Abstract: The risk profile of Cr and Pb in urban road deposited sediment Exponential urbanisation and industrial growth occur on a global scale and result in an ecological burden, of which one important part is pollution. It is well known that the extent of air pollution has escalated over the past two decades in several parts of the world, despite mitigating measures and legislation. Current research points to the fact that air pollution in urban and industrial areas is substantially different from that found in rural areas. Road dust (RD) contributes up to 35% of airborne particulate matter due to resuspension thereof, and poses a health concern due to carcinogenic and toxic components potentially present in the micron-sized fractions. Although literature does report on the concentrations of trace, toxic metals and metalloids present in RD (Hooker and Nathanail 2006), the molecular make-up of particulates generated due to the resuspension of the RD is not well documented. In vitro and animal toxicological studies have confirmed that the chemical composition of inhaled particles plays a major role in its toxic, genotoxic and carcinogenic mechanisms, but the component-specific toxic effects are still not understood. Transition metals binding to air particle matter can result in reactive oxygen species in the human body (particularly in the lungs), and this is a significant risk, especially for vulnerable population groups like elderly people, children and terminally ill patients. The characterisation of the molecular composition of the fine fraction is evidently of importance for public health. During an earlier study, road dust from an inner-city environment in the UK was collected and partially characterised (Barrett e.a. 2010). These same-size fractions were analysed for their elemental concentrations, using X-ray Fluorescence Spectrometry (XRFS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). In addition, single-particle analysis was performed on the different fractions by means of Computer Controlled Electron Probe X-ray Micro Analysis (CC-EPXMA) and their molecular structure probed by studying elemental associations. These findings were correlated with Micro Raman Spectroscopy (MRS) results. It was found that the fine fraction (<38 μm) had the highest Pb (238 ppm) and Cr (171 ppm) concentrations. The CC-EPXMA data showed >50% association of Cr-rich particles with Pb and the MRS data showed that the Cr was mostly present as lead chromate and therefore in the Cr(VI) oxidation state. Concentrations of both Pb and Cr decreased substantially (279 (<38 mm) 13 ppm (<1mm); 171 (<38 mm) 91 ppm (<1mm) respectively) in the larger fractions. Apart from rather alarmingly high concentrations of oxidative stressors (Cu, Fe, Mn), the carcinogenic and toxic potential of the inhalable fraction is evident. Preliminary bioaccessibility data indicated that both Cr and Pb are readily

Abstract: Magnetic state of Fe-57 implanted and doped ZnO samples have been reported and studied by Mossbauer spectroscopy at different temperatures. The Mossbauer spectra mainly showed four doublets and three sextets, but some ambiguous identification remains regarding the probe site location and influence of defects in the hyperfine and magnetic parameters. In the present work some possible implantation configurations are suggested and evaluated using Monte Carlo simulation and electronic structure calculations within the density functional theory. Various implantation environments were proposed and studied considering the presence of defects. The obtained Fe-57 hyperfine parameters show a good agreement with the reported experimental values for some of these configurations. The possibility of Fe pair formation, as well as a Zn site vacancy stabilization between he second and third neighborhood of the implantation site, is supported. (C) 2014 Elsevier Ltd. All rights reserved.

Abstract: Exposure to volatile organic compounds (VOCs) remains a major public health concern. Indoor VOC concentrations typically far exceed outdoor levels due to a variety of emission sources and the stringent insulation measures that are imposed today. Many attempts have been made to use photocatalysis for indoor air purification. In an ideal situation, photocatalysis is capable of complete mineralization of VOCs to H2O and CO2, without any byproduct formation. Moreover, the process can take place at standard atmospheric conditions, i.e. ambient temperature and atmospheric pressure. However, successful exploitation is still impeded due to low conversion efficiency, significant pressure loss (and hence a high energy consumption) and byproduct formation. In the first part of this thesis an attempt was made to tackles these problems by designing a novel type of photocatalytic (PCO) reactor. The PCO device consists of a cylindrical vessel filled with TiO2-coated glass tubes and equipped with UV fluorescence lamps. It was investigated in terms of fluid dynamics, coating properties, UV-light distribution and photocatalytic activity. Experimental data was later used to develop and calibrate a Multiphysics model. The model proved to be a useful tool for designing and upscaling the PCO reactor. Consequently, an optimized prototype reactor was constructed and tested according the CEN-EN-16846-1 standard for VOC removal. Although the prototype showed promising results for lab-scale conditions, it struggled with byproduct formation when purifying ppb-level VOCs. In the second part of this thesis, activated carbon adsorption was investigated in order to combine it with photocatalysis. Activated carbon fiber was opted for its fast kinetics, high adsorption capacity and thermo-electrical regeneration. The filter was studied in detail regarding the adsorption of polar and apolar VOCs at indoor air concentration levels and regeneration capabilities. Experimental data was used to develop a Multiphysics model for activated carbon adsorption as well. Consequently, a novel type of ACF filter was developed using the Multiphysics model, which was equipped with electrodes in the tips of the pleats for effective thermal regeneration. In the last part, the combination of both ACF and PCO was studied using a realistic case study. Based on the Multiphysics model, the feasibility of a so-called hybrid air purification device could be investigated. The Multiphysics model shows promising results for this hybrid PCO-ACF system and hence, a demo setup was constructed for future research.

