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The sediments of surface waters are temporary or final depository of many chemical compounds, including trace metals and metalloids (metal(loid)s) from natural and anthropogenic sources. Whether they act as a source or sink of metal(loid)s depends strongly on the dynamics of the biogeochemical processes that take place at the sediment-water interface (SWI). Important information on biogeochemical processes as well as on the exposure, the fate and the transport of pollutants at the SWI can be obtained by determining chemical concentration profiles in the sediment pore water. A major challenge is to conduct experiments with a spatial resolution, which allows to adequately record existing gradients and to log all the parameters needed, to describe and better understand the complex processes at the SWIs. At the same time, it is from major importance to prevent the formation of any artifacts during sampling, which may occur due to the labile nature of the SWIs and the very steep biogeochemical gradients.
In this context, in the first part of this work, a system was developed and tested that enables the automated, minimal invasive sampling of sediment pore water of undisturbed or manipulated sediments while simultaneously recording parameters such as redox potential, oxygen content and pH value. In an incubation experiment the impact of acidification and mechanical disturbance (re-suspension) on the mobility of 13 metal(loid)s was investigated using a triple quadrupole inductively coupled plasma-mass spectrometry (ICP-QQQ-MS) multi-element approach. Most metals were released as consequence of sulfide weathering whereas mechanical disturbance had a major impact on the mobility of the oxide forming elements As, Mo, Sb, U and V. Additionally, options were demonstrated to address with the system the size fractionation of metal(loid)s in pore water samples and the speciation of As(III/V) and Sb(III/V).
In the second part, the focus, with a similar experimental design, was placed on the processes leading to the release of metal(loid)s. For this purpose, two incubation experiments with different oxygen supply were conducted in parallel. For the first time the nonmetals carbon, phosphorus and sulfur were analyzed simultaneous to 13 metal(loid)s in sediment pore water by ICP-QQQ-MS. Throughout the experiment metal(loid) size fractionation was monitored. It was confirmed that resuspension promotes the mobility of metalloids such as As, Sb and V, while the release of most metals was largely attributed to pyrite weathering. The colloidal (0.45-16 μm) contribution in terms of mobilization was only relevant for a few elements.
Finally, the sampling system was used as part of a new approach to sediment risk assessment. Undisturbed sediment cores from differently contaminated positions in the Trave estuary were examined, considering 16 metal(loid)s, the non-metals C, P and S and the ions NH4+, PO43- and SO42-. By the first in-depth comparison with in-situ dialysis-based pore water sampling the ability of the suction-based approach to represent field conditions was proven. The pore water studies together with supplementing resuspension experiments in bio-geochemical microcosms and sequential extraction identified the most “pristine” sediment of the study area as posing the greatest risk of metal(loid) release. However, the potentially released amounts per kg of sediment are only a few parts per thousand of the average daily loads of the Trave river.
Enterprise Collaboration Systems (ECS) have become substantial for computer-mediated communication and collaboration among employees in organisations. As ECS combine features from social media and traditional groupware, a growing number of organisations implement ECS to facilitate collaboration among employees. Consequently, ECS form the core of the digital workplace. Thus, the activity logs of ECS are particularly valuable since they provide a unique opportunity for observing and analysing collaboration in the digital workplace.
Evidence from academia and practice demonstrates that there is no standardised approach for the analysis of ECS logs and that practitioners struggle with various barriers. Because current ECS analytics tools only provide basic features, academics and practitioners cannot leverage the full potential of the activity logs. As ECS activity logs are a valuable source for understanding collaboration in the digital workplace, new methods and metrics for their analysis are required. This dissertation develops Social Collaboration Analytics (SCA) as a method for measuring and analysing collaboration activities in ECS. To address the existing limitations in academia and practice and to contribute a method and structures for applying SCA in practice, this dissertation aims to answer two main research questions:
1. What are the current practices for measuring collaboration activities in Enterprise Collaboration Systems?
2. How can Social Collaboration Analytics be implemented in practice?
By answering the research questions, this dissertation seeks to (1) establish a broad thematic understanding of the research field of SCA and (2) to develop SCA as a structured method for analysing ac-tivity logs of ECS. As part of the first research question, this dissertation documents the status quo of SCA in the academic literature and practice. By answering the second research question, this dissertation contributes the SCA framework (SCAF), which guides the practical application of SCA. SCAF is the main contribution of this dissertation. The framework was developed based on findings from an analysis of 86 SCA studies, results from 6 focus groups and results from a survey among 27 ECS user companies. The phases of SCAF were derived from a comparison of established process models for data mining and business intelligence. The eight phases of the framework contain detailed descriptions, working steps, and guiding questions, which provide a step by step guide for the application of SCA in practice. Thus, academics and practitioners can benefit from using the framework.
