf σB < 1 MPa. Im Anschluss findet die Hauptfestigkeitssteigerung auf Grund von Austrocknung durch Hydratation und Verdunstung statt. Der weitere Teil der Festigkeitssteigerung wird durch die Reduzierung der Porosität durch expansive CA-Zementhydratation und die hohe spezifische Oberfläche sowie deren weitere Erhöhung durch die CA-Zementhydratation bewirkt.
Aus den einzelnen abbindekinetischen Effekten können, zusammen mit dem Stand der Technik und den neuen Erkenntnissen, mikrostrukturelle Abbindemodelle und Modelle zur Festigkeitsentwicklung der Feuerbetone abgeleitet werden. In Folge kann für die zwei Feuerbetone zu jedem Zeitpunkt des Abbindens eine Aussage zum Abbindefortschritt und zur Festigkeitsausprägung getätigt werden. Einige der Abbindemechanismen und festigkeitsbildenden Mechanismen können auf andere Feuerbetonzusammensetzungen übertragen werden.
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 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.
Refractory dry-vibratable mixes, which consist of a mineral filling material and an organic or anorganic binder system, are widely used for linings in industrial aggregates, where a very high temperature resistance is required (e.g. steel industry). During lining, all compounds are mixed and hardening is chemically or thermally initiated. The time span required for hardening is of special relevance for the application of refractory dry-vibratable mixes. It should be long enough for adequate processability, but simultaneously avoid too long downtimes. Prediction or regulation of the hardening time, necessary for an ideal processing, is currently limited. One the one hand, this is a result of the lack of an appropriate method for time-dependent determination of the harding process. On the other hand, the mechanisms responsible for this very complex process have not yet been investigated in detail and the effect of influencing factors, like the temperature or the composition of the refractory dry-vibratable mixes, are poorly documented.
To make a contribution to the understanding of the hardening mechanism of refractory dry-vibratable mixes, it was the aim of the present work, to develop an appropriate test method for the time-dependent investigation of this process. This was realized by means of the dynamic-mechanical analysis. In addition, the hardening mechanism was described for a refractory dry-vibratable mix with a binder system, which consists of a waterglass and a phosphate hardener (AlPO4 und BPO4), using supplement gravimetric investigations and determining solubility behavior of the phosphates. By means of X-ray diffraction analysis, nuclear magnetic resonance spectroscopy and scanning electron microscopy, the impact of the hardening mechanism on the crystal and amorphous structure was studied. It could be shown, that according to the two phosphates, the hardening leads to different network structures in respect of their link denseness. These structure characteristics correlate with the speed of the hardening reactions. In addition, the impact on selected properties (thermal linear deformation, temperature-dependent phase development and phase transition) could be deducted.
Within aquatic environments sediment water interfaces (SWIs) are the most important areas concerning exchange processes between the water body and the sediment. These spatially restricted regions are characterized by steep biogeochemical gradients that determine the speciation and fate of natural or artificial substances. Apart from biological mediated processes (e.g., burrowing organisms, photosynthesis) the determining exchange processes are diffusion or a colloid-mediated transport. Hence, methods are required enabling to capture the fine scale structures at the boundary layer and to distinguish between the different transport pathways. Regarding emerging substances that will probably reach the aquatic environment engineered nanomaterials (ENMs) are of great concern due to their increased use in many products and applications. Since they are determined based on their size (<100 nm) they include a variety of different materials behaving differently in the environment. Once released, they will inevitable mix with naturally present colloids (< 1 μm) including natural nanomaterials.
With regard to existing methodological gaps concerning the characterization of ENMs (as emerging substances) and the investigation of SWIs (as receiving environmental compartments), the aim of this thesis was to develop, validate and apply suitable analytical tools. The challenges were to i) develop methods that enable a high resolution and low-invasive sampling of sediment pore water. To ii) develop routine-suitable methods for the characterization of metal-based engineered nanoparticles and iii) to adopt and optimize size-fractionation approaches for pore water samples of sediment depth profiles to obtain size-related information on element distributions at SWIs.
