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The intention of this thesis was to characterise the effect of naturally occurring multivalent cations like Calcium and Aluminium on the structure of Soil Organic Matter (SOM) as well as on the sorption behaviour of SOM for heavy metals such as lead.
The first part of this thesis describes the results of experiments in which the Al and Ca cation content was changed for various samples originated from soils and peats of different regions in Germany. The second part focusses on SOM-metal cation precipitates to study rigidity in dependence of the cation content. In the third part the effects of various cation contents in SOM on the binding strength of Pb cations were characterised by using a cation exchange resin as desorption method.
It was found for soil and peat samples as well as precipitates that matrix rigidity was affected by both type and content of cation. The influence of Ca on rigidity was less pronounced than the influence of Al and of Pb used in the precipitation experiments. For each sample one cation content was identified where matrix rigidity was most pronounced. This specific cation content is below the cation saturation as expected by cation exchange capacity. These findings resulted in a model describing the relation between cation type, content and the degree of networking in SOM. For all treated soil and precipitate samples a step transition like glass transition was observed, determined by the step transition temperature T*. It is known from literature that this type of step transition is due to bridges between water molecules and organic functional groups in SOM. In contrast to the glass transition temperature this thermal event is slowly reversing after days or weeks depending on the re-conformation of the water molecules. Therefore, changes of T* with different cation compositions in the samples are explained by the formation of water-molecule-cation bridges between SOM-functional groups. No influence on desorption kinetics of lead for different cation compositions in soil samples was observed. Therefore it can be assumed that the observed changes of matrix rigidity are highly reversible by changing the water status, pH or putting agitation energy by shaking in there.
The increasing, anthropogenic demand for chemicals has created large environmental problems with repercussions for the health of the environment, especially aquatic ecosystems. As a result, the awareness of the public and decision makers on the risks from chemical pollution has increased over the past half-century, prompting a large number of studies in the field of ecological toxicology (ecotoxicology). However, the majority of ecotoxicological studies are laboratory based, and the few studies extrapolating toxicological effects in the field are limited to local and regional levels. Chemical risk assessment on large spatial scales remains largely unexplored, and therefore, the potential large-scale effects of chemicals may be overlooked.
To answer ecotoxicological questions, multidisciplinary approaches that transcend classical chemical and toxicological concepts are required. For instance, the current models for toxicity predictions - which are mainly based on the prediction of toxicity for a single compound and species - can be expanded to simultaneously predict the toxicity for different species and compounds. This can be done by integrating chemical concepts such as the physicochemical properties of the compounds with evolutionary concepts such as the similarity of species. This thesis introduces new, multidisciplinary tools for chemical risk assessments, and presents for the first time a chemical risk assessment on the continental scale.
After a brief introduction of the main concepts and objectives of the studies, this thesis starts by presenting a new method for assessing the physiological sensitivity of macroinvertebrate species to heavy metals (Chapter 2). To compare the sensitivity of species to different heavy metals, toxicity data were standardized to account for the different laboratory conditions. These rankings were not significantly different for different heavy metals, allowing the aggregation of physiological sensitivity into a single ranking.
Furthermore, the toxicological data for macroinvertebrates were used as input data to develop and validate prediction models for heavy metal toxicity, which are currently lacking for a wide array of species (Chapter 3). Apart from the toxicity data, the phylogenetic information of species (evolutionary relationships among species) and the physicochemical parameters for heavy metals were used. The constructed models had a good explanatory power for the acute sensitivity of species to heavy metals with the majority of the explained variance attributed to phylogeny. Therefore, the integration of evolutionary concepts (relatedness and similarity of species) with the chemical parameters used in ecotoxicology improved prediction models for species lacking experimental toxicity data. The ultimate goal of the prediction models developed in this thesis is to provide accurate predictions of toxicity for a wide range of species and chemicals, which is a crucial prerequisite for conducting chemical risk assessment.
The latter was conducted for the first time on the continental scale (Chapter 4), by making use of a dataset of 4,000 sites distributed throughout 27 European countries and 91 respective river basins. Organic chemicals were likely to exert acute risks for one in seven sites analyzed, while chronic risk was prominent for almost half of the sites. The calculated risks are potentially underestimated by the limited number of chemicals that are routinely analyzed in monitoring programmes, and a series of other uncertainties related with the limit of quantification, the presence of mixtures, or the potential for sublethal effects not covered by direct toxicity.