The constant evaluation of the research outcomes in focus groups ensures both rigour and relevance. This dissertation employs a qualitative-dominant mixed-methods approach. As part of the university-industry collaboration initiative IndustryConnect, this research has access to more than 30 leading ECS user companies. Being built on a key case study and a series of advanced focus groups with representatives of user companies, this dissertation can draw from unique insights from practice as well as rich data with a longitudinal perspective.
The flexible integration of information from distributed and complex information systems poses a major challenge for organisations. The ontology-based information integration concept SoNBO (Social Network of Business Objects) developed and presented in this dissertation addresses these challenges. In an ontology-based concept, the data structure in the source systems (e.g. operational application systems) is described with the help of a schema (= ontology). The ontology and the data from the source systems can be used to create a (virtualised or materialised) knowledge graph, which is used for information access. The schema can be flexibly adapted to the changing needs of a company regarding their information integration. SoNBO differs from existing concepts known from the Semantic Web (OBDA = Ontology-based Data Access, EKG = Enterprise Knowledge Graph) both in the structure of the company-specific ontology (= Social Network of Concepts) as well as in the structure of the user-specific knowledge graph (= Social Network of Business Objects) and makes use of social principles (known from Enterprise Social Software). Following a Design Science Research approach, the SoNBO framework was developed and the findings documented in this dissertation. The framework provides guidance for the introduction of SoNBO in a company and the knowledge gained from the evaluation (in the company KOSMOS Verlag) is used to demonstrate its viability. The results (SoNBO concept and SoNBO framework) are based on the synthesis of the findings from a structured literature review and the investigation of the status quo of ontology-based information integration in practice: For the status quo in practice, the basic idea of SoNBO is demonstrated in an in-depth case study about the engineering office Vössing, which has been using a self-developed SoNBO application for a few years. The status quo in the academic literature is presented in the form of a structured literature analysis on ontology-based information integration approaches. This dissertation adds to theory in the field of ontology-based information integration approaches (e. g. by an evaluated artefact) and provides an evaluated artefact (the SoNBO Framework) for practice.
We are living in a world where environmental crises come to a head. To curb aggravation of these problems, a socio-ecological transformation within society is needed, going along with human behavior change. How to encourage such behavior changes on an individual level is the core issue of this dissertation. It takes a closer look at the role of individuals as consumers resulting in purchase decisions with more or less harmful impact on the environment. By using the example of plastic pollution, it takes up a current environmental problem and focuses on an understudied behavioral response to this problem, namely reduction behavior. More concrete, this dissertation examines which psychological factors can encourage the mitigation of plastic packaging consumption. Plastic packaging accounts for the biggest amount of current plastic production and is associated with products of daily relevance. Despite growing awareness of plastic pollution in society, behavioral responses do not follow accordingly and plastic consumption is still very high. As habits are often a pitfall when implementing more resource-saving behavior, this dissertation further examines if periods of discontinuity can open a ’window of opportunity’ to break old habits and facilitate behavior change. Four manuscripts approach this matter from the gross to the subtle. Starting with a literature review, a summary of 187 studies addresses the topic of plastic pollution and human behavior from a societal-scientific perspective. Based on this, a cross-sectional study (N = 648) examines the deter-minants of plastic-free behavior intentions in the private-sphere and public-sphere by structural equation modeling. Two experimental studies in pre-post design build upon this, by integrating the determinants in intervention studies. In addition, it was evaluated if the intervention presented during Lent (N = 140) or an action month of ‘Plastic Free July’ (N = 366) can create a ‘window of opportunity’ to mitigate plastic packaging consumption. The literature review emphasized the need for research on behavioral solutions to reduce plastic consumption. The empirical results revealed moral and control beliefs to be the main determinants of reduction behavior. Furthermore, the time point of an intervention influenced the likelihood to try out the new behavior. The studies gave first evidence that a ‘window of opportunity’ can facilitate change towards pro-environmental behavior within the application field of plastic consumption. Theoretical and practical implications of creating the right opportunity for individuals to contribute to a socio-ecological transformation are finally discussed.
