The objective of this research was to evaluate the treatment efficiency of a nitrate-contaminated soil by combined technologies of the injection of palladized nanoiron slurry and electrokinetic remediation process. First, nanoiron was prepared by two synthesis processes based on the same chemical reduction principle yielding products of NZVI-A and NZVI-B, respectively. Then they were characterized by various methods. Micrographs of scanning electron microscopy have shown that a majority of these nanoparticles were in the range of 50-80 nm and 30-40 nm, respectively. Results of nitrogen gas adsorption-desorption show that NZVI-A and NZVI-B are mesorporous (ca. 30-40 Å) with BET surface areas of 128 m2/g and 77 m2/g, respectively. Results of X-ray diffractometry have shown that both types of nanoiron were poor in crystallinity. Results of zeta-potential measurements indicated that NZVI-A and NZVI-B had the same isoelectric point at pH 6.0. Although NZVI-A and NZVI-B were found to be superparamagnetic, their magnetization values were low. Poly acrylic acid (PAA), an anionic dispersant, was employed for stabilizing various types of nanoiron. Then Palladium¡]ca. 1 wt% of iron¡^ was selected as catalysis to form palladized nanoiron¡]Pd/Fe¡^. Results have demonstrated that an addition of 1 vol. % of PAA during the nanoiron preparation process would result in a good stabilization of nanoiron and nanoscale Pd/Fe slurry. Batch tests were carried out to investigate the effects of pH variation on degradation of nitrate aqueous solutions. Experimental results have indicated that palladized nanoiron outperformed nanoiron in treatment of nitrate in this study. Apparently, an employment of catalyst would enhance the treatment efficiency. Further, an exponential increase of the reaction rate was found for the systems at low pH. The final stage of this study was to evaluate the treatment efficiency of combined technologies of the injection of palladized nanoiron¡]Pd/Fe¡^ slurry and electrokinetic remediation process in treating a nitrate-contaminated soil. Test conditions used were given as follows: (1) slurry injection to four different positions in the soil matrix; (2) electric potential gradient: 1 V/cm; (3) daily addition of 20 mL of palladized nanoiron (4 g/L) slurry to the injection position; and (4) reaction time: 6 days. Test results have shown that addition of palladized nanoiron slurry to the anode reservoir yielded the lowest residual nitrate concentration in soil. Namely, about 99.5% removal of nitrate from soil. On the other hand, the acidic condition of soil matrix around the anode reservoir would enhance the degradation of nitrate therein. Based on the above findings, the treatment method employed in this work was proven to be a novel and efficient one in treating nitrate contaminated soil.

<p>Predmet izučavanja ove disertacije je pasivna bioremedijacija naftom i derivatima nafte&nbsp;zagađenih podzemnih voda na lokalitetu&nbsp; Ratno ostrvo i pospe&scaron;ivanje procesa&nbsp;<br />bioremedijacije zemlji&scaron;ta i podzemne vode zagađenih naftom i derivatima nafte na&nbsp;laboratorijskom postrojenju u ciljusanacije ugroženog lokaliteta.</p><p>Praćenjem podzemnih voda granične zone izvori&scaron;ta Ratno ostrvo i Rafinerije nafte&nbsp;utvrđeno je da je u podzemnoj vodi granične zone izvori&scaron;ta Ratno ostrvo i Rafinerije&nbsp;nafte Novi Sad prisutan proces pasivnebioremedijacije, odnosno, da na pojavu&nbsp;ugljovodoničnog zagađenja u vodi sredina odgovara povećanjem brojnosti, pre svega,&nbsp;ugljovodonik-osidujućih i lipolitskih bakterija i bakterijske enzimatske aktivnosti, i&nbsp;dolazi do transformacije mineralnih ulja u polarna jedinjenja. U vodi većine praćenih&nbsp;objekata uočene su eksponencijalne i linearne funkcionalne zavisnosti bakterijske&nbsp;brojnosti i fosfatazne aktivnosti od koncentracije ugljovodoničnog zagađenja za&nbsp;koncentracije ukupnih ugljovodonika &lt; 400 &micro;g/l (najče&scaron;će &lt; 200 &micro;g/l). Visok nivo&nbsp;podzemnih voda i prisustvo dela zagađenja u gornjim slojevima zemlji&scaron;ta ukazuje nam&nbsp;na mogućnost primene fitoremedijacije navedenog područja, jer je deo zagađenja&nbsp;dostupan korenskom sistemu.