Patrick Bräutigam

Zusammenfassung

As the demand of freshwater increases with simultaneously aggravated climatic challenges, the development of efficient and effective water purification methods is of high importance. Qualitative Structure-Property Relationships (QSPRs) can support this process by calculating a correlation between the molecular structure and the degradability of water pollutants in a defined removal procedure, expressed by the kinetic constant of their removal. This can help to receive more mechanistical interpretation of the underlying process, but also to reduce experimental costs and time. As most QSPR models in wastewater treatment research are based on experimental data using ultrapure water as reaction solutions, it is still unknown to which extent QSPR models for different water matrices differ from each other with regard to selected descriptors and performance. Therefore, in this study the sonolytic degradation of 32 phenol derivates was investigated for three different water matrices (NaCl, Glucose, NaCl+Glucose) and compared to a previous study in ultrapure water. With only very few exceptions, the addition of water additives reduced the degradability of the target analytes. Based on these four datasets, QSPR modelling, respecting all five OECD principles for reliable QSPR models, were performed using numerous internal and external validations as well as statistical quality assurances to ensure good regression abilities as well as stability and predictivity. As the final four models were compared, it was observed that the descriptor selection and model calculation were highly impacted by the water additives. This was also confirmed when the descriptor pools of the best 10 models for each water composition were compared, as the descriptor pools were also highly dissimilar, indicating a shift in structural importance when changing the water composition. It could be shown that water matrices significantly influence the results of QSPR modelling even at very low concentrations of the matrix components.

Zusammenfassung

The standard method to determine chemical oxygen demand (COD) with K2Cr2O6 uses harmful chemicals, has a long analysis time, and cannot be used for on-site online monitoring. It is therefore necessary to find a fast, cheap, and harmless alternative. The amperometric determination of COD on boron-doped diamond (BDD) electrodes is a promising approach. However, to be a suitable alternative, the electrochemical method must at least be able to determine the COD of water samples independently of the contained substances. Therefore, the current signal as a function of various organic materials was investigated for the first time. It was shown that the height of the signal current depended on the type of organic matter in single-substance solutions and that this substance dependency increases with the amount of COD. Those findings could be explained by the mechanism proposed for this reaction, showing that the selectivity of the reaction depends on the ratio of the concentration of hydroxyl radicals and organic species. We give an outlook on how to improve the method in order to increase the linear working range and avoid signal variance and how to further explain the signal variance.

Zusammenfassung

Local and climate-driven challenges combined with an increasing anthropogenic pollution of the water compartment all around the world make a sustainable handling of wastewater imperative. New additional treatment methods are under examination, including cavitation-based advanced oxidation processes. To quantify structural influences on chemical processes, quantitative structure-property relationship (QSPR) modelling can be used, which calculates a correlation between a defined endpoint and structural properties expressed by molecular descriptors. In this study, QSPR modelling has been applied to investigate the structural influence on the degradability of organic micropollutants with high-frequency sonolysis. The dataset of a previous study on 32 phenol derivates was expanded by 60 mostly aromatic compounds, whose kinetic degradation constants were obtained in a standardized experimental setup. QSPR modelling was conducted using the software PaDEL for descriptor calculation and QSARINS for the modelling process using a multiple linear regression approach and genetic algorithm. All five OECD-requirements for applicable QSPR models were respected. The obtained model included 12 model descriptors, was evaluated with numerous statistical quality parameters, and shows good regression abilities as well as robustness and predictability (R2 = 0.8651, CCCtr = 0.9277, Q2loo = 0.8010, R2ext = 0.7836, CCCext = 0.8838, Q2F1 = 0.7697). The interpretation of selected model descriptors showed interesting connections between the model results and the experimental background. A strong influence of the polarity of organic compounds on their degradability with high-frequency sonolysis could been quantified, as more nonpolar molecules are degraded faster. Additionally, the impact of specific fingerprints, including for example substituents with heteroatoms, the number of fused and non-fused aromatic rings as well as the numerical appearance of secondary carbon could be identified as relevant for this cavitation-based treatment method.

