Abstract: Globally, incorporation of agricultural lands into the urban boundary has been a common phenomenon. Governments use various alternatives to access the required land, including land expropriation procedures, which refers to the compulsorily taking of land from the landholders without their consent by paying compensation. In Ethiopia, the urban population is growing rapidly which resulted into an increase in the demand for urban land for housing construction, public services provision, and infrastructure developments. As the Ethiopian constitution prohibits sale of landholders, governments, at various levels, have been expropriating land from the surrounding farmers to meet the demand for urban land. The general objective of this thesis is to improve the understanding of the impacts of local land deals for urbanization on socioeconomics of farmers and the environment. The findings of this thesis revealed that there are gaps in the current practices of land expropriation for urban expansion that should be improved. The results showed that the compensation paid to the affected farmers is found to be economically inappropriate, i.e., not enough to restore the affected farmers’ livelihoods, in contrast with the land laws that allows a compensation amount that would put previous land users in a better or the same wellbeing as before the land expropriation. In addition, it is indicated that the land expropriation process does not take into account the value of ecosystem services, which are benefits obtain from the land, and important for the wellbeing of the society. We conclude that while land expropriation is an important tool to obtain land from the landholders when it is needed for public purposes, the practices in the study area show it is adversely affecting the socioeconomics of farmers and the environment.

Abstract: Growing global plastic production combined with poor waste collection has led to increasing amounts of plastic debris being found in oceans, rivers and on shores. The goal of this study is to provide an overview on currently available technological solutions to tackle marine plastic litter and to assess their potential use in developing countries. To compile an inventory of technological solutions, a dedicated online platform was developed. A total of 51 out of initially 75 submitted solutions along the plastics value chain were assessed by independent experts. Collection systems represent more than half of the shortlisted solutions. A quarter include processing and treatment technologies, either as a stand-alone solution (30%) or, more commonly, in combination with a first litter capturing step. Ten percent offer digital solutions. The rest focuses on integrated waste management solutions. For each stage in the source-to-sea spectrum-land, rivers, sea-two illustrative examples are described in detail. This study concludes that the most cost-effective type of solution tackles land-based sources of marine litter and combines technology with people-oriented practices, runs on own energy sources, connects throughout the plastics value chain with a convincing valorization plan for captured debris, and involves all relevant stakeholders.

Abstract: Heterogeneous catalysts are often & ldquo;black boxes & rdquo; due to the insufficient understanding of the detailed mechanisms at the catalytic sites. An atomic-level elucidation of the processes taking place in those regions is, thus, mandatory to produce robust and selective heterogeneous catalysts. We have improved the description of the whole reactive scenario for polymeric carbon nitrides (PCN) by combining atomic-level characterizations with magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy, classical reactive molecular dynamics (RMD) simulations, and quantum chemistry (QC) calculations. We disclose the structure & minus;property relationships of an ad hoc modified PCN by inserting an aryl amino group that turned out to be very efficient for the production of H2O2. The main advancement of this work is the development of a difluoromethylene-substituted aryl amino PCN to generate H2O2 at a rate of 2.0 mM & middot;h & minus;1 under the irradiation of household blue LEDs and the identification of possible active catalytic sites with the aid of 15N and 19F MAS solid-state NMR without using any expensive labeling reagent. RMD simulations and QC calculations confirm and further extend the experimental descriptions by revealing the role and locations of the identified functionalities, namely, NH linkers, & minus;NH2 terminal groups, and difluoromethylene units, reactants, and products. <comment>Superscript/Subscript Available</comment

Abstract: Hexagonal boron nitride (h-BN) has long been recognized as an ideal substrate for electronic devices due to its dangling-bond-free surface, insulating nature and thermal/chemical stability. These properties of the h-BN multilayer are mainly determined by its lattice structure. Therefore, to analyse the lattice structure and orientation of h-BN crystals becomes important. Here, the stacking order and wrinkles of h-BN are investigated by transmission electron microscopy. It is experimentally confirmed that the layers in the h-BN flakes are arranged in the AA ' stacking. The wrinkles in a form of threefold network throughout the h-BN crystal are oriented along the armchair direction, and their formation mechanism was further explored by molecular dynamics simulations. Our findings provide a deep insight about the microstructure of h-BN and shed light on the structural design/electronic modulations of two-dimensional crystals.