Graph-based data formats are flexible in representing data. In particular semantic data models, where the schema is part of the data, gained traction and commercial success in recent years. Semantic data models are also the basis for the Semantic Web - a Web of data governed by open standards in which computer programs can freely access the provided data. This thesis is concerned with the correctness of programs that access semantic data. While the flexibility of semantic data models is one of their biggest strengths, it can easily lead to programmers accidentally not accounting for unintuitive edge cases. Often, such exceptions surface during program execution as run-time errors or unintended side-effects. Depending on the exact condition, a program may run for a long time before the error occurs and the program crashes.
This thesis defines type systems that can detect and avoid such run-time errors based on schema languages available for the Semantic Web. In particular, this thesis uses the Web Ontology Language (OWL) and its theoretic underpinnings, i.e., description logics, as well as the Shapes Constraint Language (SHACL) to define type systems that provide type-safe data access to semantic data graphs. Providing a safe type system is an established methodology for proving the absence of run-time errors in programs without requiring execution. Both schema languages are based on possible world semantics but differ in the treatment of incomplete knowledge. While OWL allows for modelling incomplete knowledge through an open-world semantics, SHACL relies on a fixed domain and closed-world semantics. We provide the formal underpinnings for type systems based on each of the two schema languages. In particular, we base our notion of types on sets of values which allows us to specify a subtype relation based on subset semantics. In case of description logics, subsumption is a routine problem. For
the type system based on SHACL, we are able to translate it into a description
logic subsumption problem.
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.
Identifizierung und Quantifizierung von Mikroplastik mittels quantitativer ¹H-NMR Spektroskopie
(2021)
Plastic, and so microplastics (MP), are globally present and represent an increasingly significant problem for the environment. In order to understand the distribution and impact of MP it is important to identify and quantify MP over a wide range of sizes and to ensure comparability of studies. However, comparability of studies is made difficult or even impossible by different MP concentration data. There still is a great need for research in the field of size-independent, quantitative analysis of MP in environmental samples, especially with regard to mass-based MP concentration information. Therefore, this thesis aims to utilize quantitative ¹H-NMR spectroscopy (qNMR) as an alternative method in MP analysis. The qNMR method is a size-independent, mass-based method which can be used as an alternative for MP analysis and has potential for routine analysis. The proof-of-concept was demonstrated for LDPE, PET and PS particles (Chapter 2). Additionally, PVC, PA, and ABS particles were tested to cover the most important polymer types for MP-analysis (Chapter 3). Moreover, using PET, PVC and PS as examples it was examined whether the qNMR method can also be transferred to the more cost-effective NoD method (Chapter 4). Results of method validation of both methods (1D and NoD) show that quantification using the qNMR method is not only possible in principle, but also shows high accuracy (88.0-110 %) and detection limits (1 – 84 µg) that lie within the environmentally relevant range. Furthermore, it was examined whether not only high-field instruments are suitable for MP analysis, but also benchtop devices (low-field instruments), which are much more cost-effective in purchase and maintenance. Increasing measurement times for PET and PS to 30 min and for PVC to 140 min, the lower measuring frequency especially concerning resolving capacity could be compensated (Chapter 4). To address the question of potential matrix effects of environmental samples, matrix effects and recovery rates of sample preparation procedures, which have been developed specifically for the application of the qNMR method were investigated using PET fibers as an example (Chapter 5). It could be shown that environmental matrices do not interfere with the quantitative analysis of MP using qNMR methods. Specific sample preparation methods developed for qNMR analysis can be used with recovery rates > 80 % for different environmental matrices (Chapter 5). Finally, first orienting investigations for the simultaneous determination of several polymer types in one sample are reported (Chapter 6).