Abstract: Air pollution is one of the most serious problems the world faces today. It is highly necessary to monitor pollutants in real-time to anticipate and reduce damages caused in several fields of activities. Likewise, it is necessary to provide decision makers with useful and updated environmental data. As a solution to a part of the above-mentioned necessities, we developed a Java-based application software to collect, process and visualize several environmental and pollution data, acquired from the Mediterranean Dialog earth Observatory (MDEO) platform [1]. This application will amass data of Morocco area from EUMETSAT satellites, and will decompress, filter and classify the received datasets. Then we will use the processed data to build an interactive environmental real-time map of Morocco. This should help finding out potential correlations between pollutants and emitting sources.

Abstract: The high toxicity, endocrine-disrupting effects and low (bio)degradability commonly attributed to phenolic compounds have promoted their recognition as priority toxic pollutants. For this reason, the monitoring of these compounds in industrial, domestic and agricultural streams is crucial to prevent and decrease their toxicity in our daily life. To confront this relevant environmental issue, we propose the use of a combi-electrosensor which combines singlet oxygen (1O2)-based photoelectrochemistry (PEC) with square wave voltammetry (SWV). The high sensitivity of the PEC sensor (being a faster alternative for traditional COD measurements) ensures the detection of nmol L−1 levels of phenolic compounds while the SWV measurements (being faster than the color test kits) allow the differentiation between phenolic compounds. Herein, we report on the development of such a combi-electrosensor for the sensitive and selective detection of phenol (PHOH) in the presence of related phenolic compounds such as hydroquinone (HQ), bisphenol A (BPA), resorcinol (RC) and catechol (CC). The PEC sensor was able to determine the concentration of PHOH in spiked river samples containing only PHOH with a recovery between 96% and 111%. The SWV measurements elucidated the presence of PHOH, HQ and CC in the spiked samples containing multiple phenol compounds. Finally, the practicality of the combi-electrosensor set-up with a dual SPE containing two working electrodes and shared reference and counter electrodes was demonstrated. As a result, the combination of the two techniques is a powerful and valuable tool in the analysis of phenolic samples, since each technique improves the general performance by overcoming the inherent drawbacks that they display independently.

Abstract: Landfill mining refers to the re-circulation of resources from the previously deposited wastes–integrating resource recovery with traditional site remediation. Several resources that can be recovered include scrap metals, combustibles, and inert materials. In addition, land can be recovered or landfill void space can be liberated for future wastes. At present, landfill mining is still an emerging concept with few project implementations. Consequently, the assessments of its economic and climate implications are case study-specific, limiting the understanding of its potential in a wider geographical scope. This thesis aims to assess the economic performance and climate impact of landfill mining in Europe towards the development of sound strategies for implementation. Different project setups are assessed in relation to varying factors at the site level such as waste composition and landfill settings, and at the system level such as policy and market conditions and background material and energy. In doing so, a factor-based method is developed and applied to generate multiple scenarios (531, 441 scenarios per project setup) and determine the underlying important factors and their interrelations that drive the results. Such understanding is used to develop and discuss strategies for improvement by addressing relevant questions for specific stakeholders, including project investors (i.e., which landfill sites to prioritize?), landfill mining practitioners (i.e., how to set up such projects?), and policymakers (i.e., which policy instruments can effectively support such projects?). Results show that landfill mining is preferable in terms of climate than economy. Possible improvements are shown by internalizing thermal treatment of combustibles and extending fines residue utilization as construction aggregates. In relation to the choice of project setups, preferable site and system-level conditions are identified in general but it is also discussed that the plausibility of finding such conditions may be difficult at present. This steers the development of more tailored strategies on what can be done now by the landfill practitioners in terms of setting up projects under current policy and market conditions in specific regions, or what can be done by the policymakers in terms of implementing various policy instruments that can drive such changes at the system level. Through this thesis, the future of landfill mining research is guided towards addressing key challenges and potential solutions for improvement. Furthermore, this thesis highlights the role of assessment as a tool for learning and guiding the development of emerging concepts such as landfill mining.