</p><p>Ispitivanjem tehničke bioremedijacije zemlji&scaron;ta i podzemne vode zagađenih naftom i&nbsp;<br />derivatima nafte&nbsp; na laboratorijskom postrojenju utvrđeno je da dolazi do opadanja&nbsp;<br />koncentracije ukupnih ugljovodonika u zemlji&scaron;tu sa 38,2 na 14,6 g/kg i mineralnih ulja&nbsp;sa 27,0 na 10,2 g/kg (62%), &scaron;to se može definisati jednačinom C=C₀e^-kt, gde je&nbsp;<br />konstanta brzine degradacije ugljovodonika k=0,0082 dan^-1. U vodi je prisutan veliki&nbsp;<br />broj karboksilnih kiselinanastalih oksidacijom alkana (C10-19), kao i aromata&nbsp;(benzoeva kiselina, kao i benzaldehid), &scaron;to ukazuje na proces biooksidacije&nbsp;ugljovodonika. Proces rastvaranja i emulgovanja nafte se pospe&scaron;uje uvođenjem&nbsp;recirkulacije vode: određena je jednačina zavisnosti koncentracije ugljovodonika u&nbsp;vodenoj fazi od koncentracije u&nbsp; čvrstoj fazi, zavisno od&nbsp; brzine proticanja:&nbsp;C_voda=(f^*v+K₀)C_zemlja, gde je koeficijent ispiranja f=1400 s/m, a difuzioni koeficijent&nbsp;K₀=6^*10^-4. Proces ispiranja nafte i derivata sa zemlje značajno utiče na aktivnost&nbsp;mikroorganizama i razgradnju zagađenja. Sa porastom koncentracije ugljovodonika&nbsp;generalno opadaju brojnosti svih ispitivanih grupa bakterija i fosfatazna aktivnost i&nbsp;određene su granične vrednosti tolerancije. Proces ispiranja se &nbsp;mora voditi tako da&nbsp;koncentracija mineralnih ulja u vodenoj fazi netreba da pređe 15-35 mg/l, a kad se&nbsp;postignu koncentracije ugljovodonika manje od 400 &micro;g/l treba prepustiti pasivnoj&nbsp;bioremedijaciji da ukloni zagađenje.</p> / <p>This dissertation investigates the passivebioremediation of groundwater from Ratno&nbsp;Ostrvo contaminated by oil and oil derivatives, and a bench-scale experiment to improve the soil and groundwater bioremediation processes, with the goal of sanatising the effected area.</p><p>During groundwater monitoring of the zone between the Ratno Ostrvo spring and the&nbsp;Novi Sad oil refinery, a passive bioremediation process was observed, whereby, &nbsp;in the hydrocarbons-contaminated water, increased counts of hydrocarbon-oxidising and lipolytic bacteria and increasing bacterial enzyme activity were found, along with the transformation of mineral oils to polar&nbsp; compounds. In water, the majority of the&nbsp;monitoring points displayed either exponential or linear functionalal dependence&nbsp; between bacterial count or phosphatase activity and hydrocarbon concentration, for&nbsp; total hydrocarbon concentrations &lt; 400 &micro;g/l (most often &lt; 200 &micro;g/l). The high groundwater level and the presence of contamination inthe upper soil layers makes possible the application of phytoremediation at the site, as part of the contamination is in the rhyzosphere.</p><p>The bench-scale investigation of bioremediation in soil and groundwater contaminated by oil and oil derivatives yielded decreasing concentrations of total hydrocarbons in the soil from 38.2 to 14.6 g/kg and mineral oils from 27.0 to 10.2 g/kg&nbsp; (62%), which can be described by C=C₀e^-kt, where the rate constant of&nbsp; hydrocarbon degradation is k=0.0082 day^-1.