There has been little research on out-of-school places of learning and their effec-tiveness in the context of ESD education measures. With the help of a multi-stage analysis, this study identifies out-of-school places of learning with reference to the ESD education concept in the Rhineland-Palatinate study area. To this end, qualita-tive literature analyses were first used to generate ESD criteria, which were opera-tionalised as a methodological instrument in the form of an ESD checklist for out-of-school places of learning. The data obtained in this way provide the basis for the creation of a geographically oriented learning location database with ESD refer-ence. A cartographic visualisation of the data results in a spatial distribution pattern: Thus, there are districts and cities that are well supplied with ESD learning loca-tions, but also real ESD learning location deserts where there is a need to catch up. Furthermore, there is an accumulation of ESD learning sites in areas close to for-ests.
A guideline-based explorative interview with two ESD experts provides additional insights into the question of how ESD has been implemented in the federal state of Rhineland-Palatinate, the extent to which there is a need for optimisation, and which continuing measures are being taken for ESD outside schools within the framework of Agenda 2030.
In addition, a quantitative questionnaire study was carried out with 1358 pupils at 30 out-of-school places of learning after participation in an educational measure, in which environmental awareness, attitudes towards environmental behaviour and local learning were also considered. By including non-ESD learning locations, a comparative study on the effectiveness of ESD learning locations became possible. The statistical data evaluation leads to a variety of interesting results. Contra-intuitively, for instance, the type of learning location (ESD or non-ESD learning lo-cation) is not a significant predictor for the environmental awareness and environ-mental behaviour of the surveyed students, whereas communication structures within educational measures at extracurricular learning locations, the multimediality and action orientation and the duration of educational measures have a significant influence.
Keywords: extracurricular learning locations, education for sustainable develop-ment (ESD), ESD criteria, learning location landscape Rhineland-Palatinate, ESD learning locations, environmental awareness, environmental behaviour.
Successful export sectors in manufacturing and agribusiness are important drivers of structural transformation in Sub-Sahara African countries. Backed by industrial policies and active state involvement, a small number of successful productive export sectors has emerged in Sub-Saharan Africa. This thesis asks the question: How do politics shape the promotion of export-driven industrialisation and firm-level upgrading in Sub-Saharan Africa? It exemplifies this question with an in-depth, qualitative study of the cashew processing industry in Mozambique in the period from 1991 until 2019. Mozambique used to be one of the world’s largest producers and processors of cashew nuts in the 1960s and 1970s. At the end of the 20th century, the cashew processing industry broke down completely but has re-emerged as one of the country’s few successful agro-processing exports.
The thesis draws on theoretical approaches from the fields of political science, notably the political settlements framework, global value chain analysis and the research on technological capabilities to explore why the Mozambican Government supported the cashew processing industry and how Mozambican cashew processors acquired the technological capabilities needed to access the global cashew value chain and to upgrade. It makes an important theoretical contribution by linking the political settlements framework and the literature on upgrading in global value chains to study how politics shaped productive sector promotion and upgrading in the Mozambican cashew processing industry. The findings of the thesis are based on extensive primary data, including 58 expert interviews and 10 firm surveys, that was collected in Mozambique in 2018 as well as a broad base of secondary literature.
The thesis argues that the Mozambican Government supported the cashew processing industry because it became important for the Government’s political survival. Promoting the cashew sector formed part of an electoral strategy for the ruling FRELIMO coalition and a means to keep FRELIMO factions united by offering economic opportunities to key constituencies. In 1999, it adopted a protectionist cashew law that created strong incentives for cashew processing in Mozambique. This not only facilitated the re-emergence of the cashew processing industry after its breakdown. The law and the active involvement of the National Cashew Institute (INCAJU) also affected the governance of the local cashew value chain, the creation of backward linkages, and the upgrading paths of cashew processors. The findings of the thesis suggest that the cashew law reduced the pressure on the cashew processing industry to upgrade. The law further created opportunities for formal and informal rent creation for members of the political elite and lower level FRELIMO officials that prevented a far-reaching reform of the law. The thesis shows that international buyers do not promote upgrading among Sub-Sahara African firms in global value chains with market-based or modular governance. Moreover, firms that operate in countries where industrial policies are not enforced effectively cannot draw on the support of government institutions to enhance their capabilities and to upgrade. Firms therefore mainly depended on costly learning channels at firm level, e.g. learning by doing or hiring skilled labour, and/or on technical assistance from donors to build the technological capabilities needed to access global value chains and to remain competitive.
