One of the unsolved problems of modern science is whether the pre-Columbian peoples of the New World developed completely independently of cultural influences from the Old World or if there was a trans-oceanic contact? A number of scientists agree that there are many – and often remarkable – similarities between the cultures of pre-Columbian America and those of the Mediterranean world. Nevertheless, there is no agreement, as yet, on how cultural diffusion can be differentiated from independent invention. Scientific analysis shows that scholarly positions are often strongly pre-formed from paradigms (scientific based assumptions), which tend to hinder consideration of solid scientific data offered by geo-biology and its trans-disciplinary examination of the subject under investigation here. An unambiguous answer to the question, what historical processes led to the emergence of the ancient American agriculture, hasn\''t been given. However, the archaeological discovery of crops with clear trans-oceanic origin, in addition to advances in molecular biology, increasingly support the hypothesis that humans from the distant past influenced each other across the oceans at a much earlier stage. The vegetation and zoo-geography indicate, by numerous examples that some species could only have spread through perhaps unintentional (passive) human transmission [1]. There are two very old crops found in the „New World‟, which contradict the paradigm of a completely independent origin for American agriculture. These are the African Bottle Gourd (Lagenaria siceraria L.) and the ancestral cotton species (Gossypium herbaceum L.) of the domesticated spin able sub-genus of tetraploid cotton. The historical spread of both types has been under discussion for decades, especially in respect of trans-oceanic human contact with the American continent. There has also been a debate in the \"Old World\" ever since the discovery of nicotine and cocaine in Egyptian mummies, centering around whether \"New World\" plants (or the ingredients) might have been transmitted in the reverse direction, back to the presumed start in centers of the Ancient World\''s oldest civilizations.

This International Workshop is a high quality seminar providing a forum for the exchange of scientific achievements between research communities of different universities and research institutes in the area of innovation information technologies. It is a continuation of the Russian-German Workshops that have been organized by the universities in Dresden, Karlsruhe and Ufa before. The workshop was arranged in 9 sessions covering the major topics: Modern Trends in Information Technology, Knowledge Based Systems and Semantic Modelling, Software Technology and High Performance Computing, Geo-Information Systems and Virtual Reality, System and Process Engineering, Process Control and Management and Corporate Information Systems.

The potential of Digital twin (DT) technology outside of the industrial field has been recognized by researchers who have promoted the vision of applying DTs technology beyond manufacturing, to purposes such as enhancing human well-being and improving quality of life (QoL). The expanded definition of DTs to incorporate living and nonliving physical entities into the definition of DTs was a key motivation behind the model introduced in this thesis for building health digital twins of citizens. In contrast with DTs that have been developed in more industrial fields, this type of digital twins modeling necessitates protecting each citizen's unique identity while also representing features common to all citizens in a unified way. In nature, DNA is an example of a model that is both unified, common to all humans, and unique, distinguishing each human as an individual. DNA’s architecture is what inspired us to propose a digital twin DNA (DT-DNA) model as the basis for building health DTs for citizens. A review of the literature shows that no unified model for citizens’ health has been developed that can act as a base for building digital twins of citizens while also protecting their unique identity thus we aim to fill this gap in this research. Accordingly, in this thesis, we proposed a DT-DNA model, which is specifically designed to protect the unique identity of each citizen’s digital twin, similar to what DNA does for each human. We also proposed a DT-DNA-based framework to build standardized health digital twins of citizens on micro, meso and macro levels using two ISO standards: ISO/IEEE 11073 (X73) and ISO 37120. To achieve our goal, we started by analyzing the biological DNA model and the influencing factors shaping health in smart cities. The purpose of the first is to highlight the DNA model features which provide the building blocks for our DT-DNA model. The purpose of the latter is to determine the main bases of our DT-DNA model of health DTs. Based on the analysis results; we proposed DT-DNA to model health DTs for citizens. In keeping with our DNA analogy, we have identified four bases, A, T, G, and C, for our unified and unique DT-DNA model. The A base in the proposed model represents a citizen’s anthropometric when we build the DT-DNA on an individual level and represents the city’s regulatory authorities when we build the DT-DNA on community and city levels. The T base represents different tasks included in the provided health data that are required to model citizens’ health DT-DNA on different levels. The G base represents the geographic and temporal information of the city, where the citizen exists at the time of data collection. The C base represents the context at the time of data collection. To proof the concept, we present our initial work on building health DTs for citizens in four case studies. The first two case studies are dedicated for health DTs at the micro level, the third case study is dedicated for health DTs at the meso level and the fourth case study is dedicated for health DTs at the macro level. In addition, we developed an algorithm to compare cities in terms of their community fitness and health services status. The four case studies provide promising results in terms of applicability of the proposed DT-DNA model and framework in handling the health data of citizens, communities and cities, collected through various sources, and presenting them in a standardized, unique model.

