Abstract A novel process of combining electrokinetic remediation and nano-sized iron wall was used for studying its effectiveness of treating nitrate-containing soil. Nitrates and nitrites are commonly found in surface water and groundwater. These substances, in general, could pose a threat to both organisms in the water bodies and human health. Traditionally, nitrogen oxides in various water bodies are treated by biological denitrification processes. However, it would take a longer time to yield a satisfactory result as compared with physicochemical processes. In recent years, permeable reactive barriers (PRBs) using zero-valent iron have been successfully used for degradation of various compounds including nitrates. Electrokinetic processing (EK) also is considered as an effective in-situ technology for removing both inorganic and organic substances from the treatment zone. In this work, the synthesized nano-scale iron particles were incorporated into a PRB, which was further combined with EK to form a novel process for the degradation of nitrates. Various operating parameters were studied in this work. The nano-sized iron particles were determined to be ranging from 50-80nm in size and having specific surface area of 37.83m2. The isoelctric point of these nanoparticles was found to be at pH 7.3. Experimental results have shown that the best location of the iron wall was 5cm from the anode reservoir. Also, the optimal treatment time would be six days in this study. The treatment efficiency was found to increase with increasing dose of nano-sized iron particles in the PRB. Operating with the polarity reverse would slightly increase the overall treatment efficiency as compared with the case of no polarity reverse (92.38% versus 88.34%). An electric gradient of 1.5V/cm was determined to be the optimal electric field strength in this study. In this work, it was also found that 2.5g nano-scale iron particles outperformed 20g micro-scale iron particles (75-150µm) in terms of nitrate degradation. In a study of using an extended treatment time up to 20 days, the black colored iron wall would fade away becoming a rusty plume toward the cathode as the treatment time elapsed. Furthermore, the Fe2+ concentration was elevated throughout the soil column after the 20-day treatment. Therefore, it is evident that nano-sized iron particles would migrate when they are subjected to EK. Based on the research findings obtained, the novel process employed in this study was found to be an effective one for in-situ treatment of nitrate-containing soil.

<p>U radu je: 1. Određena efikasnost elektrokinetičkih tretmana (konvencionalni tretman, tretman sa izmenom polariteta, tretman sa dve anode i heksagonalni dvodimenzionalni elektrokinetički tretman) koji izuzimaju dodatak agenasa u tretirani sediment, za uklanjanje metala; 2. Ispitan je uticaj diskontinuiteta napajanja strujom (tokom noći), kao i uticaj oscilacija jačine električne energije pri primeni solarnih panela na efikasnost tretmana; 3. Ispitan je uticaj geohemije sedimenta, fizičko-hemijskih promena u sistemu i karakteristika prisutnog zagađenja (oblici pojavljivanja metala, koncentracije) na efikasnost elektrokinetičkog procesa. 4. Izvr&scaron;ena je procena rizika u sistemu sediment/voda pre, tokom i nakon tretmana; 5. Primenjen je matematički model na dobijene rezultate. Na osnovu određene efikasnosti i procene rizika tretmana elektrokinetičke remedijacije na realan problem Velikog Bačkog kanala zaključeno je, da je najbolja opcija dvoanodni tretman u kome se primenjuju solarne panele (e9). Dobijeni rezultati tretmana ukazuju da diskontinuiteti napajanja strujom (tokom noći), kao i uticaj oscilacija jačine električne energije pri primeni solarnih panela nemaju značajnog uticaja na efikasnost procesa. &Scaron;to se tiče, geohemije sedimenta, pokazalo se da ona ima snažan uticaj i da upravo ona određuje fizičko-hemijske promene koje se događaju u sedimentu tokom sprovođenja tretmana elektrokinetičke remedijacije. Ključ uspeha ovih tretmana sedimenta jeste i zadržavanje metala u frakcijama (karbonatna i reducibilna) koje lak&scaron;e migriraju. Primenom matematičkog modela zaključeno je da se mogu predvideti promene koncentracija metala bez sprovođenja eksperimenata, &scaron;to je od krucijalnog značaja za buduća istraživanja.