The findings of the thesis suggest that researchers, governments, development practitioners and consultants need to rethink their understanding of upgrading in GVCs in four ways. First, they need to move away from understanding upgrading in terms of moving towards more complex, higher value-added activities in GVCs (functional upgrading). Instead, it is important to consider the potential of other, more realistic types of upgrading for firms in low-income countries, such reducing risks by diversifying suppliers and buyers or increasing rewards by making production processes more efficient. Second, they need to replace an overly positive view on upgrading that neglects possible side-effects at sector and/or country level. Third, GVC participation on its own does not promote upgrading among local supplier firms in Sub-Saharan Africa. The interests of lead firms and Sub-Sahara African supplier firms may not be aligned or even conflicting. Targeted industrial policies and the creation of institutions that effectively promote capability building among firms therefore become even more important. Finally, upgrading needs to be understood as a process that is not only shaped by interactions between firms, but also by local domestic politics.
The findings of the thesis are highly relevant for scholars from the fields of political science, development studies, and economics. Its practical implications and tools, e.g. a technological capabilities matrix for the cashew industry, are of interest for development practitioners, members of public institutions in Sub-Sahara African countries, local entrepreneurs, and representatives of local business associations that are involved in promoting export sectors and upgrading among local firms.
Water is used in a way as if it were available infinitely. Droughts, increased rainfall or flooding already lead to water shortages and, thus, deprive entire population groups of the basis of their livelihoods. There is a growing fear that conflicts over water will increase, especially in arid climate zones, because life without water - whether for humans, animals or plants - is not possible.
More than 60 % of the African population depend on land and water resources for their livelihoods through pastoralism, fishing and farming. The water levels of rivers and lakes are decreasing. Hence, the rural population which is dependent on land and water move towards water-rich and humid areas. This internal migration increases the pressure on available water resources. Driven by the desire to strengthen the economic development, African governments align their political agendas with the promotion of macro international and national economic projects.
This doctoral thesis examines the complex interrelationships between water shortages, governance, vulnerability, adaptive capacity and violent and non-violent conflicts at Lake Naivasha in Kenya and Lake Wamala in Uganda. In order to satisfy the overall complexity, this doctoral thesis combines various theoretical and empirical aspects in which a variety of methods are applied to different geographical regions, across disciplines, and cultural and political boundaries.
The investigation reveals that Lake Naivasha is more affected by violent conflicts than Lake Wamala. Reasons for this include population growth, historically grown ethnic conflicts, corruption and the preferential treatment of national and international economic actors. The most common conflict response tools are raiding and the blockage of water access. However, deathly encounters, destruction of property and cattle slaughtering are increasingly used to gain access to water and land.
The insufficient implementation of the political system and the governments’ prioritization to foster economic development results, on the one hand, in the commercialization of water resources and increases, on the other hand, non-violent conflict between national and sub-national political actors. While corruption, economic favours and patronage defuse this conflict, resource access becomes more difficult for the local population. Resulting thereof, a final hypothesis is developed which states that the localization of the political conflict aggravates the water situation for the local population and, thereby, favours violent conflicts over water access and water use in water-rich areas.
Within the field of Business Process Management, business rules are commonly used to model company decision logic and govern allowed company behavior. An exemplary business rule in the financial sector could be for example:
”A customer with a mental condition is not creditworthy”. Business rules are
usually created and maintained collaboratively and over time. In this setting,
modelling errors can occur frequently. A challenging problem in this context is
that of inconsistency, i.e., contradictory rules which cannot hold at the same
time. For instance, regarding the exemplary rule above, an inconsistency would
arise if a (second) modeller entered an additional rule: ”A customer with a mental condition is always creditworthy”, as the two rules cannot hold at the same
time. In this thesis, we investigate how to handle such inconsistencies in business
rule bases. In particular, we develop methods and techniques for the detection,
analysis and resolution of inconsistencies in business rule bases