The goal of this thesis has been global geolocalization using only visual input and a 3D database for reference. In recent years Convolutional Neural Networks (CNNs) have seen huge success in the task of classifying images. The flattened tensors at the final layers of a CNN can be viewed as vectors describing different input image features. Two networks were trained so that satellite and aerial images taken from different views of the same location had feature vectors that were similar. The networks were also trained so that images taken from different locations had different feature vectors. After training, the position of a given aerial image can then be estimated by finding the satellite image with a feature vector that is the most similar to that of the aerial image.  A previous method called Where-CNN was used as a baseline model. Batch-Hard triplet loss, the Adam optimizer, and a different CNN backbone were tested as possible augmentations to this method. The models were trained on 2640 different locations in Linköping and Norrköping. The models were then tested on a sequence of 4411 query images along a path in Jönköping. The search region had 1449 different locations constituting a total area of 24km2.  In Top-1% accuracy, there was a significant improvement over the baseline, increasing from 61.62% accuracy to 88.62%. The environment was modeled as a Hidden Markov Model to filter the sequence of guesses. The Viterbi algorithm was then used to find the most probable path. This filtering procedure reduced the average error along the path from 2328.0 m to just 264.4 m for the best model. Here the baseline had an average error of 563.0 m after filtering.  A few different 3D methods were also tested. One drawback was that no pretrained weights existed for these models, as opposed to the 2D models, which were pretrained on the ImageNet dataset. The best 3D model achieved a Top-1% accuracy of 70.41%. It should be noted that the best 2D model without using any pretraining achieved a lower Top-1% accuracy of 49.38%. In addition, a 3D method for efficiently doing convolution on sparse 3D data was presented. Compared to the straight-forward method, it was almost 2.5 times faster while still having comparable accuracy at individual query prediction.  While there was a significant improvement over the baseline, it was not significant enough to provide reliable and accurate localization for individual images. For global navigation, using the entire Earth as search space, the information in a 2D image might not be enough to be uniquely identifiable. However, the 3D CNN techniques tested did not improve the results of the pretrained 2D models. The use of more data and experimentation with different 3D CNN architectures is a direction in which further research would be exciting.