Within the first part, an available microprofiling system was combined with a novel micro sampling system equipped with newly developed sample filtration-probes. The system was thoroughly validated and applied to a freshwater sediment proving the applicability for an automatic sampling of sediment pore waters in parallel to microsensor measurements. Thereby, for the first time multi-element information for sediment depth profiles were obtained at a millimeter scale that could directly be related to simultaneously measured sediment parameters.
Due to the expected release of ENMs to the environment the aim was to develop methods that enable the investigation of fate and transport of ENMs at sediment water interfaces. Since standardized approaches are still lacking, methods were developed for the determination of the total mass concentration and the determination of the dissolved fraction of (nano)particle suspensions. Thereby, validated, routine suitable methods were provided enabling for the first time a routine-suitable determination of these two, among the most important properties regarding the analyses of colloidal systems, also urgently needed as a basis for the development of appropriate (future) risk assessments and regulatory frameworks. Based on this methodological basis, approaches were developed enabling to distinguish between dissolved and colloidal fractions of sediment pore waters. This made it possible for the first time to obtain fraction related element information for sediment depth profiles at a millimeter scale, capturing the fine scale structures and distinguishing between diffusion and colloid-mediated transport. In addition to the research oriented parts of this thesis, questions concerning the regulation of ENPs in the case of a release into aquatic systems were addressed in a separate publication (included in the Appendix) discussing the topic against the background of the currently valid German water legislation and the actual state of the research.
The presence of anthropogenic chemicals in the natural environment may impact both habitats and human use of natural resources. In particular the contamination of aquatic resources by organic compounds used as pharmaceuticals or household chemicals has become evident. The newly identified environmental pollutants, also known as micropollutants, often have i) unknown ecotoxicological impacts, ii) unknown partitioning mechanisms, e.g. sorption to sediments, and iii) limited regulation to control their emission. Furthermore, like any compound, micropollutants can be transformed while in the environmental matrix to unknown transformation products (TPs), which add to the number of unknown chemicals to consider and thus increase the complexity of risk management. Transformation is at the same time a natural mechanism for the removal of anthropogenic compounds, either by complete degradation (mineralisation) or to innocuous TPs. However, how transformation occurs in real-world conditions is still largely unknown. During the transport of micropollutants from household wastewater to surface water, a large amount of transformation can occur during wastewater treatment—specifically during biological nitrifying–denitrifying treatment processes. The thesis considers the systematic optimisation of laboratory investigative techniques, application of sensitive mass-spectrometry-based analysis techniques and the monitoring of full-scale wastewater treatment plants (WWTPs) to elucidate transformation processes of five known micropollutants.
The first of the five compounds investigated was the antibiotic trimethoprim. Incubation experiments were conducted at different analyte spike concentrations and different sludge to wastewater ratios. Using high-resolution mass spectrometry, a total of six TPs were identified from trimethoprim. The types of TPs formed was clearly influenced by the spike concentration. To the best of our knowledge, such impacts have not been previously described in the literature. Beginning from the lower spike concentration, a relatively stable final TP was formed (2,4-diaminopyrimidine-5-carboxylic acid, DAPC), which could account for almost all of the transformed trimethoprim quantity. The results were compared to the process in a reference reactor. Both by the detection of TPs (e.g., DAPC) and by modelling the removal kinetics, it could be concluded that only experimental results at the low spike concentrations mirrored the real reactor. The limits of using elevated spike concentrations in incubation experiments could thus be shown.
Three phenolic micropollutants, the antiseptic ortho-phenylphenol (OPP), the plastics additive bisphenol A (BPA) and the psychoactive drug dextrorphan were investigated with regard to the formation of potentially toxic, nitrophenolic TPs. Nitrite is an intermediate in the nitrification– denitrification process occurring in activated sludge and was found to cause nitration of these phenols. To elucidate the processes, incubation experiments were conducted in purified water in the presence of nitrite with OPP as the test substance. The reactive species HNO2, N2O3 and the radicals ·NO and ·NO2 were likely involved as indicated by scavenger experiments. In conditions found at WWTPs the wastewater is usually at neutral pH, and nitrite, being an intermediate, usually has a low concentration. By conducting incubation experiments inoculated with sludge from a conventional WWTP, it was found that the three phenolic micropollutants, OPP, BPA and dextrorphan were quickly transformed to biological TPs. Nitrophenolic TPs were only formed after artificial increase of the nitrite concentration or lowering of the pH. However, nitrophenolic-TPs can be formed as sample preparation artefacts through acidification or freezing for preservation, creating optimal conditions for the reaction to take place.
