This thesis includes both experimental and modelling studies on the treatment of drinking water. Three aspects were studied: (i) removal of fluoride (F– ) by adsorption, (ii) removal of fluoride and other contaminants by solar distillation, (iii) denitrification by a microbial fuel cell. The availability of potable water on earth is about 0.2% of the total available water. This very small quantity is polluted by anthropogenic and natural contaminants. Fluoride is a classic example of a natural contaminant, wherein the dissolution of F– bearing minerals causes the release of F– into the groundwater. Exposure to concentrations > 1 mg/L over ex-tended periods of time results in dental and skeletal fluorosis. Worldwide, about 220 million people are at risk. Nitrate is an example of anthropogenic contaminant, occurring because of addition of high quantities of fertilizers to the soil for better crop yields. The excess fertilizers penetrate the soil and mix with the groundwater, resulting in nitrate contamination. The major effect of nitrate contamination is met haemoglobin , which is caused because of the oxidation of ferrous ion in haemoglobin to ferric ion by the nitrite to form haemoglobin. The effects can be noticed by the change in colour of skin to bluish grey or brownish grey in infants. To counter the drastic effects of these anions, the World Health Organization (WHO) has prescribed permissible limits of 1.5 mg/L and 45 mg/L for F– and NO3 – , respectively. For obtaining contaminant-free water, many methods have been used. Reverse osmosis (RO) is one of the widely-used methods. Even though this process removes most of the contaminants, about 50 - 70% of the inlet water is wasted as a reject stream with higher concentrations of the contaminants. This is a very unsustainable way of using water, particularly in drought-prone areas. So, in the thesis a conceptual strategy with three different methods is developed to treat reject water. In the first part of the thesis, the removal of F– using adsorption was studied. Activated alumina (AA) and a hybrid anion exchange resin embedded with hydrous zirconium oxide nanoparticles (HAIX-Zr) (sample sent by Prof. Arup K SenGupta) were used as the adsorbents. The adsorbents were tested with synthetic water samples and reverse osmosis (RO) reject water. HAIX-Zr had a better adsorption capacity compared to AA when water containing only F– was used. The presence of high concentrations of co-ions affects the uptake of F– drastically, with a decrease of up to 34% and 79% for AA and HAIX-Zr, respectively. With AA, for a synthetic water sample with a small concentration of HCO3 – , there was a two-fold increase in the uptake of F– compared to a water sample containing only F– . There was no removal of NO3 – by AA. HAIX-Zr removes NO3 – , but to a lesser extent than F– . With AA, the pH of the inlet solution affected the adsorption capacity, because of the change in the surface charge of AA. Based on the type of water sample used, the cost of treated water varied from Re. 0.1 - 1.0/L ($ 0.0015 - 0.015/L) for AA and 0.2 - 11.5/L ($ 0.003 - 0.17/L) for HAIX-Zr. A community-level plant was set up to treat the RO reject water using AA. Due to challenges at the field level, the pilot plant had to be stopped after 80 bed volumes of water were treated. From our observations and as also reported by many authors, the adsorption of F– is affected by the presence of many ions. When modelling the adsorption of F– , it is usually taken as a single entity getting adsorbed on the adsorbent. As this is not a proper assumption, a model was developed which takes into account all the speciation reactions that take place during adsorption, and all the species like H+, OH– , Na+, Cl– , and NO3 – present in the solution along with F– . Using the model, the equilibrium constants and rate constants for the reactions were obtained. For one initial concentration of F– , a good fit was obtained to the batch adsorption data, except at short times. Due to uncertainty about the amount of impurity present in the adsorbent, at higher initial concentrations of F– , there was a significant discrepancy between predictions and data. Considering column experiments, the breakthrough curve for F– was simulated using the developed model. For the special case of negligible mass transfer resistances, the predicted break-through volume was within 3% of the observed value. In the second part of the thesis, nitrate removal was investigated using microbial fuel cell (MFC). In a MFC, power is generated by