</p><p>In water, a large number of carboxylic acids were present, from the oxidation of&nbsp; alkanes (C10-19) and aromatics (benzoic acid, and also benzaldehyde), which indicates a hydrocarbon biooxidation process. The process of dissolving and emulgating the oil is enhanced by recirculating the water: the linear relation between the concentration of hydrocarbons in the liquid and solid phases was found to be dependent on the flow rate: C_water=(f^*v+K₀)C_soil, where the rinsing coefficient f=1400 s/m, and the diffusion coefficient K₀=6 x 10^-4. The process of rinsing the oil and oil derivatives from the soil significantly influences the microbial activity and the degradation of contaminants. With increasing hydrocarbon concentrations, there was&nbsp; generally decreasing bacterial counts and phosphatase activity, and an upper limit for&nbsp; hydrocarbon tolerance was determined. The rinsing process must becontrolled to&nbsp; ensure the mineral oil concentration in water does not exceed 15-35 mg/l, and once the concentration of hydrocarbons becomes less than 400&micro;g/l, passive bioremediation may be left to complete the degradation.</p>

Almost two hundred years ago, Dr John Snow identified the faecal contaminated water as a source of bacterial infections during a severe cholera outbreak. Several years later, we have developed many weapons on our arsenal to reduce the bacterial infections, from simple ones such as public hygiene measures (e.g. frequent showers & hand washing, clean water), to specialised ones such as the use of antibiotics. The antibiotics inhibit the bacterial growth, thus their use has effectively helped to treat many bacterial infections, revolutionizing medicine. Successful recovery from surgical operations would be seldom and would last exponentially without their use. Yet, antimicrobial resistance (AMR) has increased globally threatening to render antibiotics useless. However, the “golden era” of novel antibiotics development, when many novel antibiotics were discovered in a few years, belongs to the past. The bacteria developed resistance mechanisms to every single one of the antibiotics and rendered them useless. This could be reflected to an increase in the death rates, but more importantly to the increased health-care costs, which might compromise the treatment for other diseases. The Covid-19 pandemic provided such a clear paradigm on the straining of health care systems during massive parallel hospitalisation of patients. While, the misuse of antibiotics for human and veterinary was the main contributor of the increased AMR levels, other anthropogenic activities greatly contributed to AMR spread as well. Specifically, the wastewater treatment plants are considered as hotspots for AMR and agricultural practices, such as manure amendment, have been show to clearly promote AMR. Thus, the scientific community across clinical settings, environmental and agricultural sectors intensively researches on AMR, in an attempt to fully understand the AMR phenomenon. Nevertheless, the AMR is not the only problem that currently occurs in our society. The climate change, the urbanisation and the ever increasing human population has caused an increasing freshwater scarcity. The demand for treated wastewater (TWW) irrigation has increased due to this freshwater scarcity, and is expected to increase more. Since the TWW contains a high load of antibiotics, antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs), the irrigation with TWW has raised concerns regarding AMR spread in the environment. Many studies have attempted to investigate the impact of TWW on AMR spread in crops and soil; however, the impact on deeper lying environments remains not yet elucidated. This should raise concerns, since groundwater remains the most valuable drinking water source globally. Here in this thesis, I attempted to gain further understanding on whether TWW irrigation promotes the AMR spread in the soil and the so-far neglected deeper-lying subsurface environments. My outmost desire is that the present work will contribute to a framework of minimising the potential risks during TWW irrigation, rendering TWW irrigation as a safe and sustainable alternative for freshwater resources depletion.