<p>Probing the subsurface for evidence related to the degradation of porous mediums and the evolution of damage mechanisms has been a long-standing challenge in geophysics. As such imaging and predicting fracture network development has remained a difficult area for subsurface science for decades despite the seminal and significant works put forward by many researchers. While this has provide great understanding about the behaviours and properties of natural porous media, there is still much that needs to be explored particularly in regard to the mineralogical composition and chemistry of clay-rich rocks. Despite the fact that argillaceous rocks which consist of different types of clays and varied mineral composition are ubiquitous in nature and are often the target of several technologies (e.g. geotechnical engineering, nuclear waste storage and disposal,hydrocarbon exploration and extraction, carbon capture and sequestration, etc.), many studies focus primarily on the bulk properties or the percentage of components in the matrix. For these reason and due to the problems that can be encountered with natural rocks that contain a swelling clay component whether randomly distirbuted or localized in consolidated globs in zones of the matrix, the influence of clay chemistry in relation to fracture development which is not well characterized, especially during desaturation is investigated with analogue rock samples which were systematically fabricated for this purpose.</p> <p><br></p> <p>The research performed in this dissertation investigated, the applicability of  the fabrication protocol for developing synthetic rocks with desirable rock like features and behavior, the impact and relationship between the rock properties, the microstructural composition, water loss, and the macroscopic behavior of the analogue rocks, focusing on the structure and chemistry of the constituent clay materials. Synthetic rocks were fashioned with the necessary geometries, properties, and material compositions. On the macroscopic scale the fracture and drying behavior of the synthetic rocks were examined with 3D X-ray microscopy and further evaluated through the utility of acoustic emission monitoring, water loss monitoring, and unconfined compressive testing. On the finer scale (nano-microscale), the chemical and mechanical properties, and behavior of select clays was explored by exploiting several methods of material characterization which also included cation exchange experiments coupled with inductively coupled plasma – optical emission spectrometry (ICP-OES). </p> <p><br></p> <p>For the finer scale, experiments verified that calcined kaolinite clay had a different mineral structure and negligible to non-existence shrinkage abilities. In contrast, the montmorillonite clays possessed higher and similar moisture contents but, owing to the different principal cations these clays interacted a bit differently in the highly akaline environment, experienced varying degrees of shrinkage, and had observedly minor structural dissimilarities. For the relatively larger scale, the emergence of damage, extent of the damage network, and the patterns of the crack network mainly depended on the microstructural composition of the analogue rocks, particularly it's clay chemistry and/ or distribution. The location of damage depended on the emplacement and percentage of swelling clay in the matrix, and numerical investigations with peridynamics revealed that the observed damage was a consequence of the action of the swelling and non-swelling components of the matrix. Furthermore, if the microstructure consisted of no clay or calcined kaolinite the AE activity was solely attributed to interfacial processes that occurred during fluid front movement. If the microstructure consisted of a particular montmorillonite, the cracks propagated in the direction of the drying front. Conversely, for montmorillonite clay predominated by a different principal cation, the crack network developed and propagated differently during water loss. Additionally, on the laboratory core scale, properties and behavior similar to natural rocks were confirmed and the rock strength, porosity, AE activity, and velocities were primarily affected by the microstructural composition of the analogue rocks. </p> <p><br></p> <p>An added challenge for investigating and monitoring evolving systems and processes, whether on the laboratory or field scale, is the problem of extracting useful information from the physical data that can be used to identify signatures of developing processes, and changes in the properties or the behavior of a system. Here, data driven machine learning modeling and clustering techniques were undertaken to build a mechanistic understanding of the AE activity generated during drying. The intent is for this work to add to the fundamental research aimed at developing methods that will robustly detect and extract signatures related to evolutionary processes or features in the AE signals, and group them according to some degree of similarity. Such research will support reliable interpretations of the physical data for predictions of the behavior of systems, development of engineering controls, and improvement of the understanding of intrinsic dynamics related to complex processes particularly those that occur in clay-rich systems.