Rivers play an important role in the global water cycle, support biodiversity and ecological integrity. However, river flow and thermal regimes are heavily altered in dammed rivers. These impacts are being exacerbated and become more apparent in rivers fragmented by multiple dams. Recent studies mainly focused on evaluating the cumulative impact of cascade reservoirs on flow or thermal regimes, but the role of upstream reservoirs in shaping the hydrology and hydrodynamics of downstream reservoirs remains poorly understood. To improve the understanding of the hydrodynamics in cascade reservoirs, long-term observational data are used in combination with numerical modeling to investigate the changes in flow and thermal regime in three cascade reservoirs at the upper reach of the Yangtze River. The three studied reservoirs are Xiluodu (XLD), Xiangjiaba (XJB) and Three Gorges Reservoir (TGR). In addition, the effects of single reservoir operation (at seasonal/daily time scale) on hydrodynamics are examined in a large tributary of TGR. The results show that the inflow of TGR has been substantially altered by the two upstream reservoirs with a higher discharge in spring and winter and a reduced peak flow in summer. XJB had no obvious contribution to the variations in inflow of TGR. The seasonal water temperature of TGR was also widely affected by the upstream two reservoirs, i.e., an increase in winter and decrease in spring, associated with a delay in water temperature rise and fall. These effects will probably be intensified in the coming years due to the construction of new reservoirs. The study also underlines the importance of reservoir operation in shaping the hydrodynamics of TGR. The seasonal dynamics of density currents in a tributary bay of TGR are closely related to seasonal reservoir operations. In addition, high-frequency water level fluctuations and flow velocity variations were observed in response to periodic tributary bay oscillations, which are driven by the diurnal discharge variations caused by the operation of TGR. As another consequence of operation of cascade reservoirs, the changes in TGR inflow weakened spring thermal stratification and caused warming in spring, autumn and winter. In response to this change, the intrusions from TGR occurred more frequently as overflow and earlier in spring, which caused a sharp reduction in biomass and frequency of phytoplankton blooms in tributary bays of TGR. This study suggests that high-frequency bay oscillations can potentially be used as an efficient management strategy for controlling algal blooms, which can be included in future multi-objective ecological conservation strategies.
Method development for the quantification of pharmaceuticals in aqueous environmental matrices
(2021)
As a consequence of the world population increase and the resulting water scarcity, water quality is the object of growing attention. In that context, organic anthropogenic molecules — often defined as micropollutants— represent a threat for water resources. Among them, pharmaceuticals are the object of particular concerns due to their permanent discharge, their increasing consumption and their effect-based structures. Pharmaceuticals are mainly introduced in the environment via wastewater treatment plants (WWTPs), along with their metabolites and the on-site formed transformation products (TPs). Once in the aquatic environment, they partition between the different environmental compartments in particular the aqueous phase, suspended particulate matter(SPM) and biota. In the last decades, pharmaceuticals have been widely investigated in the water phase. However, extreme polar pharmaceuticals have rarely been monitored due to the lack of robust analytical methods. Moreover, metabolites and TPs have seldom been included in routine analysis methods although their environmental relevance is proven. Furthermore, pharmaceuticals have been only sporadically investigated in SPM and biota and adequate multi-residue methods are lacking to obtain comprehensive results about their occurrence in these matrices. This thesis endeavors to cover these gaps of knowledge by the development of generic multi-residue methods for pharmaceuticals determination in the water phase, SPM and biota and to evaluate the occurrence and partition of pharmaceuticals into these compartments. For a complete overview, a particular focus was laid on extreme polar pharmaceuticals, pharmaceutical metabolites and TPs. In total, three innovative multi-residue methods were developed, they include analytes covering a broad range of physico-chemical properties. First, a reliable multi-residue method was developed for the analysis of extreme polar pharmaceuticals, metabolites and TPs dissolved in water. The selected analytes covered a significant range of elevated polarity and the method would be easily expendable to further analytes. This versatility could be achieved by the utilization of freeze-drying as sample preparation and zwitterionic hydrophilic interaction liquid chromatography (HILIC) in gradient elution mode. The suitability of HILIC chromatography to simultaneously quantify a large range of micropollutants in aqueous environmental samples was thoroughly studied. Several limitations were pointed out: a very complex and time-consuming method development, a very high sensitivity with regards to modification of the acetonitrile to water ratio in the eluent or the diluent and high positive matrix effects for certain analytes. However, these limitations can be overcome by the utilization of a precise protocol and appropriate labeled internal standards. They are overmatched by the benefits of HILIC which permits the chromatographic separation of extreme