the activity of the microorganisms present in the cell. The organisms present in the anode side release electrons (e– ) by the use of substances that can be oxidized, namely, glucose, acetate, etc. On the cathode side, the organisms have the potential to take in e– and reducible substances, and release reduced products like nitrogen, hydrogen, etc. In the present case, nitrates added to the cathode side were reduced to nitrogen gas by the use of a consortium of micro-organisms taken from seawater. A similar consortium was used in the anode chamber Here, the study was focused on improving the efficiency of MFC for removal of NO3 – , by changing the buffering medium used in the cells. Commonly, phosphate buffer is used, but when using a MFC for treatment, the presence of PO43 – causes water contamination and is not suitable for drinking. There-fore, PO43 – was replaced with HCO3 – on the cathode side of the cell. This resulted in a higher removal of NO3 – and power production compared to the PO43 – buffered solution In the third part of the thesis, contaminant removal using solar distillation was investigated. For this as inclined basin still was used. Investigations were based on the evaporation rate of contaminated water, and the odour and concentrations of ions in the distillate. In order to improve the evaporation rates, different radiation absorbing materials like sand, activated charcoal, and carbon nanoparticles encapsulated in polymer sheets (PCNP) were investigated. It was observed that the evaporation rates were higher with activated carbon than the other materials. Using this technique there was about 99% removal of NO3 – , F– , SO42 – and the concentrations of ions in the distillate were well below the acceptable limits. When sand or PCNP was used as an absorbing/wicking medium, the distillate had an objectionable odour. With the use of AC, the odour could be eliminated because of the adsorption of odour-causing compounds.

In the first part of this thesis the methodic of lab trial was studied, which will be useful for studying adsorption of natural organic matter by activated carbon. As an optimal method of testing adsorption characters jar testing was chosen. Again as an indicator of organic contamination, it was decided to use permanganate chemical oxygen demand (in Czech CHSKMn) will be used. In the second part of this thesis the adsorption characters of eight types of granular activated carbon were studied. Those granular activated carbon came from two world produces, from company NORIT five type of granular activated carbon were tested: NORIT GAC 1020, NORIT PK 1-3, NORIT GAC 1240, NORIT ROW 0.8 SUPRA a TOD NORIT ROX 0.8 and from company Chemviron Carbon three types of granular activated carbon were tested: F100 FE11120A, F400 FE11210A a TL830 FE2028B. Batch kinetic tests of natural organic matter adsorption were conducted with all types of granular activated carbon at first. For description of sorption not only the batch kinetic tests and duration needed for setting equilibrium were observed, but also the process decreasing of concentration of natural organic matters to the value of equilibrium concentration known as adsorption equilibrium was followed.

No description available.

This diploma thesis deals with the study of adsorption of low-molecular components of organic substances produced by phytoplankton - AOM (Algal Organic Matter) on AC (Activated Carbon) during drinking water treatment. For the experimental purpose in this thesis, there were used selected amino acids as low molecular substances of AOM that are difficult to remove by conventional water treatment process by coagulation. As adsorbent, there was used a detailed characterized of granulated activated carbon (GAC) - Filtrasorb TL 830 (FTL830) which is intended directly for the purpose of water treatment. There were realizing the equilibrium batch adsorption experiments with three different model amino acids - arginine (Arg), phenylalanine (Phe) and aspartic acid (Asp). There was investigated the efficiency of removing amino acid depending on the solution temperature and pH. Results of the adsorption experiments have shown that the temperature affects the adsorption efficiency. Adsorption is essentially described as an exothermic process but the adsorption of Arg and Phe from an aqueous solution to GAC occurs more efficiently at higher temperatures. It means that the adsorption is the endothermic process. In the case of Arg adsorption, the temperature was found to influence adsorption efficiency less than...