</p> <p><br></p> <p>Combined chemical and mechanical investigations have great potential for unraveling practical challenges in subsurface science, especially regarding damage processes in clay-rich rock systems, and identifying and interpreting the presence of discontinuities from geophysical data. The present findings are useful for establishing a link between the constituent clay and observed damage, and improving our understanding of the development of damage in clay-bearing systems. These results provide insight on the influence of swelling clay and the chemistry of such clays on the generation of cracks and crack networks in rock like materials which can be useful for the characterization of damage in both laboratory and the field. The work presented here can also be a basis for further experiments that aim to uncover methods and protocols that will help with the indirect characterization of evolutionary processes, damage mechanisms, and damage in clay rich porous media. Additionally support for the use of analogue rocks in experimental rock physics, architected with specific material compositions, pore structures, crack systems, or clay fractions, is provided here. </p>

Logistics and supply chain in the Architecture, Engineering and Construction (AEC) industry can be seen as coordinated collaboration that is subject to managerial risks. The managerial risks are mitigated by Building Information Modelling (BIM) and Geo-Information Science (GIS), which are two distinctive digital transformative tools which are revolutionizing and accelerating the AEC industry in recent years. Many gains have been achieved concerning the capacity of BIM and GIS to enable collaborative workflows that minimize data loss and reduce inefficiencies in construction. In the past decade, most scholarly literature on BIM and GIS integration for supply chain management have focused on coordination and visualization to improve supply chain operational efficiency. While BIM optimizes visualization and manages the data related to specific projects, GIS coordinates and manages the data related to the outside environment of the project. An integrated BIM-GIS adoption for Construction Supply Chain Management (CSCM) offers value propositions for client and contracting organizations as information/data is seamlessly shared among them to guide decision making at every phase of the construction project.  However, no detailed study has been conducted so far on assessments of the value creation 4D BIM-GIS brings to the AEC industry when espoused for CSCM. To fill this gap, this paper aims to identify and prioritize the value propositions to 4D BIM-GIS adoption for CSCM in the Swedish AEC industry. Based on the reflective perceptions and evaluations of the AEC industry, the paper demonstrated the varied opinions from current active users and those who are yet to adopt 4D BIM-GIS for CSCM. ‘Time savings, ‘Increased efficiency and productivity and ‘Improved communication and information sharing’ were ranked as topmost drivers for 4D BIM-GIS adoption. The paper recommends corporate level training as pivotal in familiarizing workers with the new techniques that combine BIM and GIS in AEC practice. / Logistik och försörjningskedjan inom arkitektur, teknik och konstruktion (ABE) kan ses som ett samordnat samarbete med överhängande ledningsrisker. Riskerna som hanteras kan mildras av Byggnadsinformationsmodellering (BIM) och Geografiskt informationssystem (GIS), som är två digitalt distinkta transformativa verktyg som revolutionerat och påskyndat ABE-sektorn de senaste åren. Många vinster har uppnåtts med avseende på kapaciteten av BIM och GIS, vilket har möjliggjort ett samarbetsflöde som minimerat dataförlust och minskat ineffektiviteten i byggandet. Under det senaste decenniet har den mest vetenskapliga litteraturen om BIM- och GIS-integration för ledning av försörjningskedjan fokuserat på samordning och visualisering för att förbättra effektiviteten i försörjningskedjan. BIM optimerar visualisering och hantering av data, relaterat till specifika projekt, medan GIS samordnar och hanterar data relaterat till projektets omgivning. En integrerad BIM-GIS-antagande för konstruktionsledningen av försörjningskedjan (CSCM) erbjuder värdeförslag för klient- och beställarorganisationer, eftersom information / data sömlöst delas mellan dem för att kunna guida beslutsfattandet i varje fas av byggprojektet. Emellertid har ingen detaljerad studie hittills genomförts om bedömningar av värdeskapandet som 4D BIM-GIS ger till ABE-sektorn när de används för CSCM. För att fylla denna kunskapslucka syftar denna studie till att identifiera och prioritera värdeförslag till 4D BIM-GIS-antagande för CSCM i den svenska ABE-sektorn. Baserat på de reflekterande uppfattningarna och utvärderingarna från ABE-sektorn, visar studien de olika åsikterna från de nuvarande aktiva användare och de som ännu inte har antagit 4D BIM-GIS för CSCM. ”Tidsbesparingar,” Ökad effektivitet och produktivitet” och ”Förbättrad kommunikation och informationsdelning” rankades som de främsta drivkrafterna för 4D BIM-GIS-antagande. Studien rekommenderar utbildning på företagsnivå som en central faktor för att bekanta sig med de nya teknikerna som kombinerar BIM och GIS i ABE-sektorn.