Pour de nombreux pays, la sécurité alimentaire est le défi majeur que l’agriculture doit relever, tout en assurant la durabilité environnementale. L’intensification durable de la production et la prévention des pertes de récoltes sont des éléments clés pour augmenter les productions et garantir leur régularité, l’utilisation massive d’intrants (Engrais, pesticides) est le plus souvent la solution la plus facile et la sure à court terme. Ces pratiques d’intensification entrainant des consommations parfois excessives d’engrais et de produits phytosanitaires ont un impact négatif sur l’environnement et la santé, ce qui pose aujourd’hui le problème de la durabilité de ces modes de production. Assurer la sécurité alimentaire par des processus d’intensification et la durabilité environnementale semblent être alors en opposition. Les conséquences sur l’environnement et la santé humaine de l’intensification des pratiques agricoles avec l’utilisation croissante de produits chimiques ont amené la société civile, et les pouvoirs publics à s’interroger sur la pérennité de ce système de développement et à interroger le monde scientifique pour proposer d’autres modes de production permettant un développement durable. Comment mettre en place des systèmes de production agricole durables dans les territoires, tout en répondant aux objectifs d’accroissement de la production pour assurer un niveau acceptable de sécurité alimentaire. Cette question aujourd’hui, s’inscrivant dans un contexte de changement climatique est devenue centrale pour les responsables des politiques. L’agriculture est associée à la notion de territoire, la durabilité environnementale à une problématique collective, ce qui modifie les paramètres de formulation des actions de politiques publiques. Il faut aujourd’hui construire des démarches de gestion intégrées et collectives de l’agriculture dans ses territoires, en prenant en compte les acteurs locaux et les potentialités et les spécificités de l’environnement physique. Pour construire un projet collectif, il est donc nécessaire de comprendre les représentations que les usagers et parties prenantes dans la gestion et l’utilisation de l’écosystème se font de sa dynamique et des interactions entre règles d’usages et comportements des acteurs locaux. Quels outils et méthodes doivent mettre en place les décideurs dans les territoires pour répondre à ces objectifs ? Le cadre de travail se situe à l’interface de différents champs scientifiques ; agronomie, géographie et économie. Une modélisation du fonctionnement du territoire comme instrument de support au dialogue semble être appropriée pour une telle démarche ; devant permettre de simuler différentes alternatives et de permettre des regards croisés. La première partie de la thèse va s’attacher à une revue de littérature des instruments et méthodes existant dans ce domaine, notamment en termes d’indicateurs de caractérisation et de solutions alternatives en terme de production. Le choix en terme de méthode générique s’oriente pour l’instant vers l’élaboration d’outils de simulation spatialisés, collectifs et interactifs. L’objectif est de pouvoir construire une méthode d’élaboration de plans stratégiques agricoles permettant de poser les fondements d’une politique publique territorialisée. Le terrain d’application sera la région de la Bekaa au Liban , qui est une zone d’intensification agricole au Liban, et contribuant de manière très importante à la production agricole du Liban. / For many countries, food security is the biggest challenge facing agriculture, while ensuring environmental sustainability. Sustainable intensification of production and preventing crop losses are key element to increase production and ensure their consistency, massive inputs (fertilizers, pesticides) use is most often the easiest and the safe solution in the short term. These intensification practices resulting sometimes in increasing excessive consumption of fertilizers and pesticides have a negative impact in both environment and human health, which today pose the problem of the sustainability of these production methods. Ensuring food security through process intensification and environmental sustainability seem to be in opposition. The impact on the environment and human health from the intensification of agricultural practices with the increase in using chemicals has carry civil society and governments to query the sustainability of this development system and to question the scientific community to provide other types of production for sustainable development. How to build sustainable systems of agricultural production in the territories, while responding to the objectives of increased production to ensure an acceptable level of food security. This question as part of climate change today has become central to policy makers. Agriculture is associated to the concept of territory, environmental sustainability to a collective problem; modify the parameters for the formulation of public policy actions. We must now build integrated management approaches and collective agriculture in these territories, taking into consideration the local stakeholders, the potentialities and the specifications of the physical environment. To build a collective project, it is crucial to understand the representations that users and stakeholders in the management and the ecosystem uses should be done in dynamics and interactions between rules of practice and behavior of local actors. What tools and methods must implement policy-makers in the territories to meet these goals? The framework is at the interface of different scientific fields; agronomy, geography and economics. A model of the operation planning as an instrument of support for the dialogue seems to be appropriate for such approach; possible to simulate different alternatives and allow viewpoints. The first part of the thesis will focus on a literature review of existing instruments and methods in this area, particularly in terms of indicators of characterization and alternative solutions in terms of production. The choice in terms of generic method is oriented on elaborating of tools in spatially, collective and interactive simulation. The goal is to build a method for developing an agricultural strategic planning to allow the basis of a territorial public policy. The field of application will be the Bekaa region in Lebanon, which is an intensive farming area in Lebanon, and contributing very significantly to agricultural production in Lebanon.

