Contaminated land is a widespread, global issue affecting millions of people. Atrazine is a commonly used herbicide which often contaminates groundwater and drinking water supplies and is associated with adverse health outcomes. Biochar is the solid product of pyrolysis and is associated with several environmental benefits. It may be an effective remediation tool when used as a soil amendment. This thesis investigates the mechanisms through which biochar can immobilise atrazine, and the implications of the mechanisms for remediating contaminated land. Nine biochar samples were obtained from the United Kingdom Biochar Research Centre , which were produced from softwood pellets (SWP), wheat straw pellets (WSP), miscanthus straw pellets (MSP), rice husk (RH) and oil seed rape (OSR) each at pyrolysis temperatures of 550°C and 700°C (excluding OSR at 700°C). The sorption mechanisms controlling atrazine sorption to these biochars were determined through various characterisation methods and batch sorption experiments. The sorption tests showed that sorption to each of the standard biochars occurs via multiple simultaneously occurring mechanisms, which are each promoted under certain conditions. Studies investigating sorption kinetics, isotherms and interactions with humic acids showed that for all biochars in this study, pore filling was a significant process through which atrazine is transported to adsorption sites, although poor intraparticle diffusion for softwood and oil seed rape biochars can prevent efficient transport. Wheat straw and rice husk biochars showed effective pore diffusion, resulting in high sorption capacities. Partitioning was associated with poor remediation outcomes and was significant to softwood biochars, although adsorption dominated overall sorption for all other biochars. pH was shown to significantly influence the occurrence of various sorption mechanisms. At low pH values, most biochars showed evidence of electrostatic repulsion between positive atrazine species and the positively charged biochar surface. At intermediate pH values, all biochars showed strong hydrogen bonding between H+ groups on the surface of the biochar and atrazine. A meta-analysis of previous relevant studies provided further evidence for hydrogen bonding of atrazine to biochar and showed that hydrophobic effects likely play little role in adsorption after accounting for the effects of surface area. Varying contributions of π-π EDA interactions, hydrogen bonding involving biochar O- groups, and interactions with ash minerals resulted in different sorption profiles for each biochar at high pH values. In order to further determine the mechanisms controlling sorption at high pH, surface compositions of SWP550, RH700 and OSR550 biochars were modified using hydrofluoric acid. Modification with hydrofluoric acid successfully removed the ash contents of rice husk and oil seed rape biochars and reduced atrazine removal at high pH values. This suggested that the ash fraction increases atrazine removal at high pH through complexation or catalytic hydrolysis. The roles of the various mechanisms are related to remediation outcomes in a novel manner allowing for the improved design of biochar for environmental remediation.

Content removed due to copyright restrictions: Anderson, C., Moreno, F., & Meech, J. (2005). A field demonstration of gold phytoextraction technology. Minerals Engineering, 18(4), 385-392. / Mercury (Hg) is a toxic heavy metal that is concentrated in organisms. Injudicious use of Hg and its compounds have resulted in widespread soil contamination. This study investigates the potential use of plants for the remediation of Hg-contaminated mine wastes. Plants can remove soil Hg via phytoextraction and phytovolatilisation. I investigated both of these strategies by focusing on a methodology for Hg analyses in plants and soils with a view to the determination of volatile Hg emitted from plants. Secondly, I determined the feasibility of Hg phytoextraction and phytovolatilisation from contaminated mine wastes. An accurate method for the analysis of Hg in air, plant and various soil fractions was a key component of this study. I developed a hydride-generation atomic absorption spectroscopy method for total Hg analyses in digest and liquid matrices of the aforementioned samples. Quality assurance was ensured by comparing results with those of an external certified laboratory. The maximum discrepancy was 15 %. To measure plant Hg-volatilisation, a method that captures Hg-vapour in solution for subsequent analyses was developed. Initially this system was used to trap Hg vapours released from the root system of Brassica juncea plants grown in hydroponic solutions. A subsequent study improved the Hg trapping system, allowing the capture of volatile Hg from both roots and shoots. Mercury recoveries from the whole plant system (traps + plant + solutions) averaged 90 % using this experimental apparatus. In most contaminated substrates, plant Hg uptake is insignificant, possibly due to the low bioavailability of Hg. This represents an obstacle for effective remediation using phytoextraction. Geochemical studies were carried out in Hg-contaminated substrates to examine the potential of chemical agents to induce Hg solubility and subsequent plant uptake. These studies utilised Hg-contaminated mine tailings collected from three locations: the Tui base-metal mine, in the North Island of New Zealand, the Gold Mountain mine, in North-Central China and, the Serra Pelada artisanal mine site, in Northern Brazil. The results demonstrated that Hg solubility in all tested substrates is increased in the presence of sulphur-containing chemical ligands. The effectiveness of these ligands was influenced by site-specific geochemistry. Plants species were able to accumulate up to 60 mg/kg of Hg in shoot tissues upon addition of sulphur-containing ligands to Tui and Gold Mountain substrates. The degree of plant-Hg accumulation was shown to be dependant on plant species and on the thioligand-induced soluble Hg fraction. Shoot Hg transport was inhibited for Gold Mountain substrate amended with 1.25g/kg of humic acid. The maximum Hg extraction yield for B. juncea plants growing in Tui field sites averaged 25 g per hectare following application of sodium thiosulphate. Volatilisation of Hg vapour from barren substrates occurred as a result of biotic (microorganisms) and abiotic (chemical and photochemical reduction) processes. The presence of B. juncea plants in substrates enhanced the volatilisation process up to 23 fold. Phytovolatilisation was the dominant pathway responsible for between 75 to 99.5 % of the total Hg removed from substrates. It was concluded that Hg removal from contaminated mine wastes can be accomplished by both thioligand-induced phytoextraction and phytovolatilisation. There are risks of groundwater contamination by Hg species mobilised after application of thioligands to substrates. Estimated Hg (0) emissions from plant-based operations at contaminated sites ranged between 1.5 to 3.6 kg of Hg/ha per year. Due to extensive atmospheric dilution, Hg emissions from small-scale phytoremediation operations would not cause serious harm to the local population or the regional environment. Phytoremediation combined with gold-phytoextraction can help to mitigate Hg-pollution in artisanal mine sites in the developing world.