</p> / <p>This work includes: 1. An investigation into efficiency of various electrokinetic treatments (a conventional treatment, and treatments with changing polarity, two anodes and two-dimensional hexagonal electrodes) without the addition of agents to the treated sediment, for the removal of metals; 2. An investigation of the influence of discontinuous (off during the night) and oscillating power supplies on the application of solar panels and their effect on the efficacy of the treatment; 3. A study on the influence of sediment geochemistry, physico-chemical changes in the system and the characteristics of the pollution present (metals speciation and concentration) on the efficiency of the electrokinetic process; 4. A risk assessment of the sediment/water system before, during and after the treatment; 5. Mathematical modelling of the results obtained. Based on the risk assessment and the efficiency of the electrokinetic treatments in the Veliki Backa canal sediment, it was concluded that the best remediation option was a two anode treatment using solar panels (e9). The investigation into the influence of treatments using discontinuous (off during the night) and oscillating power supplies showed they did not have a significant impact on the efficiency of the process. Sediment geochemistry was shown to have a strong influence, determining the physical and chemical changes that occur in the sediment during the implementation of the electrokinetic remediation. The key to success for these treatments is the retention of metals in the fractions (carbonate and reducible) which more easily migrate. It is concluded that the mathematical model can be applied to successfully predict thechanges in the concentration of metals without experimentation, which is of crucial importance for future studies.</p>

Sites contaminated with polycyclic aromatic hydrocarbons can be simultaneously contaminated with trace elements. Co-contaminated soil is considered a complex problem since inorganic and organic contaminants behave differently and thereby often require different remediation strategies. Despite the fact that co-contaminated soils are a common problem, existing research on remediation of contaminated soil mostly focuses on either organic or inorganic contaminants. In the present study, the possibilities of electrokinetic remediation as an alternative to commonly used remediation technologies was investigated. An experiment was setup to evaluate the effects of electrokinetic remediation on both polycyclic aromatic hydrocarbons and trace elements, such as arsenic, cadmium, chromium, copper, lead and zinc, simultaneously. The experiment was performed in 12 litre large plexiglass cells. Two cells with electrokinetic treatment, equipped with iron electrodes, to amend the soil with iron via intentional corrosion of the electrodes, and one control. The cells were filled with contaminated soil and deionized water was pumped through the cells to simulate a groundwater flow. The experiment ran for two months, during which pore water was sampled weekly and simulated groundwater monthly, to monitor changes in contaminant concentrations. Soil samples were taken at the start and at the end of the experiment. Results showed that the concentration of polycyclic aromatic hydrocarbons in the simulated groundwater decreased from 0.39 ± 0.15 μg L-1 to 0.12 ± 0.064 μg L-1 during the experiment. However, at the point of writing, samples of soil at the end of the experiment has not yet been analysed for concentration of polycyclic aromatic hydrocarbons, something that needs to be done to validate previously described results. In terms of the trace elements, the applied method did not increase their mobility, nor did it decrease it. Moreover, the trace elements behaved similarly in the control cell as in the treatment cells. This was observed for all the tested trace elements, indicating that electrokinetic remediation in this particulate case may be a suitable remediation technology for organic, but not that successful for inorganic contaminants. In regard to this, further research is required to establish whether electrokinetic remediation is a promising remediation technology for co- contaminated soil and how it can be optimized to ensure remediation success for both organic and inorganic contaminants.