Ce travail contribue à l'acquisition des connaissances sur les mécanismes et les facteurs contrôlant le transfert des éléments traces dans le système sol-nappes d'eaux souterraines. Le nombre de plus en plus important de sols contaminés par les éléments traces potentiellement toxiques suite aux activités industries a reçu beaucoup d'attention au cours des deux dernières décennies. Les polluants accumulés dans ces sols peuvent alors être transférés dans différents compartiments de l'environnement en fonction de leur origine, leur spéciation et les conditions physico-chimiques et biologiques du milieu. Ainsi, une des problématiques est la pollution des nappes d'eau souterraine par ces éléments traces. Les flux massiques d'éléments traces dans les sols vers les nappes d'eau souterraines sont un paramètre d'entrée important pour prévoir le devenir des pollutions des aquifères et donc à évaluer le potentiel de la contamination des ressources en eau potable. L’objectif de cette thèse a été de proposer une méthode de mesure des flux en laboratoire qui permette de simuler au mieux les conditions naturelles des transferts des éléments traces vers les nappes. Pour cela, nous avons mis au point une colonne de laboratoire non-saturée. Cette colonne a été testée dans différentes conditions de lixiviation, comparée aux méthodes de lixiviations normées et testée en condition d’immobilisation des éléments traces lors de l’apport d’amendements. Dans un premier temps, la colonne de laboratoire permet de diminuer l’erreur sur l’estimation des flux. Elle permet des mettre en évidence des phénomènes de sorption, désorption et complexation des éléments traces sur les substrats, contrôlant ainsi les transferts verticaux.Dans un deuxième temps nous avons évaluer l’effet d’amendements minéraux sur la mobilité des éléments traces sur deux sols contaminés par des extractions chimiques. Nous avons ensuite étudié la lixiviation de ces éléments suite à l’apport d’amendements: de l’hydroxyapatite et de la Grenaille d’acier dans ces deux sols en utilisant les colonnes de sol développés précédemment. L'étude de la localisation des éléments traces sur les minéraux nouvellement formés suite à l'apport de ces amendements minéraux et leur interaction avec les constituants minéraux d'origine des sols (microscopie couplé à des spectromètres de fluorescence X) nous a permis de comprendre et de déterminer les réactions mis en jeu au cours de la lixiviation de ces éléments. Ainsi, l’apport d’hydroxyapatite (HA) et de Grenaille d’acier (GA) ont permis de diminuer significativement les concentrations en Cd, Zn dans les lixiviats. En revanche, l’apport de HA et GA aux sols augmente significativement la libération de As (dans le cas de HA) et Pb suite a l’apport de GA et HA. Les phases minérales porteuses de ces éléments traces, ont pu être caractériser et ainsi les mécanismes responsables de l’immobilisation ou du relargage ont pu être identifiés. / This work contributes to the knowledge of the mechanisms and factors controlling the transfer of trace elements, particularly in the soil- groundwater pathway. Extensive soil contamination with potentially toxic traces elements from various industries has in many industrialized countries received significant attention over the last two decades. Mass fluxes of trace elements in soils to groundwater are important input parameter for predicting the fate of pollution of aquifers and thus to assess the potential for contamination of drinking water resources. The objective of this study was to propose a method for measuring the fluxes in laboratory to simulate the natural conditions. For this, we have developed an unsaturated soil column. This column was then tested in various leaching conditions (compared to standardized leaching methods and tested under conditions of immobilization of trace elements). At first, the laboratory column reduces the error in the estimation of flux. And allows to highlight sorption, desorption and complexation of trace elements on the substrates. In a second step we evaluate the effect of mineral amendments on the mobility of trace elements in two contaminated soils (extraction), the study their location on the newly formed minerals (microscopy coupled with X-ray fluorescence spectrometers) and finally the leaching of these. The addition of hydroxyapatite (HA) and Steel Shot (GA) have significantly reduced the concentrations of Cd, Zn and As (in the case of the contribution of GA). In contrast, the addition of HA and GA in soils significantly increases the release of As (in the case of HA) and Pb following the addition of GA and HA). Mineral phases carrying these trace elements have been well characterized and the mechanisms responsible for the retention or release have been identified.