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)

IntroductionLes chutes et les blessures dues aux chutes représentent un véritable enjeu de santé publique. Les programmes d’exercices physiques axés sur l’équilibre permettent de réduire de 30 à 40% le taux de chutes chez les personnes âgées vivant à leur domicile. Cependant, leur efficacité sur la prévention des traumatismes dus aux chutes n’a pas été établie.Ce travail comporte 2 parties :- Une revue systématique de la littérature et méta-analyse des résultats d’essais contrôlés randomisés (ECR) qui évaluent l’efficacité de l’exercice sur différents types de chutes traumatiques chez les personnes âgées en milieu communautaire. - L’analyse des données de l’ECR multicentrique ‘Ossébo’, qui évalue l’efficacité d’un programme d’exercice physique de prévention de chutes traumatiques chez des femmes âgées.MéthodesRevue systématiqueDes recherches bibliographiques ont été effectuées pour repérer les ECR de prévention des chutes par l’exercice physique, réalisés chez des personnes âgées vivant à leur domicile, et présentant des données sur les chutes traumatiques.Ensuite, on a regroupé les définitions des chutes traumatiques trouvées dans les études sélectionnées en 4 catégories :A/ avec conséquence.B/ avec recours à des soins médicaux. C/ ayant entraîné un traumatisme grave.D/ avec fracture.On a réalisé une méta-analyse (MA) pour chaque catégorie, donc on a calculé un effet global (effet poolé) de l’exercice correspondant au ratio des taux d’incidence dans les 2 groupes par un modèle à effet aléatoire.L’essai OsséboLes participantes à l’essai sont des femmes âgées de 75 à 85 ans, vivant à leur domicile, et ayant des capacités physiques diminuées. Au total, 706 femmes, dans 20 centres en France, ont été randomisées en 2 groupes : le groupe intervention (GI), et le groupe contrôle (GC).L’intervention comprend des ateliers hebdomadaires d’exercice en petits groupes pendant 2 ans, et des exercices au domicile.La survenue de chutes a été enregistrée à l’aide des cartes-calendriers. Les circonstances et les conséquences de la chute étaient demandées en cas de signalement d’une chute, afin de classer la chute (sans conséquence, traumatisme modéré, traumatisme grave).Des bilans ont été effectués à 1 an et 2 ans après l’inclusion, selon le même protocole que le bilan initial, qui comprenait notamment des tests fonctionnels simples.Le critère principal est le taux d’incidence des ‘chutes traumatiques’ (modérée et graves). Des modèles à fragilité (modèles de survie avec un effet aléatoire) ont été utilisés pour modéliser ce taux dans les 2 groupes.L’évolution au cours du temps des capacités physiques, et d’autres facteurs ont été comparés grâce à un modèle marginal avec un effet aléatoire au niveau du centre.RésultatsRevue systématique17 essais totalisant 4305 participants ont été sélectionnés. Toutes les interventions évaluées comprenaient des exercices de l’équilibre. Les résultats de la MA montrent que l’exercice est associé à une réduction du taux de chutes traumatiques dans chacune des catégories considérées, avec un effet poolé de 0.63 (IC95% : 0.51-0.77) pour la catégorie A(10 essais). Le RaR poolé était de 0.70 (0.54-0.92) pour la catégorie B (8 essais), de 0.57 (0.36-0.90) pour la catégorie C (7 essais), et de 0.39 (IC 95% : 0.22-0.66) pour la catégorie C (6 essais). L’essai OsséboOn a recensé 397 chutes traumatiques dans le GC, et 305 dans le GI, correspondant à une réduction significative de 19% du taux de chutes traumatiques (‘hazard ratios’ HR= 0.81 IC95% : (0.67 - 0.99). A 2 ans, les femmes du GI ont des performances significativement meilleures que les femmes du GC sur l’ensemble des tests physiquesDiscussionLes programmes d’exercice destinés à prévenir les chutes sont également efficaces pour réduire les traumatismes dus à la chute, y compris les plus graves. Aussi, il est possible de mettre en place à large échelle un programme efficace d’exercice de prévention des chutes traumatiques de longue durée chez des personnes âgées / Context: Exercise programmes can prevent falls in older community-dwellers. However, evidence that these programmes can also prevent injurious falls was poor.Objectives : Systematic review of evidence of the effect of exercise interventions on injurious fall prevention from randomised controlled trials (RCT).Evaluate the effectiveness of ‘Ossébo’, a multi-centre RCT assessing the effectiveness of a 2-year injurious fall prevention balance training programme.Methods:Systematic reviewThe definitions