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Erscheinungsjahr
- 2015 (3) (entfernen)
Schlagworte
- Biodegradation (2)
- Anticancer Drug (1)
- Aquatic environment (1)
- Energieeffizienz (1)
- Hydrological tracers (1)
- Pesticide formulation (1)
- Photodegradation (1)
- Photolysis (1)
- Thermal energy storage (1)
- Toxicity (1)
Institut
- Institut für Nachhaltige Chemie und Umweltchemie (INUC) (3) (entfernen)
Uranine (sodium fluorescein, UR) has been routinely used in hydrological research to monitor surface and subsurface water flow, transport and mixing processes since the end of nineteenth century. Based on such obtained data, further conclusions can be drawn on the spread and behavior of pollutants (partly on models). Use of UR for qualitative (visual) studies of underground contamination is common, however data available on its environmental behavior (e.g., conversion, degradation or formation and fate of the transformation products, TPs) are incomplete or not readily comparable. UR observations of biodegradation are still speculative. S-metolachlor (SM) is a popular worldwide chloroacetamide herbicide, which highly correspond to the global pesticide use. It is offered on the French market as an effective multicrop herbicide against annual grasses and certain broadleaf weeds under the trade name Mercantor Gold (MG). Photodegradation contributes to the fate of SM in the aquatic environment. TPs were already found in surface and groundwater. However, further fate and assessment of the TPs was not done. Moreover, adjuvants in MG´s formula can affect the solubility, biodegradation, photolysis and sorption properties of the active compound SM. TPs can have different properties (e.g. more mobile, toxic or present at higher concentrations) that enable them to reach the environmental compartments not affected by the parent compound (PC) itself. To assess the ecological impact of pesticides, tracers, and their respective TPs on water organisms, their behavior can be investigated in laboratory screening biodegradation tests. Yet, incomplete data was available on SM, MG and UR transformation or their photo- TPs´ fate in surface and water-sediment systems. The combination of photolysis with aerobic biodegradation in order to identify persistent photo-TPs could provide new insight into the environmental behavior of the selected compounds. Therefore, principle of this thesis was to 1) identify the impact of MG´s adjuvants on the biodegradation, photolysis (Xe lamp) and sorption compared to the SM alone, 2) examine the photolysis and biodegradability of UR 3) monitor the primary elimination (photolysis) of the PCs by HPLC (-UV, -FLD) and measure the degree of mineralization by means of nonpurgeable organic carbon (NPOC) 4) elucidate the photo-TPs of SM, MG and UR by using LCMS/ MS 5) analyze biodegradability of the photo-TPs in order to determine their fate and persistence in aquatic environment 6) conduct in silico toxicity predictions (pesticides) in human (carcinogenicity, genotoxicity and mutagenicity) and eco-toxicity (microtoxicity, bioconcentration factor and toxicity in rainbow trouts). SM, MG and UR were found not readily biodegradable in Closed Bottle test (CBT), Manometric Respiratory test (MRT) and in water-sediment test (WST). Chemical analysis of photolysis samples showed higher elimination of SM in MG compared to SM alone whereas UR displayed high primary elimination rate in general. The overall low degree of mineralization indicated that abundant photo-TPs were formed. Furthermore, the photo-TPs were found not biodegradable in performed biodegradation tests. Only small degradation rates for UR could be observed in the CBT and WST. Additionally, in the MRT and WST new bio-TPs were generated from the photo-TPs of SM and SM in MG. Obtained results suggest that the MG formulation did not significantly affect the biodegradation, however it influenced the diffusion of the active substance (SM) to sediment and potentially affected the photolysis efficiency, which might result in faster formation of photo-TPs in the environment. In silico predictions showed that for many endpoints, biotransformation might lead to an increased toxicity in humans and to water organisms compared with the parent compound SM. No indications were found for UR toxicity. Still, target-oriented investigations on long term impacts of photo-TPs from UR are warranted. The present work demonstrates that a combination of laboratory tests, analytical analysis and in silico tools result in valuable information regarding environmental fate of the TPs from selected compounds. Furthermore, it was shown that photo-TPs formed in the aquatic environment should be taken into account not only the parent compound and its decay.