Zusammenfassung

Advanced oxidation processes are promising techniques for water remediation and degradation of micropollutants in aqueous systems. Since single processes such as sonolysis and photocatalysis exhibit limitations, combined AOP systems can enhance degradation efficiency. The present work addresses the synergistic intensification potential of an ultrasound-assisted photocatalysis (sonophotocatalysis) for bisphenol A degradation with a low-frequency sonotrode (f = 20 kHz) in a batch-system. The effects of energy input and suspended photocatalyst dosage (TiO2-nanoparticle, m = 0–0.5 g/L) were investigated. To understand the synergistic effects, the sonication characteristics were investigated by bubble-field analysis, hydrophone measurements, and chemiluminescence of luminol to identify cavitation areas due to the generation of hydroxyl radicals. Comparing the sonophotocatalysis with sonolysis and photocatalysis (incl. mechanical stirring), synergies up to 295% and degradation rates of up to 1.35 min−1 were achieved. Besides the proof of synergistic intensification, the investigation of energy efficiency for a degradation degree of 80% shows that a process optimization can be realized. Thus, it could be demonstrated that there is an effective limit of energy input depending on the TiO2 dosage.

Zusammenfassung

The endocrine disruptor bisphenol A (BPA) is one of the most commonly found micropollutants in the environment. However, the biodegradation of BPA under anaerobic (methanogenic) conditions is still an understudied process in wastewater treatment systems. The current study thus addresses the need for a simple and user-friendly analytical method for the rapid and accurate quantification of BPA in complex matrices such as digested and co-digester sludges. We established a microwave-assisted extraction method, followed by derivatization and gas chromatography–mass spectrometry to quantify BPA by comparing it with a deuterated internal standard. The BPA removal capabilities of three digester sludges and three co-digester sludges were examined under mesophilic methanogenic conditions in biogas plants. The endogenous BPA concentration (dry weight) ranged from 1596 to 10,973 µg kg−1 in digested sewage sludges, and from below the limit of quantification to 9069 µg kg−1 in co-digester sludges. When BPA was added to the sludges, the removal capabilities ranged from not significant to 50% after 21 days of incubation. Biogas production was unaffected by the addition of BPA (228 µg kg−1) to the aqueous sludge. The study demonstrated that BPA could be removed under anaerobic conditions in accustomed inoculates. The findings have far-reaching implications for understanding BPA persistence and detoxification under anaerobic conditions.

Zusammenfassung

Pyrocatalysis uses thermally excited pyroelectric materials for the generation of reactive oxygen species in water. This unique feature allows it to harvest energy in the form of natural temperature gradients or waste heat from industrial processes in order to degrade organic pollutants at low costs. Its further development into an advanced oxidation process for water remediation is dependent on the availability of pH-robust and nonspecific redox assays for the determination of its oxidation capability. Nevertheless, previous studies neglected the influence of pH changes and they were focused mainly on the degradation of one organic compound or specific chemical dosimetries. In this study, a pH-robust and nonspecific reaction protocol of the dichlorofluorescein assay was established for the investigation of the oxidation capability of the pyrocatalytic process. This reaction protocol was tested on three pyroelectric powders (LiNbO3, LiTaO3, BaTiO3) in different amounts and it overcomes major constraints of a previously used dichlorodihydrofluorescein diacetate-based reaction protocol. Instead of its diacetate, dichlorodihydrofluorescein was used as fluorogenic probe and its concentration was drastically reduced to 1 μM. For the first time, these changes enable the determination and comparison of the oxidation capability independently of pH-rising processes, which are present for all investigated pyroelectric powders up to a pH of 11. Additionally, the precision of the dichlorofluorescein assay was drastically increased and the determination and consideration of autoxidation processes was enabled. Of all three pyroelectric powders, BaTiO3 exhibited the highest oxidation capability with a linear increase with respect to the powder amount.