of injurious falls from included studies were classified into more homogeneous categories. This allowed the estimation of a pooled rate ratio for each injurious falls category based on random effects models. Ossébo trial706 women aged 75-85 years ; home-living with diminished functional capacities were included. The 2 groups were compared for rates of injurious falls with a frailty model. Other outcomes included physical functional capacities, and quality of life indicators. Results:Systematic review17 trials involving 4305 participants were included. Four categories were identified: all injurious falls, falls resulting in medical care, severe injurious falls, and falls resulting in fractures. Exercise had a significant preventive effect in all categories.OsséboThere were 305 injurious falls in the intervention group and 397 in the control group, for a HR of 0.81 (0.67 to 0.99). At 2 years, women in the intervention group had significantly better performances on all physical tests and a better perception of their overall physical function. Conclusion:Fall prevention exercise programmes are effective in preventing injurious falls, and are feasible for long-term, wide-spread dissemination

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)

The need to consider groundwater and surface water as a single resource has fostered the interest of the scientific community on the interactions between surface water and groundwater. The region below and alongside rivers where surface hydrology and subsurface hydrology concur is the hyporheic zone. This is the region where water exchange determines many biogeochemical and ecological processes of great impact on the functioning of rivers. However, the complex processes taking place in the hyporheic zone require a multidisciplinary approach. The combination of innovative point and distributed techniques originally developed in separated disciplines is of great advantage for the indirect identification of water exchange in the hyporheic zone. Distributed techniques using temperature as a tracer such as fiber-optic distributed temperature sensing can identify the different components of groundwater-surface water interactions based on their spatial and temporal thermal patterns at the sediment-water interface. In particular, groundwater, interflow discharge and local hyporheic exchange flows can be differentiated based on the distinct size, duration and sign of the temperature anomalies. The scale range and resolution of fiber-optic distributed temperature sensing are well complemented by geophysics providing subsurface structures with a similar resolution and scale. Thus, the use of fiber-optic distributed temperature sensing to trace flux patterns supported by the exploration of subsurface structures with geophysics enables spatial and temporal investigation of groundwater-surface water interactions with an unprecedented level of accuracy and resolution. In contrast to the aforementioned methods that can be used for pattern identification at the interface, other methods such as point techniques are required to quantify hyporheic exchange fluxes. In the present PhD thesis, point methods based on hydraulic gradients and thermal profiles are used to quantify hyporheic exchange flows. However, both methods are one-dimensional methods and assume that only vertical flow occurs while the reality is much more complex. The study evaluates the accuracy of the available methods and the factors that impact their reliability. The applied methods allow not only to quantify hyporheic exchange flows but they are also the basis for an interpretation of the sediment layering in the hyporheic zone. For upscaling of the previous results three-dimensional modelling of flow and heat transport in the hyporheic zone combines pattern identification and quantification of fluxes into a single framework. Modelling can evaluate the influence of factors governing groundwater-surface water interactions as well as assess the impact of multiple aspects of model design and calibration of high impact on the reliability of the simulations. But more importantly, this modelling approach enables accurate estimation of water exchange at any location of the domain with unparalleled resolution. Despite the challenges in 3D modelling of the hyporheic zone and in the integration of point and distributed data in models, the benefits should encourage the hyporheic community to adopt an integrative approach comprising from the measurement to the upscaling of hyporheic processes.