In the discourse on pharmaceuticals in the environment, hardly any attention has been paid to anticancer drugs. Because of their none-selective modes of action, that is, because they affect both cancerous and healthy cells, these drugs are regarded as potentially carcinogenic, genotoxic, mutagenic, and teratogenic substances. It is, however, not known how and to what extent these substances affect organisms and the environment in the long run. For this reason, this dissertation evaluated, addressing several endpoints and using organisms from different trophic levels and in silico predictions, the fate (bio- and photo degradation) and ecotoxicity of these substances. Four anticancer drugs (cyclophosphamide (CP), 5-fluorouracil (5-FU), methotrexate (MTX), and imatinib (IM) were selected. None of these anticancer compounds can be classified as ´readily biodegradable,´ a classification that indicates that biodegradation will only play a minor role in the elimination of these compounds and that they cannot be removed by the conventional processes used in sewage treatment plants and will most likely remain in the water cycle. Despite the high degrees of mineralization achieved in advanced (photo)oxidation processes, it was not possible to fully mineralize the compounds, a result that indicates that transformation products were created during these reactions. The ecotoxicity assays performed with V. fischeri indicated that 5-FU was, of all the substances tested, likely to be the most toxic (very toxic), followed by MTX (toxic) and IM (toxic/harmful), whereas CP was nontoxic. MTX presented the highest phytoxicity activity in the Lactuca sativa assay, followed by 5-FU, IM, and CP. The results of the tests performed with A. cepa showed cytotoxic (5-FU, MTX, and CP) and genotoxic effects (5-FU, CP, and IM) and mutagenic activity (5-FU, MTX, CP, and IM) of the compounds. Photo transformation products (PTPs) of CP, MTX, and 5-FU were nontoxic towards V. fischeri. However, some PTPs formed during the photodegradation of 5-FU led to positive mutagenic and genotoxic alerts in several in silico models. Not one of the compounds examined in this dissertation is likely to be fully eliminated from the water cycle by (natural) photolysis and/or advanced oxidation. Moreover, some of the treatments resulted in the formation of stable intermediates that were even less biodegradable than parent compounds. This finding shows that it is not enough to focus on primary elimination because TPs are not necessarily better biodegradable than their respective parent compounds. As indicated by the genotoxic and mutagenic positive alerts presented by different in silico models, the PTPs observed here are likely to require, despite their lower toxicity in comparison to the parent compounds, screening after treatments.
Heating is most important part of thermal energy demand, and accounts for large amounts ofenergy consumption in cold regions. Renewable energy sources will be of great importance inorder to cover future energy demands. However, their intermittency is rightly considered asinconvenient. Thus, a more effective management of demand, coupled with efficient storagesystems is required. Based on this perception, thermal systems coupled with electricityproduction have been efficiently designed, they are the so called “combined heat and power”(micro-CHP). Nonetheless, heat losses from the thermal part of their system lead to electricityfluctuation. Therefore, the use of micro-CHP in combination with a volume-efficient and nearlylossless heat storage system to counteract electricity fluctuations is a viable solution.The heat storage system in this work is based on reversible thermochemical reactions, suchas dehydration and hydration of inorganic salts, which exhibits very high energy density (up to628 kWh·m-3 of storage material). The chosen inorganic salt (SrBr2·6H2O) reacting with purewater vapour operates within a closed system. The objective of this work is to design a systemthat thermodynamically matches the combination with micro-CHP. Therefore, investigationshave been performed from the material at micro-scale to the system at lab-scale. Models weredeveloped on the basis of heat and mass transfer with chemical reaction and were done in orderto numerically analyse the system. Experiments were additionally performed to consolidate thenumerical tools for future studies. Characterization experiments have been designed and tested.Thermo-physical properties (thermal conductivity, specific heat capacity, permeability, chemicalkinetics) of the reactive salt were then determined to be used as parameters into the sodeveloped models.The numerical simulations lead to the time-space evolution of heating fluid, reactive bedtemperatures and reactor pressure. The originality of this study is to model the coupled heat andmass transfer with chemical reaction on a 3D geometry to be close to the reality. Results help tonumerically and experimentally analyse the thermochemical heat storage performances. Thebed energy density is experimentally found to be 531 kWh·m-3 of salt hydrate. Based on thecondensation temperature during the experimentation, a reactor energy density of 140 kWh·m-3and a storage capacity of 65 kWh with a thermal efficiency of 0.78 are obtained. This systemproves the recovery capacity of more than 2/3 of the input energy. Various aspects of design andrecommendation for optimisation aspect that could help during prototype development aretaken into account and addressed. Comparison simulation-experiment is then performed anddiscussed, showing encouraging results, even if limited at lab-scale.