Abstract: High strength 7XXX aluminium series reach exceptional strength, higher than all other industrial aluminium alloys. However, they suffer from a lack of ductility compared to softer series. This work presents a procedure to improve the ductility of 7475 Al alloy in high strength condition, reaching a true fracture strain of 70% at full 500 MPa T6 yield strength. Using friction stir processing (FSP) and post-FSP heat treatments, 100% of industrial rolled material T6 yield stress is maintained but a 180% increase in fracture strain is measured for the processed material. This ductility improvement is studied by in-situ synchrotron X-ray tomography and is explained by the reduction of intermetallic particles size and the homogenization of their spatial distribution. Furthermore, the microstructure after FSP shows equiaxed refined grains which favour crack deviation as opposed to large cracks parallel to the elongated coarse grains in rolled plate. These results are paving the way to better formability and crashworthiness of 7XXX alloys.

Abstract: Household packaging waste sorting facilities consist of complex networks of processes to separate diverse waste streams. These facilities are a key first step to re-enter materials into the recycling chain. However, so far there are no general methods to predict the performance of such sorting facilities, i.e.
how efficiently the heterogeneous packaging waste is sorted into fractions with value for further recycling. In this paper, a model of the material flow in a sorting facility is presented, which allows changing the incoming waste composition, split factors on the sorting units as well as the setup of the sorting facility. The performance of the sorting facility is judged based on the purity of the output material (grade) and the recovery of the input material. A validation of the model was performed via a case study on Belgian post-consumer packaging waste with a selection of typical waste items that can be found in this stream. Moreover, the model was used to predict the possible sorting qualities of future Belgian postconsumer packaging waste after an extension of the allowed waste packaging items in the waste stream. Finally, a sensitivity analysis was performed on the split factors, which are a key data source in the model. Overall, the developed model is flexible and able to predict the performance of packaging waste sorting facilities as well as support waste management and design for recycling decisions, including future
design of packaging, to ensure proper sorting and separation.

Abstract: Hyperbolic polaritons in ultra thin materials such as few layers of van derWaals heterostructures provide a unique control over light-matter interaction at the nanoscale and with various applications in flat optics. Natural hyperbolic surface plasmons have been observed on thin films of WTe2 in the light wavelength range of 16-23 mu m (similar or equal to 13-18 THz) [Nat. Commun. 11, 1158 (2020)]. Using time-dependent density functional theory, it is found that carbon doped monolayer phosphorene (beta-allotrope of carbon phosphide monolayer) exhibits natural hyperbolic plasmons at frequencies above similar or equal to 5 THz which is not observed in its parent materials, i.e. monolayer of black phosphorous and graphene. Furthermore, we found that by electrostatic doping the plasmonic frequency range can be extended to the mid-infrared. (C) 2021 Elsevier Ltd. All rights reserved.

Abstract: Illicit drugs use and abuse remains an increasing challenge for worldwide authorities and, therefore, it is important to have accurate methods to detect them in seized samples, biological fluids and wastewaters. They are recently classified as the latest group of emerging pollutants as their consumption increased tremendously in recent years. Nanomaterials have gained much attention over the last decade in the development of sensors for a myriad of applications. The applicability of these nanomaterials, functionalized or not, significantly increases and it is therefore highly suitable for use in the detection of illicit drugs. We have assessed the suitability of various nanoplatforms, such as graphene (GPH), multi-walled carbon nanotubes (MWCNTs), gold nanoparticles (AuNPs) and platinum nanoparticles (PtNPs) for the electrochemical detection of illicit drugs. GPH and MWCNTs were chosen as the most suitable platforms and cocaine, 3,4-methylendioxymethamfetamine (MDMA), 3-methylmethcathinone (MMC) and alpha-pyrrolidinovalerophenone (PVP) were tested. Due to the hydrophobicity of the nanomaterials-based platforms which led to low signals, two strategies were followed namely, pretreatment of the electrodes in sulfuric acid by cyclic voltammetry and addition of Tween 20 to the detection buffer. Both strategies led to an increase in the oxidation signal of illicit drugs. Binary mixtures of illicit drugs with common adulterants found in street samples were also investigated. The proposed strategies allowed the sensitive detection of illicit drugs in the presence of most adulterants. The suitability of the proposed sensors for the detection of illicit drugs in spiked wastewaters was finally assessed.