Abstract: In this work, the carbon (C) and silicon (Si) doping and codoping effects on beta-arsenene (As) monolayer structural, electronic, and magnetic properties have been comprehensively investigated using first-principles calculations. The studied two-dimensional (2D) materials exhibit good stability. Pristine beta-As single layer is an indirect gap semiconductor with a band gap of 1.867(2.441) eV as determined by PBE(HSE06) functional. Due to the difference in atomic size and electronic interactions, C and Si substitution induces a significant local structural distortion. Depending upon dopant concentration and doping sites, feature-rich electronic properties including non-magnetic semiconductor, magnetic semiconductor and half-metallicity may be obtained, which result from p-p interactions. High spin-polarization at the Fermi level vicinity and significant magnetism suggest As:1C, As:2C, As:1Si, As:2Si, and As:CSi systems as prospective spintronic 2D materials. While, the C-C, Si-Si, and C-Si dimer doping decreases electronic band gap, making the layer more suitable for applications in optoelectronic devices. Results presented herein may suggest an efficient approach to create novel multi-functional 2D materials from beta-As monolayer.

Abstract: The use of temperature-time series measured in streambed sediments as input to coupled water flow and heat transport models has become standard when quantifying vertical groundwater-surface water exchange fluxes. We develop a novel methodology, called LPML, to estimate the parameters for 1-D water flow and heat transport by combining a local polynomial (LP) signal processing technique with a maximum likelihood (ML) estimator. The LP method is used to estimate the frequency response functions (FRFs) and their uncertainties between the streambed top and several locations within the streambed from measured temperature-time series data. Additionally, we obtain the analytical expression of the FRFs assuming a pure sinusoidal input. The estimated and analytical FRFs are used in an ML estimator to deduce vertical groundwater-surface water exchange flux and its uncertainty as well as information regarding model quality. The LPML method is tested and verified with the heat transport models STRIVE and VFLUX. We demonstrate that the LPML method can correctly reproduce a priori known fluxes and thermal conductivities and also show that the LPML method can estimate averaged and time-variable fluxes from periodic and nonperiodic temperature records. The LPML method allows for a fast computation of exchange fluxes as well as model and parameter uncertainties from many temperature sensors. Moreover, it can utilize a broad frequency spectrum beyond the diel signal commonly used for flux calculations.

Abstract: Differential-pulse stripping voltammetry is applied to measure zinc, cadmium, lead and copper by anodic stripping and selenium(IV) by cathodic stripping in rain water at pH 2; subsequently, at pH 9,1, manganese is measured by anodic stripping on the same portion, and cobalt and nickel are measured in the adsorptive mode after formation of their dimethylglyoximates. The instrumental parameters are optimized. The linear ranges, mutual interferences and detection limits are studied. Excellent accuracy is demonstrated; the standard deviation is around 15% at 2.550 μg l−1 levels. The method is shown to be applicable for rain water.

Abstract: A flow injection hydride generation graphite furnace atomic absorption spectrometric (FI-HG-GFAAS) method was applied to the determination of Se in Se-doped and undoped cereals and bakery products. For the purpose of doping, the soils used for the cultivation of the cereals were dosed with Se- doped foliar fertilizers. The samples were dissolved in a mixture of HNO(3) and H(2)O(2) solutions using micro-waveassisted digestion. The decomposition of H(2)Se generated from the sample solutions and the trapping of elemental Se were performed at a temperature of 300 degrees C on an Ir-pretreated integrated graphite platform of a transversally heated graphite atomizer(THGA). For release of the trapped Se within a fairly short atomization time (5s), an atomization temperature of 2200 degrees C was observed to be optimal. The overall efficiency of hydride generation, transport and trapping was similar to 86%. The upper limit of the linear dynamic range of calibration was 10 mu gL(-1), which corresponds to 0.5 mu g g(-1) for solid samples. Recovery of the samples spiked with Se(VI) solutions was found to be 93 +/- 6% on average. The relative standard deviation of the determinations was less than 8%. The limit of detection was found to be 0.06 mu gL(-1), corresponding to 3 ng g(-1) for solid samples. The accuracy of the method was verified with the use of IAEA-155 ( whey powder) certified reference material. End-capped THGA tubes resulted in an extension of the linear calibration range compared to that of standard THGAs. The Se content in bakery products made of undoped cereals ranged from 7.7 to 68 ng g(-1) ( wet weight) in 18 samples, whereas the Se content of the corresponding cereals was found to be below 100 ng g(-1) ( wet weight). The Se level of cereals grown on soils treated with Se- doped fertilizers ranged from 128 to 1046 ng g(-1) ( wet weight), and it depended linearly on the Se concentration of the corresponding foliar fertilizer.