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Method development for the quantification of pharmaceuticals in aqueous environmental matrices (2021)
Boulard, Lise
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.
Efficient and predictable thread synchronization mechanisms for mixed-criticality systems on shared-memory multi-processor platforms (2021)
Züpke, Alexander
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.
Effects of damming and reservoir operation on hydrodynamics and thermal regimes in large cascade reservoirs of the Yangtze River, China (2021)
Long, Lianghong
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.
A conflict over water in water abundant regions: The case of Lake Naivasha in Kenya and Lake Wamala in Uganda (2021)
Renner, Julia
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.
Handling Inconsistency in Business Rule Bases (2021)
Corea, Carl
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
Accessing global value chains: The politics of promoting export-driven industrialisation and upgrading in the Mozambican cashew processing industry (2021)
Saulich, Christina Lisa
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.
What impedes Consumers’ Delivery Drone Service Adoption? (2020)
Knobloch, Marius ; Schaarschmidt, Mario
Despite widespread plans of big companies like Amazon and Google to develop unmanned delivery drones, scholarly research in this field is scarce, especially in the information systems field. From technical and legal perspectives, drone delivery in last-mile scenarios is in a quite mature state. However, estimates of user acceptance are varying between high skepticism and exaggerated optimism. This research follows a mixed method approach consisting both qualitative and quantitative research, to identify and test determinants of consumer delivery drone service adoption. The qualitative part rests on ten interviews among average consumers, who use delivery services on a regular basis. Insights gained from the qualitative part were used to develop an online survey and to assess the influence of associated risks on adoption intentions. The quantitative results show that especially financial and physical risks impede drone delivery service adoption. Delivery companies who are currently thinking about providing a delivery drone service may find these results useful when evaluating usage behaviors in the future market for delivery drones.
Railway Safety Research – A Cross-Disciplinary Literature Review (2020)
Schneider, André
Railway safety is a topic which gains the public attention only if major railway accidents happen. This is because railway is considered as a safe mode of travel by the public. However, to ensure the safety of the railway system railway companies as well as universities conduct a broad spectrum of research. An overview of this research has not yet been provided in the scholarly literature. Therefore, this thesis follows two objectives. First an overview and ranking of railway safety research universities should be provided. Second, based on these universities, it should be identified which are the most relevant and influential research topics. The ranking is based on the research method “literature review” which forms the methodical basis for this thesis. To evaluate the universities based on a measurable and objective criterion, the number of citations of the researchers from each university is gathered. As a result, the University of Leuven for the civil engineering, Milan Politechnico for mechanical enginering and the University of Loughborough for electrical engineering are identified as the leading university in their field of railway safety research. The top universities for each discipline are distributed all over Europe, North America and Asia. However, a clear focus on the US and British universities is observed. For identification of the most relevant and influential topics the keywords from the publications which are considered in the ranking procedure are analyzed. Focus areas among these keywords are revealed by calculating the count of each keyword. High-speed trains as well as maintenance are recognized as the highly relevant topics in both civil and mechanical engineering. Furthermore, the topic of railway dynamics for mechanical engineering and noise and vibration for civil engineering are identified as the leading topics in the respective discipline. Achieving both research goals required exploratory approaches. Therefore, this thesis leaves open space for future research to deepen the individual topics which are approached in each section. A validation of the results through experts interviews as well as a deepening of the analysis through increasing the number of analyzed universities as well as applying statistical methods is recommended.
Model-based privacy by design (2020)
Ahmadian, Amirshayan
Nowadays, almost any IT system involves personal data processing. In such systems, many privacy risks arise when privacy concerns are not properly addressed from the early phases of the system design. The General Data Protection Regulation (GDPR) prescribes the Privacy by Design (PbD) principle. As its core, PbD obliges protecting personal data from the onset of the system development, by effectively integrating appropriate privacy controls into the design. To operationalize the concept of PbD, a set of challenges emerges: First, we need a basis to define privacy concerns. Without such a basis, we are not able to verify whether personal data processing is authorized. Second, we need to identify where precisely in a system, the controls have to be applied. This calls for system analysis concerning privacy concerns. Third, with a view to selecting and integrating appropriate controls, based on the results of system analysis, a mechanism to identify the privacy risks is required. Mitigating privacy risks is at the core of the PbD principle. Fourth, choosing and integrating appropriate controls into a system are complex tasks that besides risks, have to consider potential interrelations among privacy controls and the costs of the controls. This thesis introduces a model-based privacy by design methodology to handle the above challenges. Our methodology relies on a precise definition of privacy concerns and comprises three sub-methodologies: model-based privacy analysis, modelbased privacy impact assessment and privacy-enhanced system design modeling. First, we introduce a definition of privacy preferences, which provides a basis to specify privacy concerns and to verify whether personal data processing is authorized. Second, we present a model-based methodology to analyze a system model. The results of this analysis denote a set of privacy design violations. Third, taking into account the results of privacy analysis, we introduce a model-based privacy impact assessment methodology to identify concrete privacy risks in a system model. Fourth, concerning the risks, and taking into account the interrelations and the costs of the controls, we propose a methodology to select appropriate controls and integrate them into a system design. Using various practical case studies, we evaluate our concepts, showing a promising outlook on the applicability of our methodology in real-world settings.
Environmental processes transforming inorganic nanoparticles: implications on aquatic invertebrates (2020)
Lüderwald, Simon
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.
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