Zusammenfassung

Microplastics are ubiquitous in the environment. Due to still rising global production, the emission of polymers into the environment and the abundance of microplastics have increased accordingly. Due to the long mineralization processes of microplastics, distribution in all compartments can be found. The hydrophobic surfaces of the particles can sorb chemical pollutants, therefore providing a potential pathway to accumulation by organisms within the food web. However, little is known about how long-term aging and degradation processes of microplastics can affect the sorption behaviours of organic pollutants on the particles. In this study, important industrial additives of emerging environmental concern, such as hydrophobic aromatic amines, were studied in relation to their sorption behaviour on high-density polyethylene and low-density polyethylene microplastics. Diphenylamine (log POW (logarithmic octanol–water partition coefficient) = 3.5) showed strong sorption, carbamazepine (log POW = 2.5) showed moderate sorption, and aniline (log POW = 0.9) showed no detectable sorption behaviour. Artificially aged particles exposed to photochemical aging and long-term mechanical treatment in water were compared to pristine microplastics. While mechanically aged microplastics promoted the sorption of aromatic amines, photochemically aged particles showed a decrease in sorption capacity due to changed surface chemistry. Importantly, the sorption capacity increased with increasing salinity, leading to strong implications for ocean systems, as an elevated uptake of pollutants could occur under marine conditions. Moreover, our study demonstrates that the ecotoxicological effects of diphenylamine on the growth of the seaweed Ulva (sea lettuce, Chlorophyta) were reduced in the presence of microplastics. As the plastic particles withdrew enough contaminants from solution, even toxic levels of diphenylamine (c = 10−4 M) became tolerable for the algae. However, the pollutants initially sorbed on the microplastics can be released again at a later point in the ageing process, thus having delayed pollution potential.

Zusammenfassung

Pyrocatalysis is an emerging advanced oxidation process for wastewater remediation with the potential for thermal energy harvesting and utilization. Although several studies explored the potential of new pyrocatalyst materials to degrade harmful organic water pollutants, the role of important material properties and electric poling procedures on the pyrocatalytic activity is still unclear. In this work, we investigate the interdependence between particle size, electric poling and pyrocatalytic activity of BaTiO3 powders with nominal particle sizes of 100, 200 and 500 nm by using the dichlorofluorescein redox assay. Depending on the particle size, the influence of surface area or phase composition on the pyrocatalytic activity predominates. Moreover, we demonstrate that poling of pyrocatalysts leads to a strong size-dependent increase of pyrocatalytic activity. This poling effect increases with particle size up to +247% and can be explained with size-dependent changes in phase composition and domain structure. Combining all results, the progression of the pyrocatalytic activity as a function of particle size was derived and a future strategy for maximizing the catalytic performance of pyrocatalysts was developed. This study greatly improves the understanding about the role of important material properties and electric poling on pyrocatalytic activity, thus enabling an effective catalyst design. With the help of highly active catalysts, the pyrocatalytic process can take the next step in its development into a new and energy-efficient advanced oxidation process for water remediation.

Zusammenfassung

The pyro-electro-catalytic induced generation of hydrogen gas is an environmentally friendly and sustainable way to convert excess thermal energy into a storable form. The main idea is to make use of spontaneous polarization of pyroelectric materials that can be altered by temperature changes. Thus, surface potential changes and subsequent electron exchange with surrounding molecules can be induced. In this work, a fundamental model to describe the behavior of a thermally excited pyroelectric material in pure water is developed. The model combines the fields of pyroelectricity, electrochemistry, diffusion and semiconductor theory. After derivation, it was used to explore some basic questions on pyro-electro-catalytic hydrogen production and the accuracy was tested with experimental data. The results show that p/εr has to be balanced depending on the temperature gradient to maximize the hydrogen production. The validation of the experimental data revealed good agreement.