Through progressive industrialization and the relentless consumption of natural raw materials, man is exerting a negative influence on his habitat. In particular, water as the basis of life and almost all processes of our economy is contaminated by various pollutants due to excessive use and insufficient purification. Here, oxyanions, heavy metal ions and organic pollutants pose a high risk to aquatic habitats and ultimately to humans. Due to insufficient removal, they also contribute to the loss of non-renewable raw materials for industrial cycles. Due to a mostly low effect concentration and potential interactions with diverse living organisms, the removal of many contaminants is extremely important to avoid further altering existing ecosystems. Adsorption represents an energy-efficient method of removal using adsorbents suitable for this purpose. Highly cross-linked resin polymers such as poly(melamine-co-formaldehyde) (PMF) with its excellent chemical resistance, high number of functional groups and ease of preparation, represent promising starting points for adsorbents. This dissertation describes the colloidal aqueous synthesis of nanoporous resin particles (e.g. PMF) by templating with SiO2 nanoparticles (SiO2 NPs), which are subsequently used to adsorb water pollutants. An overall goal of this work consists of elucidating the mechanism for particle and pore formation by systematically varying various synthesis parameters. Electron microscopy, N2-soprtion and particle size measurement are used to analyze the morphology, size and pore structure of the particles. Comprehensive investigations thus allow to determine the influence of each tested synthesis parameter on these properties. A very important goal, especially for future large-scale applicability, is the colloidal production of uniform particles, which have both a high ordered porosity and particle diameters in the range of a few micrometers. This enables an application as a fixed-bed adsorber that can be flowed through. This goal is closely linked to the mechanistic elucidation of pore and particle formation in the synthesis. The prepared nanoporous PMF particles were tested for various adsorption applications after their characterization. In order to obtain a comprehensive picture of the applicability of PMF particles, experiments with oxyanions, with pharmaceuticals as representatives of organic pollutants and with heavy metal ions will be carried out respectively. On the one hand, these experiments will focus on investigating the adsorption performance and mechanism of PMF with the respective pollutant. On the other hand, the influence of the changed porosity on the adsorption mechanism is investigated by using different particles of a varied synthesis parameter. Sulfate and phosphate ions were investigated in the oxyanion class. Extremely high separation rates were demonstrated for both ions, significantly outperforming previous commercially available materials. In experiments concerning a potential selective adsorption and thus separation of both species, the PMF/SiO2 hybrid particles, in which the template had not yet been removed, showed a selective sulfate adsorption. The immobilization of heavy metal ions was analyzed with special focus on the simultaneous separation of the Cu2+ ions and respective anions used here. Investigations of the adsorbent after the adsorption experiments by means of electron microscopy, X-ray scattering and electron spin resonance spectroscopy elucidated the adsorption mechanism, which had been insufficiently analyzed so far. Here, adsorption and surface-induced precipitation were identified as partially separate subprocesses, both of which are responsible for the separation of both metal and anions from solution. In adsorption experiments with the monovalent ions nitrate and chloride, a two-step uptake process was identified, which was mathematically described for the first time via a new adsorption isotherm. In the scope of organic water pollutants, the separation of the pharmaceutical diclofenac is being tested. In particular, the adsorption of pharmaceuticals is an urgent issue due to their low effect concentration and ubiquity in surface and tap waters. Pharmaceutical separation using PMF has hardly been investigated