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Institute
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.
Groundwater is essential for the provision of drinking water in many areas around the world. The ecosystem services provided by groundwater-related organisms are crucial for the quality of groundwater-bearing aquifers. Therefore, if remediation of contaminated groundwater is necessary, the remediation method has to be carefully selected to avoid risk-risk trade-offs that might impact these valuable ecosystems. In the present thesis, the ecotoxicity of the in situ remediation agent Carbo-Iron (a composite of zero valent nano-iron and active carbon) was investigated, an estimation of its environmental risk was performed, and the risk and benefit of a groundwater remediation with Carbo-Iron were comprehensively analysed.
At the beginning of the work on the present thesis, a sound assessment of the environmental risks of nanomaterials was impeded by a lack of guidance documents, resulting in many uncertainties on selection of suitable test methods and a low comparability of test results from different studies with similar nanomaterials. The reasons for the low comparability were based on methodological aspects of the testing procedures before and during the toxicity testing. Therefore, decision trees were developed as a tool to systematically decide on ecotoxicity test procedures for nanomaterials. Potential effects of Carbo-Iron on embryonic, juvenile and adult life stages of zebrafish (Danio rerio) and the amphipod Hyalella azteca were investigated in acute and chronic tests. These tests were based on existing OECD and EPA test guidelines (OECD, 1992a, 2013a, 2013b; US EPA, 2000) to facilitate the use of the obtained effect data in the risk assessment. Additionally, the uptake of particles into the test organisms was investigated using microscopic methods. In zebrafish embryos, effects of Carbo-Iron on gene expression were investigated. The obtained ecotoxicity data were complemented by studies with the waterflea Daphnia magna, the algae Scenedesmus vacuolatus, larvae of the insect species Chironomus riparius and nitrifying soil microorganisms.
In the fish embryo test, no passage of Carbo-Iron particles into the perivitelline space or the embryo was observed. In D. rerio and H. azteca, Carbo-Iron was detected in the gut at the end of exposure, but no passage into the surrounding tissue was detected. Carbo-Iron had no significant effect on soil microorganisms and on survival and growth of fish. However, it had significant effects on the growth, feeding rate and reproduction of H. azteca and on survival and reproduction in D. magna. Additionally, the development rate of C. riparius and the cell volume of S. vacuolatus were negatively influenced.
A predicted no effect concentration of 0.1 mg/L was derived from the ecotoxicity studies based on the no-effect level determined in the reproduction test with D. magna and an assessment factor of 10. It was compared to measured and modelled environmental concentrations for Carbo-Iron after application to an aquifer contaminated with chlorohydrocarbons in a field study. Based on these concentrations, risk quotients were derived. Additionally, the overall environmental risk before and after Carbo-Iron application was assessed to verify whether the chances for a risk-risk trade-off by the remediation of the contaminated site could be minimized. With the data used in the present study, a reduced environmental risk was identified after the application of Carbo-Iron. Thus, the benefit of remediation with Carbo-Iron outweighs potential negative effects on the environment.
Assessment of bat activity in agricultural environments and the evaluation of the risk of pesticides
(2013)
Although agriculture dominates with around 50% area much of Europe- landscape, there is virtually no information on how bats use this farmed environment for foraging. Consequently, little is known about effective conservation measures to compensate potential negative effects of agrarian management practice on the food availability for bats in this habitat. Moreover, there are currently no specific regulatory requirements to include bats in European Union risk assessments for the registration of pesticides since no information about pesticide exposure on this mammal group is available. To evaluate the potential pesticide exposure of bats via ingestion of contaminated insects, information about bat presence and activity in agricultural habitats is required. In order to examine bat activity on a landscape scale it was necessary to establish a suitable survey method. Contrary to capture methods, telemetry, and direct observations, acoustic surveys of bat activity are a logistically feasible and cost-effective way of obtaining bat activity data. However, concerns regarding the methodological designs of many acoustic surveys are expressed in the scientific literature. The reasons are the failing of addressing temporal and spatial variation in bat activity patterns and the limitations of the suitability of the used acoustic detector systems. By comparing different methods and detector systems it was found that the set up of several stationary calibrated detector systems which automatically trigger the ultrasonic recording has the highest potential to produce reliable, unbiased and comparable data sets on the relative activity of bats.
By using the proposed survey method, bat diversity and activity was recorded in different crops and semi-natural habitats in southern Rhineland-Palatinate. Simultaneously, the availability of aerial prey insects was studied by using light and sticky traps. In more than 500 sampling nights about 110,000 call sequences were acoustically recorded and almost 120,000 nocturnal insects were sampled. A total of 14 bat species were recorded, among them the locally rare and critically endangered northern bat (Eptesicus nilssonii) and the barbastelle (Barbastella barbastellum), all of them also occurring over agricultural fields. The agricultural landscape of southern Palatinate is dominated by vineyards, a habitat that was shown to be of low quality for most bat species because of the demonstrated low availability of small aerial insects. By surveying bat activity and food availably in a pair-wise design on several rain water retention ponds and neighbouring vineyards it was demonstrated that aquatic insect emergence in artificial wetlands can provide an important resource subsidy for bats. The creation of artificial wetlands would be a possibility to create important foraging habitats for bats and mitigate negative effects of management practice in the agricultural landscape.
In several other agricultural crops, however, high abundances of suitable prey insects and high bat activity levels, comparable or even higher than in the nearby forests and meadows known to be used as foraging habitats were demonstrated. Especially high bat activity levels were recorded over several fruit orchards and vegetable fields where insects were also present. Both crops are known for high pesticide inputs, and, therefore, a pesticide exposure through ingestion of contaminated insects can not be excluded. To follow the current risk assessment approach for birds and mammals pesticide residues were measured on bat-specific food items in an apple orchard following insecticide applications and bat activity was recorded in parallel. The highest residue values were measured on foliage-dwelling arthropods which may results in a reproductive risk for all bat species that, even to a small extent, include this prey group in their diet. The presence of bats in agricultural landscapes that form a majority of the land area in Europe but also on a global scale leads to exposure of bats by contaminated food and depletion of their food resources by pesticide use. So far conservation efforts for bats focussed on securing hibernation sites and the creation of artificial roost sites since especially the latter were thought to be limiting population growth. However the potential pesticide effects might be also crucial for the population persistence in agricultural landscapes of bats and need to be addressed adequately, especially in risk assessment procedures for the regulation of pesticides.