Abstract: Immobilization of two single transition metal (TM) atoms on a substrate host opens numerous possibilities for catalyst design. If the substrate contains more than one vacancy site, the combination of TMs along with their distribution patterns becomes a design parameter potentially complementary to the substrate itself and the bi-metal composition. By means of DFT calculations, we modeled three dissimilar bi-metal atoms (Ti, Mn, and Cu) doped into the six porphyrin-like cavities of porous C24N24 fullerene, considering different bi-metal distribution patterns for each binary complex, viz. TixCuz@C24N24, TixMny@C24N24, and MnyCuz@C24N24 (with x, y, z = 0-6). We elucidate whether controlling the distribution of bi-metal atoms into the C24N24 cavities can alter their catalytic activity toward CO2, NO2, H-2, and N-2 gas capture. Interestingly, Ti2Mn4@C24N24 and Ti2Cu4@C24N24 complexes showed the highest activity and selectively toward gas capture. Our findings provide useful information for further design of novel few-atom carbon-nitride-based catalysts.

Abstract: Improving the efficiency and longevity of energy storage systems based on Li- and Na-ion rechargeable batteries presents a major challenge. The main problems are essentially capacity loss and limited cyclability. These effects are due to a hierarchy of factors spanning various length and time scales, interconnected in a complex manner. As a consequence, and in spite of several decades of research, a proper understanding of the ageing process has remained somewhat elusive. In recent years, however, combinations of advanced spectroscopy techniques and first-principles simulations have been applied with success to tackle this problem. In this Special Issue, we are pleased to present a selection of articles that, by precisely applying these methods, unravel key aspects of the reduction-oxidation reaction and intercalation processes. Furthermore, the approaches presented provide improvements to standard diagnostic and characterisation techniques, enabling the detection of possible Li-ion flow bottlenecks causing the degradation of capacity and cyclability.

Abstract: In most semiconducting metal chalcogenides, a large deformation is usually accompanied by a phase transformation, while the deformation mechanism remains largely unexplored. Herein, a phase-transformation-induced deformation in Ag2Se is investigated by in situ transmission electron microscopy, and a new ordered high-temperature phase (named as alpha '-Ag2Se) is identified. The Se-Se bonds are folded when the Ag+-ion vacancies are ordered and become stretched when these vacancies are disordered. Such a stretch/fold of the Se-Se bonds enables a fast and large deformation occurring during the phase transition. Meanwhile, the different Se-Se bonding states in alpha-, alpha '-, beta-Ag2Se phases lead to the formation of a large number of nanoslabs and the high concentration of dislocations at the interface, which flexibly accommodate the strain caused by the phase transformation. This study reveals the atomic mechanism of the deformation in Ag2Se inorganic semiconductors during the phase transition, which also provides inspiration for understanding the phase transition process in other functional materials.

Abstract: In recent decades, as crop production has increased in many areas where irrigation projects have been implemented, the global agricultural development community has promoted irrigation investments. However, due to the disappointing performance of irrigation farming in developing countries, irrigation intervention in Africa South of the Sahara including Ethiopia is an issue of debate. Moreover, several gaps exist in the Ethiopian irrigation farming literature. For instance, evidence about the direct and indirect effects of irrigation water on agriculture is not well documented. The irrigation farming literature has not disentangled the indirect effects of having access to irrigation water from the direct effect and the indirect effects have been underrepresented. Furthermore, most previous studies have applied either a quantitative or qualitative approach and have relied only on revealed data as main type of methodology, making studies that combine qualitative and quantitative research and that use both stated and revealed data underrepresented. In this study, different approaches have been applied to investigate how irrigation water impacts Ethiopia agriculture with special attention being given to disentangling the direct and indirect effects of irrigation water on Ethiopian agriculture. Using a structural equation model, a stochastic production frontier approach, and a discrete choice experiment, I drew evidence regarding the direct and indirect effects of irrigation water on crop revenue of smallholder farmers, the technical efficiency of irrigation user farmers, and the farmers’ willingness to pay to improve poor irrigation schemes from field observations, semi-structured interviews and focus group discussions with farmers, and key informant interviews with the local agricultural agents from the Koga and Fogera Districts of Amhara Region Ethiopia. The results indicate that irrigation water in general has both direct and indirect positive effects on agriculture, and the indirect effect is mediated by both improved farm inputs and the type of crops produced. The results also show that – due to poor extension services and backward agronomic practices, the mean technical efficiency of farmers in Ethiopia is very low, and that large-scale irrigation users are less technically efficient than small-scale irrigation users. Moreover, the results show that improving irrigation schemes shifts the frontier up, and smallholder farmers are strongly willing to contribute financially to the maintenance costs of irrigation schemes. The results offer relevant lessons for policymakers that providing irrigation water supply must be embedded in a comprehensive support package including access to extension services, improved input supply, and access to stable markets.