worldwide despite its promising properties. In these experiments, particles templated with SiO2 NPs of different sizes and stabilized in different ways were tested. This resulted in pore systems that varied from each other especially in their accessibility of the pore system and in the diameter of the connecting channels between the main cavities. These characteristics significantly affected the adsorption capacity and separation rates in low concentration range. A final goal is to synthesize a resin network that uses an equally highly functional triazine-based monomer instead of melamine. The monomer 2,4,6-tris(2,4,6-trihydroxyphenyl)-1,3,5-triazine (3PT) possesses nine hydroxyl groups each, whereby a polymer based on it should exhibit strongly modified adsorption properties compared to PMF. This monomer was used in an aqueous polymerization analogous to PMF to produce a previously unknown polymer network, which was designated P(3PT-F). Here, templating was omitted because the newly prepared material already exhibited intrinsic nanoporosity due to the size of the 3PT monomer. In subsequent adsorption experiments, very high separation rates were demonstrated for the toxic metal ions Pb2+, Cd2+ and Ni2+. In realistic initial concentrations, the contamination was reduced to drinking water quality in each case. P(3PT-F) also showed highly selective removal of Pb2+ over the common ions Ca2+, Mg2+, K+ and Fe2+. As fundamental evidence, reusability was also demonstrated by complete desorption with dilute HCl and subsequent re-adsorption without significant reduction in capacity. Overall, starting from the fundamental study of PMF particle synthesis, a more general understanding of aqueous dispersion polymerization of hydrophobic resins was first derived and templating with hydrophilic SiO2 NPs was implemented. With the help of understanding the particle growth processes and interactions responsible for templating, the properties of the resulting particles could be controlled. Subsequently, the influence of the changed porosity in particular on the separation performance could be investigated in the adsorption studies. In addition, it was possible to analyze which interactions PMF enters into with the respective pollutant types. By replacing the monomer melamine with a hydroxyl-containing monomer, a novel resin polymer could be produced. With its altered porosity and reactivity, this can now serve as a new starting point for adsorption experiments with strongly altered adsorption performance, e.g. towards heavy metal ions.:Abstract 1 Kurzfassung 5 List of Publications 9 First-Author Publications 9 Co-Author Publications 10 Patent 12 Conference Proceedings 12 Oral Presentations 12 Poster 12 List of Figures 13 Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 14 Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 15 Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 16 SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 18 Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 19 List of Tables 21 Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 21 Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 21 Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 22 SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 22 Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 23 Abbreviations 25 Symbols 26 1. Introduction 1 2. Objectives and Experimental Design 5 3. Scientific Background 11 3.1. Poly(melamine-co-formaldehyde) 11 3.1.1. Polymerization Mechanism 11 3.1.2. Synthesis Strategies for the Preparation of Porous PMF Particles. 13 3.1.3. Fields of Application of PMF 13 3.2. Adsorption 15 3.2.1. Adsorption Isotherms and Mathematical Modeling 16 3.3. Surface Precipitation 20 4. Fundamentals of Instrumental Analytics 23 4.1. Gas Sorption Measurements 23 4.1.1. Determination of Pore Sizes 26 4.1.2. Determination of Specific Surface Area 27 4.2. Transmission Electron Microscopy 29 4.3. Inductively Coupled Plasma Optical Emission Spectroscopy 31 Results and Discussion 33 Chapter Overview 33 5. Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal 37 Graphical Abstract 37 Abstract 37 1. Introduction 38 2. Results and Discussion 39 2.1. Synthesis and Characterization of the PMF Particles 40 2.2. Sorption Experiments 47 3. Materials and Methods 54 3.1. Materials 54 3.2. Methods 54 3.3. Synthesis of the PMF Particles 56 3.4. Water Treatment Experiments 57 4. Conclusions 59 6. Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal 65 Graphical Abstract 65 Abstract 65 1. Introduction 66 2. Materials 68 3. Methods 68 3.1. Synthesis of the PMF particles 70 3.2. Water treatment experiments with diclofenac solution 72 3.3. Theoretical model 72 3. Results and Discussion 73 3.1. Synthesis and characterization of the PMF particles 74 3.2. Adsorption of Pharmaceutics 80 4. Conclusion 84 7. Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles 89 Graphical Abstract 89 Abstract 89 1. Introduction 90 2. Materials and methods 91 2.1. Materials 91 2.2. Synthesis of the Poly(melamine-co-formaldehyde) particles 92 2.3. Methods 93 2.4. Water treatment experiments 96 3. Results and discussion 97 3.1. Synthesis and characterization of the PMF particles 98 3.2. Cu2+ uptake experiments 102 3.3. Mechanism for Cu2+ and Anion Removal 115 3.4. Investigation of other heavy metal salts 116 4. Conclusions 117 8. SiO₂ Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles 121 Graphical Abstract 121 Abstract 121 1. Introduction 122 2. Materials and methods 123 2.1. Materials 123 2.2. Methods 124 2.3. Synthesis of the PMF particles 125 2.4. Water treatment experiments 128 2.5. Theoretical model 129 3. Results and Discussion 132 3.1. PMF-Std 133 3.2. Influence of the reaction mixture composition 136 3.3. Variation of the process parameters 140 3.4. Conclusion on the templating mechanism for PMF-Std 146 3.5. Acquiring µm-sized porous PMF particles for adsorption application 149 3.6. Adsorption experiments with K2Cr2O7 solution 151 4. Conclusion 155 9. Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions 161 Graphical Abstract 161 Abstract 161 1. Introduction 162 2. Materials and methods 163 2.1. Materials 163 2.2. Synthesis 164 2.3. Characterization 166 2.4. Batch adsorption experiments 169 2.5. Calculation and theoretical models 170 3. Results and discussion 172 3.1. Synthesis and characterization of the polymer particles 172 3.2. Adsorption experiments with Ni2+, Cd2+, and Pb2+ onto P(3PT-F)-3L 178 4. Conclusions 184 10. Conclusion and Outlook 191 Contribution to Publications 197 Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal 197 Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal 198 Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles 199 SiO₂ Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles 200 Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions 201 Danksagung 203 Appendix 205 References 207 Eidesstattliche Versicherung 217 / Durch fortschreitende Industrialisierung und den schonungslosen Verbrauch natürlicher Rohstoffe übt der Mensch negativen Einfluss auf seinen Lebensraum aus. Insbesondere Wasser als Grundlage des Lebens und fast aller Prozesse unserer Wirtschaft wird durch eine übermäßige Nutzung und unzureichende Reinigung mit diversen Schadstoffen kontaminiert. Hierbei stellen Oxyanionen, Schwermetallionen und organische Schadstoffe ein hohes Risiko für aquatische Lebensräume und letztendlich auch den Menschen dar. Durch unzureichende Entfernung tragen sie außerdem zum Verlust nicht-erneuerbarer Rohstoffe für industrielle Kreisläufe bei. Durch eine meist geringe Effektkonzentration und potentielle Wechselwirkungen mit diversen Lebewesen ist die Entfernung vieler Verunreinigungen extrem wichtig, um bestehende Ökosysteme nicht weiter zu verändern. Adsorption stellt eine energieeffiziente Methode zur Entfernung dieser Schadstoffe durch hierfür geeignete Adsorbentien dar. Hochgradig vernetzte Harzpolymere wie Poly(melamin-co-formaldehyd) (PMF) stellen mit ihrer sehr hohen chemischen Beständigkeit, einer hohen Zahl funktioneller Gruppen und einfachen Herstellbarkeit einen vielversprechenden Ausgangspunkt für Adsorbentien dar. Diese Dissertation beschreibt die kolloidale, wässrige Synthese nanoporöser Harzpartikel (z. B. PMF) durch eine Templatierung mit SiO2 Nanopartikeln (SiO2 NPs), welche anschließend zur Adsorption von Wasserschadstoffen eingesetzt werden. Ein übergeordnetes Ziel dieser Arbeit besteht aus der Aufklärung des Mechanismus zur Partikel- und Porenbildung durch systematische Variation verschiedener Syntheseparameter. Mittels