polar micropollutants. Investigation of environmental samples showed elevated concentrations of the analytes in the water phase. In particular, gabapentin, metformin, guanylurea and oxypurinol were measured at concentrations in the µg/L range in surface water. Subsequently, a reliable multi-residue method was established for the determination of 57 pharmaceuticals, 47 metabolites and TPs sorbed to SPM down to the low ng/g range. This method was conceived to cover a large range of polarity in particular with the inclusion of extreme polar pharmaceuticals. The extraction procedure was based on pressurized liquid extraction (PLE) followed by a clean-up via solvent exchange and detection via direct injection-reversed-phase LC-MS/MS and freeze-drying HILIC-MS/MS. Pharmaceutical sorption was examined using laboratory experiments. Derived distribution coefficients Kd varied by five orders of magnitude among the analytes and confirmed a high sorption potential for positively charged and nonpolar pharmaceuticals. The occurrence of pharmaceuticals in German rivers SPM was evaluated by the investigation of annual composite SPM samples taken at four sites at the river Rhine and one site at the river Saar between the years 2005 and 2015. It revealed the ubiquitous presence of pharmaceuticals sorbed to SPM in these rivers. In particular, positively charged analytes, even very polar and nonpolar pharmaceuticals showed appreciable concentrations. For many pharmaceuticals, a distinct correlation was observed between the annual quantities consumed in Germany and the concentrations measured in SPM. Studies of composite SPM spatial distribution permitted to get hints about specific industrial discharge by comparing the pollution pattern along the river. For the first time, these results showed the potential of SPM for the monitoring of positively charged and nonpolar pharmaceuticals in surface water. Finally, a reliable and generic multi residue method was developed to investigate 35 pharmaceuticals and 28 metabolites and TPs in fish plasma, fish liver and fish fillet. For this matrix, it was very challenging to develop an adequate clean-up allowing for the sufficient separation of the matrix disturbances from the analytes. In the final method, fish tissue extraction was performed by cell disruption followed by a non-discriminating clean-up based on silica gel solid-phase extraction(SPE) and restrictive access media (RAM) chromatography. Application of the developed method to the measurement of bream and carp tissues from German rivers revealed that even polar micropollutants such as pharmaceuticals are ubiquitously present in fish tissues. In total, 17 analytes were detected for the first time in fish tissues, including 10 metabolites/TPs. The importance of monitoring metabolites and TPs in fish tissues was confirmed with their detection at similar concentrations as their parents. Liver and fillet were shown to be appropriate for the monitoring of pharmaceuticals in fish, whereas plasma is more inconvenient due to very low concentrations and collection difficulties. Elevated concentrations of certain metabolites suggest possible formation of human metabolites in fish. Measured concentrations indicate a low bioaccumulation potential for pharmaceuticals in fish tissues.
Real-time operating systems for mixed-criticality systems
must support different types of software, such as
real-time applications and general purpose applications,
and, at the same time, must provide strong spatial and
temporal isolation between independent software components.
Therefore, state-of-the-art real-time operating systems
focus mainly on predictability and bounded worst-case behavior.
However, general purpose operating systems such as Linux
often feature more efficient---but less deterministic---mechanisms
that significantly improve the average execution time.
This thesis addresses the combination of the two contradicting
requirements and shows thread synchronization mechanisms
with efficient average-case behavior, but without sacrificing
predictability and worst-case behavior.
This thesis explores and evaluates the design space of fast paths
in the implementation of typical blocking synchronization
mechanisms, such as mutexes, condition variables, counting
semaphores, barriers, or message queues. The key technique here
is to avoid unnecessary system calls, as system calls have high
costs compared to other processor operations available in user
space, such as low-level atomic synchronization primitives.
In particular, the thesis explores futexes, the state-of-the-art
design for blocking synchronization mechanisms in Linux
that handles the uncontended case of thread synchronization
by using atomic operations in user space and calls into the
kernel only to suspend and wake up threads. The thesis also
proposes non-preemptive busy-waiting monitors that use an
efficient priority ceiling mechanism to prevent the lock holder
preemption problem without using system calls, and according
low-level kernel primitives to construct efficient wait and
notify operations.
The evaluation shows that the presented approaches
improve the average performance comparable
to state-of-the-art approaches in Linux.
At the same time, a worst-case timing analysis shows
that the approaches only need constant or bounded temporal
overheads at the operating system kernel level.
Exploiting these fast paths is a worthwhile approach
when designing systems that not only have to fulfill
real-time requirements, but also best-effort workloads.