Les travaux de cette thèse sont consacrés principalement à l'optimisation d'une méthode de remédiation électrocinétique (EK) comme une technologie appropriée pour le traitement de sédiments de dragage de faible perméabilité hydraulique et multi-contaminés (en éléments traces (ET), hydrocarbures aromatiques polycycliques (HAP) et polychlorobiphényles (PCB)). Cette étude porte également sur l’effet du traitement EK sur l’évolution de la toxicité des sédiments. Après une revue bibliographique, une seconde partie a été dédiée aux méthodes d’analyse des contaminants, avec un focus sur leur extraction de la matrice sédimentaire ; ainsi, une nouvelle méthode d’extraction par dispersion de la matrice solide (MSPD) a été développée, pour une extraction rapide et simultanée des HAP et de PCB et une purification de l’échantillon, qui s’est avérée plus efficace que la méthode d’extraction assistée par micro-ondes (MAE). Plusieurs études expérimentales (à différentes échelles) de remédiation électrocinétique ont été décrites dans une troisième partie ; ces études ont été menées sur un sédiment reconstitué ou des sédiments de dragage portuaire. De nombreuses combinaisons de tensioactifs et d’agents chélatants ont été testées comme agents d’amélioration pour abaisser simultanément la concentration en métaux (Cd, Cr, Cu, Pb, Zn) et des HAP/PCB. Le choix a été effectué en raison notamment de leur faible toxicité potentielle, en vue de pouvoir les appliquer ultérieurement pour une restauration sur site : (bio)surfactants (Rhamnolipides, Saponine et Tween 20) combinés avec des agents chélatants (acide citrique (CA) et EDDS). Les résultats obtenus montrent que les métaux (à l'exception de Cr) sont difficiles à extraire de ces sédiments de dragage portuaire à caractère réducteur, qui présentent une capacité tampon élevée, une perméabilité hydraulique très faible et une teneur en matière organique élevée. En revanche, les HAP et les PCB fournissent de meilleurs taux d'abattement (29,2% et 50,2%, respectivement). Dans une quatrième partie, l'efficacité du procédé EK a également été évaluée à travers l’évolution de la toxicité aiguë des sédiments traités sur les copépodes E. affinis exposés aux élutriats de sédiments. Les résultats ont montré que l'utilisation de CA,des biosurfactants et du Tween 20 n'a pas eu d'impact significatif sur la toxicité des sédiments traités. Cependant, les copépodes E. affinis étaient sensibles aux faibles valeurs de pH et aux conditions très oxydantes, ainsi qu’à la présence de Cu et, dans une moindre mesure, de Pb, à condition toutefois qu’ils soient rendus plus mobiles et biodisponibles. En revanche, la toxicité a été peu et même négativement corrélée aux concentrations des HAP et des PCB après le traitement EK, probablement en raison de la production de métabolites oxydés des HAP et des PCB, plus toxiques que les composés natifs. / This thesis research is mainly devoted to the optimization of an electrokinetic (EK) remediation process as a promising technology for treating multi-contaminated (trace metals, polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyles (PCBs)) dredged harbor sediments of low permeability. This study is also investigating the effect of the EK treatment on the evolution of sediment toxicity. After a bibliographic review, asecond part of this study was dedicated to the analytical methods carried out for the characterization of the sediment and its contaminants, particularly to their extraction from the sediment matrix; thus a new extraction method, through matrix solid phase dispersion (MSPD) was developed, for a fast and simultaneous extraction of both PAHs and PCBs, and a sample purification.MSPD appeared more efficient than the microwave assisted extraction (MAE) method. Thereafter many EK experiments (at different scales) were described in a third part. EK remediation tests were performed using a spiked model sediment or natural harbor dredged sediments. Many combinations of surfactants and chelators were tested as EK enhancing agents for decreasing simultaneously metal (Cd, Cr, Cu, Pb, Zn) and PAH/PCB levels. Their choice was done because of their possible low toxicity with a view to use them for future site restoration: (bio)surfactants (rhamnolipids, saponin and Tween 20) combined with chelators (citric acid (CA) and EDDS). The results showed that metals (except Cr) were difficult to remove from this kind of dredged sediment owing to its reductive character, to its high buffering capacity, to its very low hydraulic permeability and to its high organic matter content. However PAHs and PCBs showed better removal levels (29.2% and 50.2%, respectively). In a fourth part, the efficiency of the EK process was also assessed by measuring the evolution of the acute toxicity of the treated sediment on E. affinis copepods exposed to sediment elutriates. The results showed that using CA, biosurfactants or Tween 20 as enhancing agents did not significantly impact the toxicity of the treated sediment. However, E. affinis copepods were significantly sensitive to low pH values and oxidative conditions, to Cu, and to a lesser extent to Pb amounts, if they were transformed in more mobile and bioavailable forms. In contrast, acute toxicity was only slightly and even negatively correlated to PAH and PCB amounts after EK treatment, probably due to the production of oxidized metabolites of PAHs and PCBs, more toxic than the parent compounds.