Elektronenmikroskopie, N2-Sorption und Partikelgrößenmessung wird die Morphologie, Größe und Porenstruktur der Partikel analysiert. Umfassende Untersuchungen ermöglichen somit, den Einfluss der einzelnen getesteten Syntheseparameter auf diese Eigenschaften zu bestimmen. Ein sehr wichtiges Ziel, besonders für eine zukünftige großtechnische Anwendbarkeit, ist dabei die kolloidale Herstellung uniformer Partikel, welche sowohl eine hohe geordnete Porosität als auch Partikeldurchmesser im Bereich einiger Mikrometer aufweisen. Dies ermöglicht einen Einsatz als durchströmbaren Festbett-Adsorber. Dieses Ziel ist eng mit der mechanistischen Aufklärung der Poren- und Partikelbildung in der Synthese verknüpft. Die hergestellten nanoporösen PMF-Partikel wurden nach ihrer Charakterisierung für verschiedene Adsorptionsanwendungen getestet. Um ein umfassendes Bild über die Einsetzbarkeit von PMF-Partikeln zu erhalten, sollen jeweils Versuche mit Oxyanionen, mit Schwermetallionen und mit Pharmazeutika als Vertreter organischer Schadstoffe durchgeführt werden. Bei diesen Versuchen steht zum einen die Untersuchung der Adsorptionsleistung und des Adsorptionsmechanismus des jeweiligen Schadstoffes an PMF im Vordergrund. Zum anderen wird durch die Verwendung verschiedener Partikel, bei welchen ein einzelner Syntheseparameter variiert wurde, der Einfluss der veränderten Porosität auf den Adsorptionsmechanismus untersucht. Sulfat- und Phosphationen wurden in der Klasse der Oxyanionen untersucht. Für beide Ionen wurden extrem hohe Abtrennraten nachgewiesen, welche bisherige kommerziell erhältliche Materialien signifikant übertraf. In Versuchen hinsichtlich einer potentiellen selektiven Adsorption und somit Trennung beider Spezies, zeigten die PMF/SiO2-Hybridpartikel, bei welchen das Templat noch nicht entfernt wurde, eine selektive Sulfatadsorption. Die Immobilisierung von Schwermetallionen wurde mit besonderem Fokus auf die gleichzeitig auftretende Abtrennung der dafür verwendeten Cu2+-Ionen und jeweiliger Anionen analysiert. Durch Untersuchungen des Adsorbens nach den Adsorptionsversuchen mittels Elektronenmikroskopie, Röntgenstreuung und Elektronenspinresonanz-Spektroskopie wurde der bisher unzureichend analysierte Adsorptionsmechanismus aufgeklärt. Hierbei wurden Adsorption und oberflächeninduzierte Fällung als separate Teilprozesse identifiziert, welche beide jeweils für die Abscheidung von sowohl Metall- als auch Anionen aus der Lösung verantwortlich sind. Bei Adsorptionsversuchen mit den einwertigen Ionen Nitrat und Chlorid wurde ein zweistufiger Prozess identifiziert, welcher erstmals über eine neue Adsorptionsisotherme mathematisch beschrieben wurde. Im Bereich organischer Wasserschadstoffe wird die Abtrennung des Pharmazeutikums Diclofenac getestet. Insbesondere die Adsorption von Pharmazeutika stellt aufgrund von deren geringen Effektkonzentration und Allgegenwärtigkeit in Oberflächen- und Leitungswässern ein dringliches Thema dar. Die Pharmazeutika-Abtrennung mittels PMF wurde trotz seiner vielversprechenden Eigenschaften weltweit bisher kaum untersucht. Im Rahmen dieser Versuche wurden Partikel getestet, welche mit unterschiedlich großen und unterschiedlich stabilisierten SiO2 NPs templatiert wurden. Dadurch entstanden Porensysteme, die besonders in derer Zugänglichkeit ihres Porensystems und in dem Durchmesser der Verbindungskanäle zwischen den Hauptkavitäten voneinander variierten. Diese Eigenschaften wirkten sich signifikant auf die Adsorptionskapazität und die Abtrennraten im niedrigen Konzentrationsbereich aus. Ein abschließendes Ziel ist die Synthese eines Harznetzwerkes, welches statt Melamin auf einem ebenso hochfunktionellen, triazinbasierten Monomer basiert. Das Monomer 2,4,6-Tris(2,4,6-trihydroxyphenyl)-1,3,5-triazin (3PT) besitzt jeweils neun Hydroxylgruppen, wodurch ein darauf basierendes Polymer stark veränderte Adsorptionseigenschaften gegenüber PMF aufweisen soll. Mit diesem Monomer wurde in einer analog zu PMF durchgeführten wässrigen Polymerisation ein bisher unbekanntes Polymernetzwerk hergestellt, welches als P(3PT-F) bezeichnet wurde. Hierbei wurde auf Templatierung verzichtet, da das neu hergestellte Material bereits intrinsische Nanoporosität durch die Größe des verwendeten 3PT-Monomers aufwies. In