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Water scarcity is already an omnipresent problem in many parts of the world, especially in sub-Saharan Africa. The dry years 2018 and 2019 showed that also in Germany water resources are finite. Projections and predictions for the next decades indicate that renewal rates of existing water resources will decline due the growing influence of climate change, but that water extraction rates will increase due to population growth. It is therefore important to find alternative and sustainable methods to make optimal use of the water resources currently available. For this reason, the reuse of treated wastewater for irrigation and recharge purposes has become one focus of scientific research in this field. However, it must be taken into account that wastewater contains so-called micropollutants, i.e., substances of anthropogenic origin. These are, e.g., pharmaceuticals, pesticides and industrial chemicals which enter the wastewater, but also metabolites that are formed in the human body from pharmaceuticals or personal care products. Through the treatment in wastewater treatment plants (WWTPs) as well as through chemical, biological and physical processes in the soil passage during the reuse of water, these micropollutants are transformed to new substances, known as transformation products (TPs), which further broaden the number of contaminants that can be detected within the whole water cycle.
Despite the fact that the presence of human metabolites and environmental TPs in untreated and treated wastewater has been known for a many years, they are rarely included in common routine analysis methods. Therefore, a first goal of this thesis was the development of an analysis method based on liquid chromatography - tandem mass spectrometry (LC-MS/MS) that contains a broad spectrum of frequently detected micropollutants including their known metabolites and TPs. The developed multi-residue analysis method contained a total of 80 precursor micropollutants and 74 metabolites and TPs of different substance classes. The method was validated for the analysis of different water matrices (WWTP influent and effluent, surface water and groundwater from a bank filtration site). The influence of the MS parameters on the quality of the analysis data was studied. Despite the high number of analytes, a sufficient number of datapoints per peak was maintained, ensuring a high sensitivity and precision as well as a good recovery for all matrices. The selection of the analytes proved to be relevant as 95% of the selected micropollutants were detected in at least one sample. Several micropollutants were quantified that were not in the focus of other current multi-residue analysis methods (e.g. oxypurinol). The relevance of including metabolites and TPs was demonstrated by the frequent detection of, e.g., clopidogrel acid and valsartan acid at higher concentrations than their precursors, the latter even being detected in samples of bank filtrate water.
By the integration of metabolites, which are produced in the body by biological processes, and biological and chemical TPs, the multi-residue analysis method is also suitable for elucidating degradation mechanisms in treatment systems for water reuse that, e.g., use a soil passage for further treatment. In the second part of the thesis, samples from two treatment systems based on natural processes were analysed: a pilot-scale above-ground sequential biofiltration system (SBF) and a full-scale soil aquifer treatment (SAT) site. In the SBF system mainly biological degradation was observed, which was clearly demonstrated by the detection of biological TPs after the treatment. The efficiency of the degradation was improved by an intermediate aeration, which created oxic conditions in the upper layer of the following soil passage. In the SAT system a combination of biodegradation and sorption processes occurred. By the different behaviour of some biodegradable micropollutants compared to the SBF system, the influence of redox conditions and microbial community was observed. An advantage of the SAT system over the SBF system was found in the sorption capacity of the natural soil. Especially positively charged micropollutants showed attenuation due to ionic interactions with negatively charged soil particles. Based on the physicochemical properties at ambient pH, the degree of removal in the investigated systems and the occurrence in the source water, a selection of process-based indicator substances was proposed.
Within the first two parts of this thesis a micropollutant was frequently detected at elevated concentrations in WWTPs effluents, which was not previously in the focus of environmental research: the antidiabetic drug sitagliptin (STG). STG showed low degradability in biological systems and thus it was investigated to what extend chemical treatment by ozonation can ensure attenuation of it. STG contains an aliphatic primary amine as the principal point of attack for the ozone molecule. There is only limited information about the behaviour of this functional group during ozonation and thus, STG served as an example for other micropollutants containing aliphatic primary amines. A pH-dependent degradation kinetic was observed due to the protonation of the primary amine at lower pH values. At pH values in the range 6 - 8, which is typical for the environment and in WWTPs, STG showed degradation kinetics in the range of 103 M-1s-1 and thus belongs to the group of readily degradable substances. However, complete degradation can only be expected at significantly higher pH values (> 9). The transformation of the primary amine moiety into a nitro group was observed as the major degradation mechanism for STG during ozonation. Other mechanisms involved the formation of a diketone, bond breakages and the formation of trifluoroacetic acid (TFA). Investigations at a pilot-scale ozonation plant using the effluent of a biological degradation of a municipal WWTP as source water confirmed the results of the laboratory studies: STG could not be removed completely even at high ozone doses and the nitro compound was formed as the main TP and remained stable during further ozonation and subsequent biological treatment. It can therefore be assumed that under realistic conditions both a residual concentration of STG and the formed main TP as well as other stable TPs such as TFA can be detected in the effluents of a WWTP consisting of conventional biological treatment followed by ozonation and subsequent biological polishing steps.