Abstract: In the biogeochemical flows on Earth, the reactive nitrogen (Nr) level has three times surpassed the safe boundary. The severe transgression of this boundary goes against sustainable planetary development. The modern food production process excessively relies on synthetic Nr fertilizers from the Haber– Bosch process. However, the massive loss of valuable nitrogen resources (i.e., 78-89%) from agriculture has been causing severe nitrogen cascade. Besides, the domestic wastewater in some local areas is discharged without proper treatment, making it a nonnegligible source of Nr pollution for local water bodies. Anthropogenic activities keep pumping out Nr pollution via point-source and non-point-source (NPS) emissions. Compared to the NPS emissions, point sources give visible and identified waste streams. It is vital to intervene the nitrogen cascade from point sources and facilitate humanity back to the safe Nr boundary. The collected and collectible Nr streams from food production, waste management, and recycling secondary raw materials can be used as waste-based fertilizers for agricultural cultivation. Besides the well-investigated recovery of inorganic Nr, organic Nr accounts for a massive Nr proportion on the Earth. Proper handling and treatment make these useful organic fertilizers for soil-based cultivation. However, these organic Nr fertilizers cannot directly apply to fertigation or hydroponic cultivation systems, and further biological conversion via nitrogen mineralization and nitrification to nitrate is essential. Besides the direct Nr cycling, the indirect Nr cycling ‘over the atmosphere’ should also be considered. In this way, the nitrogen cycle can be completed via converting the waste Nr back to nitrogen gas (i.e., Nr removal) and then synthesizing into Nr again. The municipal wastewater treatment plants receive a vast amount of low-strength Nr wastewater (mainly as ammonium) daily. Compared to the conventional nitrification/denitrification process, partial nitritation/anammox (PN/A) is considered a resource- and cost-effective technology for wastewater with a low COD/N ratio. Moreover, the novel autotrophic denitratation/anammox process could be a good Nr removal process for wastewater containing both ammonium and nitrate. This Ph.D. thesis aimed to develop Nr recovery, conversion, and removal bioreactor strategies for different types of waste streams and biomass. Nr recovery was investigated on high-strength Nr waste streams for fertigation or hydroponic applications in Chapters 2 and 3. On the other hand, Nr removal was studied on the medium- to low-strength Nr waste streams in Chapters 4 and 5. In Chapter 2, a novel mineralization and nitrification system was proposed, producing nutrient solutions from solid organic fertilizers for hydroponic systems. Batch tests showed that aerobic incubation at 35°C could realize the NO₃⁻-N production efficiency above 90% from a novel microbial fertilizer. Subsequently, in the stirred tank bioreactor test, NO₃⁻-N production efficiency stabilized in a range of 44-51% under the influent loading rate of 400 mg TN L⁻¹ d⁻¹ at a 5-day HRT. Using Ca(OH)₂ and Mg(OH)₂ as pH control reagents generated the nutrient solutions with different P, Ca, and Mg nutrient levels. After modeling the nutrient balancing process, the proportion of organic-sourced NO₃⁻-N in the Hoagland nutrient solution (HNS) of Ca(OH)₂ scenario was 92.7%, while only 37.4% in the Mg(OH)₂ scenario. Compared to commercial scenarios, the total costs of the organic-sourced HNS can be cost-competitive for hydroponic cultivation. In Chapter 3, the Nr recovery as nitrate (NO₃⁻-N) from diluted human urine (around 670 mg N L⁻¹) was explored in a trickling filter (TF) for the first time. A novel concept of in-situ integrating the TF system into hydroponic systems was proposed as meaningful progress towards sustainable agriculture. The difference between synthetic and real urine in nitrification efficiency was found to be negligible. The full nitrification of alkalinized real urine was realized in the pH-controlled TF by calcium hydroxide (Ca(OH)₂) at around pH 6. The TF could handle different urine collection batches and maintain relatively stable nitrification performance, with NO₃⁻-N production efficiency and rate of 88±3% and 136±4 mg N L⁻¹ d⁻¹, respectively. The optimal HLR to realize this nitrification performance was 2 m³ m⁻² h⁻¹, with energy consumption of 1.8 kWh electricity kg⁻¹ NO₃⁻-N production. Ca(OH)₂, as a cheap base, its triple advantages on urine alkalinization, full nitrification, and macronutrient supplementation were successfully demonstrated in our proposed concept. In Chapter 4, towards more sustainable wastewater treatment, the feasibility of one-stage partial nitritation/anammox (PN/A) was investigated in three parallel packed-bed trickling filters (TFs), with three types of carrier materials of different specific surface areas. Synthetic wastewater containing 100-250 mg NH₄⁺-N L⁻¹ was tested to mimic medium-strength household waste streams after carbon removal. Interestingly, the cheap carrier based on expanded clay achieved similar rates as commercially used plastic carrier materials. The top passive ventilation combined with an optimum hydraulic loading rate of 1.8 m³ m⁻² h⁻¹ could reach approximately 60% total nitrogen (TN) removal at a rate of 300 mg N L⁻¹ d⁻¹. A relatively low NO₃⁻-N production (13%) via PN/A was achieved in TFs. Most of the TN removal took place in the top compartment, where anammox activity was the highest. Energy consumption estimation (0.78 kWh electricity g⁻¹ N removed) suggested that the proposed process could be a suitable low-cost alternative for nitrogen removal. In Chapter 5, coupling sulfur-driven denitratation (SDN) with anammox was proposed to treat the wastewater containing both NO₃⁻-N and NH₄⁺-N, like the secondary effluents of mainstream PN/A processes. To explore the feasibility of sufficient and stable NO₂⁻-N accumulation via SDN in the long term, the effects of pH setpoints, residual NO₃⁻-N level, and biomass-specific NO₃⁻-N loading rate (BSNLR) were investigated. Alternating the pH setpoints between 7.0 and 8.5 could temporarily stimulate the NO₂⁻-N accumulation. Both the residual NO₃⁻-N and BSNLR showed highly positive correlations with the NO₂⁻-N accumulation efficiency. Under the control of pH 8.5, 1.0±0.8 mg NO₃⁻-N L⁻¹ and 150±42 mg NO₃⁻-N g⁻¹ VSS d⁻¹, SDN could produce 6.4±1.0 mg NO₂⁻-N L⁻¹ in the short term. Thiobacillus members may play a crucial role in managing the NO₂⁻-N accumulation, but the reduction of abundance and possible adaptation significantly impaired the efficacy of control strategies in the long run. Overall, novel technologies have been proposed to sustainably convert Nr in waste streams and biomass. The decision for Nr recovery versus removal and synthesis should be based on specific cases with the best environmental, economic, and human-health sustainability. In the future, the Nr management concepts should be further improved to make the nitrogen cycle more sustainable with higher resource use efficiency and less Nr emissions to the environment. Although the thesis is mainly focused on limited types of Nr waste streams, it pointed out the direction of sustainable Nr management and could facilitate the Nr back to the safe boundary in the long run.

