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- Institut für Umweltwissenschaften (3) (remove)
Perfluorocarboxylic acids (PFCA) are substances of anthropogenic origin and have been used for several decades. These compounds are a new class of environmental pollutants. Their high surface activity, thermal stability, amphipathicity and weak intermolecular interactions lead to persistence and bioaccumulation. Therefore, there is a great need for reliable analytical methods for detecting the presence and determination of concentration in both environmental samples and everyday products. GC-MS is a cost-effective alternative and supplement to established LC-MS/MS methods. The greatest challenge in the method development is the derivatization reaction. Many of the previously published derivatization reactions for PFCA are time consuming and require high reaction temperatures or toxic reagents.
In the present dissertation, two new derivatization reactions for PFCA have been developed and optimized. The first part of the thesis shows the development and optimization of the reaction with triethylsilanol in water. In addition to optimizing the reaction, classical solid-phase extraction was modified to simplify the sample preparation.
In the second part of the work, the reaction products of perfluorooctanoic acid (PFOA) with N,N-dimethylformamide dimethyl acetal (DMF-DMA) and -diethyl acetal (DMF-DEA) were identified. From these measurements, it follows that both DMF-DMA and DMF-DEA in the presence of PFOA form an iminium cation, which leads to salt formation. This PFOA salt react further in the GC injector and a corresponding amine is produced.
In the last part of the thesis, an analytical method based on the DMF-DMA reaction was developed. The matrix effects have been described in detail. The method has been successfully applied for three different types of samples: dental floss, textiles and sewage sludge. The results were verified by LC-MS/MS analysis in an external laboratory. The differences between the PFCA values for a spiked sample measured by GC-MS and LC-MS/MS were less than 10%.
Stream ecosystems are one of the most threatened ecosystems worldwide due to their exposure to diverse anthropogenic stressors. Pesticides appear to be the most relevant stressor for agricultural streams. Due to the current mismatch of modelled and measured pesticide concentrations, monitoring is necessary to inform risk assessment or improve future pesticide approvals. Knowing if biotic stress responses are similar across large scales and long time frames could ultimately help in estimating protective stressor thresholds.
This thesis starts with an overview of entry pathways of pesticides to streams as well as the framework of current pesticide monitoring and gives an outline of the objectives of the thesis. In chapter 2, routine monitoring data based on grab sampling from several countries is analysed to identify the most frequently occurring pesticide mixtures. These mixtures are comprised of relatively low numbers of pesticides, of which herbicides are dominating. The detected pesticide mixtures differ between regions and countries, due to differences in the spectrum of analysed compounds and limits of quantification. Current routine monitoring does not include sampling during pesticide peaks associated with heavy rainfall events which likely influences the detected pesticide mixtures. In chapter 3, sampling rates of 42 organic pesticides for passive sampling are provided together with recommendations for the monitoring of field-relevant peaks. Using this information, in chapter 4 a pesticide gradient is established in an Eastern European region where agricultural intensity adjacent to sampled streams ranges from low to high. In contrast to current routine monitoring, rainfall events were sampled and a magnitude of pesticides were analysed. This led to the simultaneous detection of numerous pesticides of which one to three drive the pesticide toxicity. The toxicity, however, showed no relationship to the agricultural intensity. Using microcosms, the stress responses of fungal communities, the hyphomycetes, and the related ecosystem function of leaf decomposition, is investigated in chapter 5. Effects of a field-relevant fungicide mixture are examined across three biogeographical regions for three consecutive cycles of microbial leaf colonisation and decomposition. Despite different initial communities, stress responses as well as recoveries were similar across biogeographical regions, indicating a general pattern.
Overall, this thesis contributes to an improved understanding of occurrence and concentrations of pesticides mixtures in streams, their monitoring and impact on an ecosystem function. We showed that estimated pesticide toxicities reach levels that affect non-target organisms and thereby potentially whole ecosystems. Routine monitoring, however, likely underestimates the threat by pesticides. Effects leading to a loss in biodiversity or functions in streams ecosystems can be reduced by reassessing approved pesticides with ongoing targeted monitoring and increased knowledge of effects caused by these pesticides.
Environmental processes transforming inorganic nanoparticles: implications on aquatic invertebrates
(2020)
Engineered inorganic nanoparticles (EINPs) are produced and utilized on a large scale and will end up in surface waters. Once in surface waters, EINPs are subjected to transformations induced by environmental processes altering the particles’ fate and inherent toxicity. UV irradiation of photoactive EINPs is defined as one effect-inducing pathway, leading to the formation of reactive oxygen species (ROS), increasing EINP toxicity by exerting oxidative stress in aquatic life. Simultaneously, UV irradiation of photoactive EINP alters the toxicity of co-occurring micropollutants (e.g. pesticides) by affecting their degradation. The presence of natural organic matter (NOM) reduces the agglomeration and sedimentation of EINPs, extending the exposure of pelagic species, while delaying the exposure of benthic species living in and on the sediment, which is suggested as final sink for EINPs. However, the joint impact of NOM and UV irradiation on EINP-induced toxicity, but also EINP-induced degradation of micropollutants, and the resulting risk for aquatic biota, is poorly understood. Although potential effects of EINPs on benthic species are increasingly investigated, the importance of exposure pathways (waterborne or dietary) is unclear, along with the reciprocal pathway of EINPs, i.e. the transport back from aquatic to terrestrial ecosystems. Therefore, this thesis investigates: (i) how the presence of NOM affects the UV-induced toxicity of the model EINP titanium dioxide (nTiO2) on the pelagic organism Daphnia magna, (ii) to which extent UV irradiation of nTiO2 in the presence and absence of NOM modifies the toxicity of six selected pesticides in D. magna, (iii) potential exposure pathway dependent effects of nTiO2 and silver (nAg) EINPs on the benthic organism Gammarus fossarum, and (iv) the transport of nTiO2 and gold EINPs (nAu) via the merolimnic aquatic insect Chaetopteryx villosa back to terrestrial ecosystems. nTiO2 toxicity in D. magna increased up to 280-fold in the presence of UV light, and was mitigated by NOM up to 12-fold. Depending on the pesticide, UV irradiation of nTiO2 reduced but also enhanced pesticide toxicity, by (i) more efficient pesticide degradation, and presumably (ii) formation of toxic by-products, respectively. Likewise, NOM reduced and increased pesticide toxicity, induced by (i) protection of D. magna against locally acting ROS, and (ii) mitigation of pesticide degradation, respectively. Gammarus’ energy assimilation was significantly affected by both EINPs, however, with distinct variation in direction and pathway dependence between nTiO2 and nAg. EINP presence delayed C. villosa emergence by up to 30 days, and revealed up to 40% reduced lipid reserves, while the organisms carried substantial amounts of nAu (~1.5 ng/mg), and nTiO2 (up to 2.7 ng/mg). This thesis shows, that moving test conditions of EINPs towards a more field-relevant approach, meaningfully modifies the risk of EINPs for aquatic organisms. Thereby, more efforts need to be made to understand the relative importance of EINP exposure pathways, especially since a transferability between different types of EINPs may not be given. When considering typically applied risk assessment factors, adverse effects on aquatic systems might already be expected at currently predicted environmental EINP concentrations in the low ng-µg/L range.