anschließenden Adsorptionsversuchen wurden sehr hohe Abtrennraten für die toxischen Metallion Pb2+, Cd2+ und Ni2+ nachgewiesen. In realistischen Ausgangskonzentrationen wurde die Kontamination mit diesen Ionen jeweils auf Trinkwasserqualität reduziert. P(3PT-F) zeigte außerdem eine sehr selektive Abtrennung von Pb2+ gegenüber den häufig vorkommenden Ionen Ca2+, Mg2+, K+ und Fe2+. Als grundlegender Beweis konnte eine Wiederverwendbarkeit durch die vollständige Desorption mit verdünnter HCl gezeigt werden und eine anschließende erneute Adsorption ohne signifikante Verringerung der Kapazität. Insgesamt wurde ausgehend von der grundlegenden Untersuchung der PMF-Partikelsynthese erst ein generelleres Verständnis der wässrigen Dispersionspolymerisation hydrophober Harze abgeleitet und die Templatierung mit hydrophilen SiO2 NPs implementiert. Mithilfe des Verständnisses der Partikelwachstumsprozesse und der Wechselwirkungen, welche für die Templatierung verantwortlich sind, konnten die Eigenschaften der entstehenden Partikel gesteuert werden. Im Rahmen der Adsorptionsuntersuchungen konnte anschließend der Einfluss insbesondere der veränderten Porosität auf die Abtrennleistung untersucht werden. Außerdem konnte analysiert werden, welche Wechselwirkungen PMF mit den jeweiligen Schadstoffarten eingeht. Durch den Austausch des Monomers Melamin gegen das hydroxylhaltiges Monomer 3PT konnte ein neuartiges Harzpolymer hergestellt werden. Dieses kann mit seiner veränderten Porosität und Reaktivität nun als neuer Ausgangspunkt für Adsorptionsexperimente mit stark veränderter Adsorptionsleistung z. B. gegenüber Schwermetallionen dienen.:Abstract 1 Kurzfassung 5 List of Publications 9 First-Author Publications 9 Co-Author Publications 10 Patent 12 Conference Proceedings 12 Oral Presentations 12 Poster 12 List of Figures 13 Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 14 Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 15 Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 16 SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 18 Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 19 List of Tables 21 Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 21 Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 21 Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 22 SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 22 Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 23 Abbreviations 25 Symbols 26 1. Introduction 1 2. Objectives and Experimental Design 5 3. Scientific Background 11 3.1. Poly(melamine-co-formaldehyde) 11 3.1.1. Polymerization Mechanism 11 3.1.2. Synthesis Strategies for the Preparation of Porous PMF Particles. 13 3.1.3. Fields of Application of PMF 13 3.2. Adsorption 15 3.2.1. Adsorption Isotherms and Mathematical Modeling 16 3.3. Surface Precipitation 20 4. Fundamentals of Instrumental Analytics 23 4.1. Gas Sorption Measurements 23 4.1.1. Determination of Pore Sizes 26 4.1.2. Determination of Specific Surface Area 27 4.2. Transmission Electron Microscopy 29 4.3. Inductively Coupled Plasma Optical Emission Spectroscopy 31 Results and Discussion 33 Chapter Overview 33 5. Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal 37 Graphical Abstract 37 Abstract 37 1. Introduction 38 2. Results and Discussion 39 2.1. Synthesis and Characterization of the PMF Particles 40 2.2. Sorption Experiments 47 3. Materials and Methods 54 3.1. Materials 54 3.2. Methods 54 3.3. Synthesis of the PMF Particles 56 3.4. Water Treatment Experiments 57 4. Conclusions 59 6. Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal 65 Graphical Abstract 65 Abstract 65 1. Introduction 66 2. Materials 68 3. Methods 68 3.1. Synthesis of the PMF particles 70 3.2. Water treatment experiments with diclofenac solution 72 3.3. Theoretical model 72 3. Results and Discussion 73 3.1. Synthesis and characterization of the PMF particles 74 3.2. Adsorption of Pharmaceutics 80 4. Conclusion 84 7. Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles 89 Graphical Abstract 89 Abstract 89 1. Introduction 90 2. Materials and methods 91 2.1. Materials 91 2.2. Synthesis of the Poly(melamine-co-formaldehyde) particles 92 2.3. Methods 93 2.4. Water treatment experiments 96 3. Results and discussion 97 3.1. Synthesis and characterization of the PMF particles 98 3.2. Cu2+ uptake experiments 102 3.3. Mechanism for Cu2+ and Anion Removal 115 3.4. Investigation of other heavy metal salts 116 4. Conclusions 117 8. SiO₂ Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles 121 Graphical Abstract 121 Abstract 121 1. Introduction 122 2. Materials and methods 123 2.1. Materials 123 2.2. Methods 124 2.3. Synthesis of the PMF particles 125 2.4. Water treatment experiments 128 2.5. Theoretical model 129 3. Results and Discussion 132 3.1. PMF-Std 133 3.2. Influence of the reaction mixture composition 136 3.3. Variation of the process parameters 140 3.4. Conclusion on the templating mechanism for PMF-Std 146 3.5. Acquiring µm-sized porous PMF particles for adsorption application 149 3.6. Adsorption experiments with K2Cr2O7 solution 151 4. Conclusion 155 9. Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions 161 Graphical Abstract 161 Abstract 161 1. Introduction 162 2. Materials and methods 163 2.1. Materials 163 2.2. Synthesis 164 2.3. Characterization 166 2.4. Batch adsorption experiments 169 2.5. Calculation and theoretical models 170 3. Results and discussion 172 3.1. Synthesis and characterization of the polymer particles 172 3.2. Adsorption experiments with Ni2+, Cd2+, and Pb2+ onto P(3PT-F)-3L 178 4. Conclusions 184 10. Conclusion and Outlook 191 Contribution to Publications 197 Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal 197 Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal 198 Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles 199 SiO₂ Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles 200 Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions 201 Danksagung 203 Appendix 205 References 207 Eidesstattliche Versicherung 217

The dissertation thesis focuses on the application of activated carbon for the removal of low molecular weight algal organic matter (AOM) produced by phytoplankton during drinking water treatment, as well as on the effect of AOM on adsorption of anthropogenic micropollutants contained in raw water. The results of this study have been published in international peer-reviewed journals in 4 papers and in 2 conference contributions. The efficiency of AOM removal was studied in laboratory equilibrium and kinetic experiments using different types of granular activated carbon and cellular peptides with molecular weight < 10 kDa produced by cyanobacterium Microcystis aeruginosa. It has been previously confirmed that these peptides are removed with difficulty during the conventional water treatment based on coagulation/flocculation processes and therefore, other methods need to be applied for their restriction. The effect of solution properties on peptide adsorption was assessed by the tests at different pH values and at variable ionic strengths. The negative impact of peptides on the adsorption of organic micropollutants present in raw water was simulated using competitive adsorption experiments with herbicides alachlor and...

The Ph.D. thesis deals with the characterization of algal organic matter (AOM), which is difficult to remove in water treatment, and on the basis of AOM character, various methods for its elimination, e.g. coagulation, oxidation with subsequent coagulation and adsorption onto activated carbon are assesed. Special emphasis is placed on identifying the optimal conditions of the processes and on describing the mechanisms and interactions involved. In terms of anthropogenic micropollutants, the thesis deals with the highly topical issue of the occurrence of microplastics in water. It was found that the removal efficiency of the individual AOM components varies substantially depending on the elimination method used. The identified optimum conditions of individual methods and especially the mechanisms that apply to the removal of target substances varied widely. The non-proteinaceous fraction of AOM was removed with very low efficiency (max. 25%) by conventional coagulation even under optimized conditions (pH 6.6- 7.5 for aluminium sulfate as the coagulating agent and pH 7.5-9.0 for polyaluminium chloride) and it was given by the high content of low molecular weight (LMW) substances that are difficult to coagulate. The dominant coagulation mechanism was adsorption onto aluminium hydroxide precipitates....