Abstract: In the present work two different cold working and annealing schemes were utilized, and the asymmetric superelastic response of thermomechanically processed materials were then assessed through cyclic tensile and compressive modes of deformation. The values of transformation stress, transformation strain, and pseudoelastic strain were measured for each treated and solutionized specimens and the asymmetric response was compared. In the solution annealed state, the difference of these parameters at different deformation modes was negligible due to the weak texture of the material, while for thermomechanically treated ones, development of specific deformation and recrystallization texture components was identified to be one of the underlying reasons of intensified asymmetry. The evolved substructure during the thermomechanical processing also played a substantial role in determining the asymmetric response. The presence of fine grains and dense dislocation substructure could hinder the movement of the transformation front, thus limiting the range of transformation. In tensile mode, the transformation stress was lower, but higher transformation strain was achieved, which was discussed relying on the slip activity in specified oriented grains. The lower transformation strain in compression mode led to lower pseudoelastic strain due to the narrow transformation range which finally degraded superelastic response of the material. (C) 2021 Elsevier B.V. All rights reserved.

Abstract: In this chapter, a statistical model-based method to count the number of atoms of monotype crystalline nanostructures from high-resolution annular dark-field (ADF) scanning transmission electron microscopy (STEM) images is discussed in detail together with a thorough study on the possibilities and inherent limitations. We show that this method can be applied to nanocrystals of arbitrary shape, size, and atom type. The validity of the atom-counting results is confirmed by means of detailed image simulations and it is shown that the high sensitivity of our method enables us to count atoms with single atom sensitivity.