Furthermore, chemical risk was related to agricultural and urban areas in the upstream catchments. The analysis of ecological data indicated chemical impacts on the ecological status of the river systems; however, it is difficult to discriminate the effects of chemical pollution from other stressors that river systems are exposed to. To test the hypothesis of multiple stressors, and investigate the relative importance of organic toxicants, a dataset for German streams is used in chapter 5. In that study, the risk from abiotic (habitat degradation, organic chemicals, and nutrients enrichment) and biotic stressors (invasive species) was investigated. The results indicated that more than one stressor influenced almost all sites. Stream size and ecoregions influenced the distribution of risks, e.g., the risks for habitat degradation, organic chemicals and invasive species increased with the stream size; whereas organic chemicals and nutrients were more likely to influence lowland streams. In order to successfully mitigate the effects of pollutants in river systems, co-occurrence of stressors has to be considered. Overall, to successfully apply integrated water management strategies, a framework involving multiple environmental stressors on large spatial scales is necessary. Furthermore, to properly address the current research needs in ecotoxicology, a multidisciplinary approach is necessary which integrates fields such as, toxicology, ecology, chemistry and evolutionary biology.
Ein grundlegendes Verständnis der Anlagerung von künstlich hergestellten Nanopartikeln ist für die Prognose des Schicksals und Transports von Nanopartikeln in der Umwelt unerlässlich.
In dieser Arbeit wurde die Anlagerung von unbedeckten und mit Citrat bedeckten Silbernanopartikeln an unterschiedliche Modell- und Umweltoberflächen in An- und Abwesenheit der Huminsäure untersucht.
Für diese Untersuchungen wurden Sorptionsexperimente durchgeführt. Das Ziel dieser Arbeit ist es zu untersuchen, wie die Silbernanopartikel mit Oberflächen wechselwirken, die verschiedene chemische funktionelle Gruppen besitzen. Dabei wurde ebenfalls der Effekt der Huminsäure auf die Wechselwirkungen zwischen Partikel und Oberfläche untersucht. Die Wechselwirkungen zwischen Nanopartikel und Oberfläche sind in Abwesenheit der Huminsäure wahrscheinlich durch die chemische Natur der wechselwirkenden Oberflächen beeinflusst. In Anwesenheit der Huminsäure wurde diese chemische Sensitivität gegen Anlagerung von Nanopartikeln nicht beobachtet und die Sorption war durch die spezifische Oberfläche von Sorbentien beeinflusst. Die Sorptionsisothermen wurden für die Sorption von Silbernanopartikeln an allen Oberflächen in Abwesenheit der Huminsäure durch Langmuir-Modell beschrieben. Das deutete auf Monoschicht-Sorption der Nanopartikel an Oberflächen hin. Das kann durch den bei der Partikel-Partikel-Abstoßung generierten blockierenden Effekt erklärt werden. In Anwesenheit der Huminsäure zeigten alle Sorptionsisothermen ein lineares Verhalten. Wenn die Huminsäure im Wechselwirkungsmedium vorhanden war, waren die Nanopartikel und Oberflächen mit Huminsäure bedeckt. Dadurch wird die chemische Funktionalität von Oberflächen maskiert. Das führt zu den Unterschieden zwischen Partikel-Oberfläche-Wechselwirkungen in An- und Abwesenheit der Huminsäure. Die mit Citrat und Huminsäure bedeckten Silbernanopartikel zeigten eine Abnahme der Sorption an Oberflächen im Vergleich zu unbedeckten Silbernanopartikeln. Im Falle der mit Citrat bedeckten Silbernanopartikel kann die Abnahme der Sorption durch elektrostatische Kräfte erklärt werden, da diese Partikel ein mehr negatives Zetapotential zeigten. Die Sorptionsabnahme für die mit Huminsäure bedeckten Nanopartikel ist offensichtlich eine Folge der sterischen Behinderung, da es auf Grund der Sorption der Huminsäure an Oberflächen zur Konkurrenz zwischen Nanopartikeln und Huminsäuremolekülen für die Sorptionsplätze kommt. Durch die chemischen Eigenschaften der Nanopartikeloberfläche wird die Effizienz der Anlagerung an Oberflächen beeinflusst. Deswegen ist die Charakterisierung der Nanopartikeloberfläche ein wichtiger Schritt bei der Untersuchung des Schicksals von Nanopartikeln in der Umwelt.
Ein anderes Ziel dieser Arbeit ist es das Potential der chemischen Kraftmikroskopie für die Charakterisierung von Nanopartikeloberflächen mit chemischer Sensitivität zu zeigen. Durch die Anwendung dieser Methode war es möglich zwischen unbedeckten, mit Citrat und Huminsäure bedeckten Silbernanopartikeln zu unterscheiden. Das wurde durch die Messung der Adhäsionskräfte zwischen Nanopartikeln und fünf verschiedenen Atomkraftmikroskope-Spitzen mit unterschiedlichen chemischen Funktionalisierungen ermöglicht.