The final micropollutant to be studied was the pain-reliever diclofenac, a micropollutant on the EU-watch list due to ecotoxicological effects on rainbow trout. The transformation was compared in two different treatment systems, one employing a reactor with suspended carriers as a biofilm growth surface, while the other system employed conventional activated sludge. In the biofilm-based system, the pathway was found to produce many TPs each at relatively low concentration, many of which were intermediate TPs that were further degraded to unknown tertiary TPs. In the conventional activated sludge system some of the same reactions took place but all at much slower rates. The main difference between the two systems was due to different reaction rates rather than different transformation pathways. The municipal WWTPs were monitored to verify these results. In the biofilm system, a 10-day monitoring campaign confirmed an 88% removal of diclofenac and the formation of the same TPs as those observed in the laboratory experiments. The proposed environmental quality standard of 0.05 μg/L might thus be met without the need for additional treatment processes such as activated carbon filtration or ozonation.
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.
Die vorliegende Doktorarbeit hatte zum Ziel zu prüfen, ob Emulsionspolymere auf Acrylatbasis als neuartige Photokatalysatoren bzw. Katalysatoren genutzt werden können.
Auf Grund der Beschaffenheit und der Eigenschaften von Emulsionspolymeren ist davon auszugehen, dass die Nutzung selbiger als Katalysatoren eine neue Art einer chemischen Katalyse ermöglicht. So sollen die Vorteile der heterogenen und homogenen Katalyse vereint und die jeweiligen Nachteile minimiert werden. Als besonders erfolgversprechend hat sich während der praktischen Arbeit die Nutzung von Emulsionspolymeren als Photokatalysatoren herausgestellt.
Die Anbindung der photokatalytisch aktiven Moleküle an/in den Polymerstrang soll kovalent erfolgen. Deshalb war ein erstes Teilziel dieser Arbeit prototypische Katalysatormoleküle zu synthetisieren, die über einen Acrylat-Substituenten verfügen, der in einer radikalischen Polymerisationsreaktion reagieren kann. Als Photokatalysatoren wurden Ruthenium- Polypyridin-Komplexe ausgewählt, die sowohl für eine inter- als auch intramolekulare Photokatalyse zur Herstellung von Wasserstoff aus Wasser geeignet sind. Für organokatalytische Zwecke wurde ein L-Prolin-Derivat synthetisiert, welches jedoch nicht auf seine Polymerisierbarkeit getestet wurde.
In einem ersten Schritt wurden die prototypischen 2,2’-Bipyridin-Liganden synthetisiert. Dabei konnte eine verbesserte Synthesemethode für 4-Brom-2,2’-bipyridin ausgearbeitet werden. Die Funktionalisierung erfolgte letztendlich durch eine Horner-Wadsworth-Emmons-Reaktion, die anschließend an eine Eintopfsynthese zur Darstellung von 4-Formyl-2,2’-biypridin erfolgte. Die prototypischen Photokatalysatoren zeigten mäßige Erfolge (TON: 37-136, 6h, 10% H2O, 470 nm) in Bezug auf die photokatalytische Wasserstoffproduktion, sodass an dieser Stelle eine Verbesserung der entsprechenden katalytischen Systeme erfolgen sollte.
Die Polymerisationsreaktion konnte für zwei intermolekulare Photokatalysatoren und zwei intramolekulare Photokatalysatoren durchgeführt werden. Dabei fiel auf, dass die intermolekularen Photokatalysatoren besser polymerisieren als die intramolekularen Photokatalysatoren. Es wird angenommen, dass dies mit der Löslichkeit der Substanzen im Monomer Ethylmethacrylat zusammen hängt.
Die photokatalytisch funktionalisierten Emulsionspolymere zeigten eine ähnliche photokatalytische Aktivität (TON: 9-101, 6h, 10% H2O, 470 nm) wie die jeweiligen Ausgangsstoffe selbst. Es konnte jedoch bewiesen werden, dass Emulsionspolymere als Photokatalysatoren genutzt werden können, wenn auch noch weitere Arbeiten zur Optimierung der Systeme nötig sind.
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.