Thesis (Ph.D.) -- Mississippi State University. Dave C. Swalm School of Chemical Engineering. / Title from title screen. Includes bibliographical references.

The influence of crude oil-contaminated and remediated sites on agrifood production is not clearly understood. To address this knowledge gap, the research was divided into two stages involving: (1) assessment of the efficiency of two bioremediation strategies to support hydrocarbons degradation as well as agrifood production with the initial analysis of the experimental materials, and (2) evaluation of the effect of different crude oil remediation intervention values (CRIV) on selected vegetables (Brassica juncea, Brassica oleracea, Lactuca sativa and two different cultivars of Solanum lycopersicum). Results from the first stage showed that the crude oil used had a pristane/phytane ratio of 0.98 (within the 0.8 – 3.0 range of most crude oils), higher concentrations of C10 – C14, C15 – C20 and C21 – C27 alkanes than the C28 – C36 alkanes including higher concentrations of two of the US EPA priority pollutant polycyclic aromatic hydrocarbons (PAHs) - phenanthrene and anthracene. Four treatments were prepared in which weekly tillage enhanced the degradation of C15 – C20 and C21 - C27 alkanes in the Remediation by Enhanced Natural Attenuation (RENA) treatment. The two bioremediation strategies (RENA and bioaugmentation) enhanced PAHs degradation compared with the remediation-study control treatment while only RENA application among the two approaches supported the growth of B. juncea. Although there was no statistical significant difference (p > 0.05) between the major dietary mineral contents of samples from the various treatments compared with the control treatment samples, RENA application affected the Cr, Zn and Pb contents. Meanwhile, the Ca/P (> 1.0) and Na/K (< 0.60) ratios of all the harvested samples imply that they provide a good source of these minerals for bone formation and would not contribute to high blood pressure. The crude oil used also deterred the attack of juvenile caterpillars of cabbage white butterfly. Findings from the second stage revealed that the yield of the green leafy vegetables including one of the selected tomato cultivars (Micro-Tom), was in most cases impaired at CRIV ≥ 3,000 mg/kg total petroleum hydrocarbon (TPH). Compared with the control treatment samples’ composition, crude oil stress at 10,000 mg/kg TPH enhanced the concentration of K, Mn and crude protein of B. oleracea and L. sativa as well as the sucrose, total sugars, total phenolics and total flavonoids contents of the latter vegetable. Sucrose was also only detected in M82 tomato cultivar samples from the crude oil-containing treatments. The Cd content of B. oleracea, Pb contents of: L. sativa and M82 tomato harvested samples were all below the FAO/WHO Codex Alimentarius Commission 2015 recommended maximum levels. However, tartaric acid was only detected in B. oleracea and L. sativa samples from the 10,000 mg/kg TPH treatment as well as in M82 tomato cultivar samples from the treatment involving CRIV of 5,000 mg/kg TPH. Generally, the yield of these crops in response to crude oil contamination varied in which B. juncea had the least tolerance to crude oil stress among the green leafy vegetables tested. Most of the quality parameters in the two tomato cultivars were not affected by CRIV between 750 - 5,000 mg/kg TPH with p-xylene having the greatest toxic potential among the VOCs emitted from the 5,000 mg/kg TPH treatment. The research findings, under the experimental conditions, indicated the effectiveness of RENA for the degradation of low molecular weight PAHs and its agricultural benefits. They also suggest that crude oil-contaminated sites at ≤ 3,000 mg/kg TPH present a similar growing environment to a clean site for agrifood production and the possibility that crude oil stress at 10,000 mg/kg TPH could enhance crop quality. Nonetheless, the contribution of bio- accumulated PAHs in these crops to the food chain demands further investigation.

Water pollution has become an environmental catastrophe due to the rapid urbanization. The treatment of dumping of waste chemicals in water bodies has contributed to the increase in pollution. In addition to the pollution caused by waste chemicals, faecal bacteria such as Escherichia, Staphylococcus, Pseudomonas etc., can cause serious health issues. Techniques such as filtration and chlorination provide clean water but are associated with disadvantages such as toxic by-products. Although clean water can be still obtained by these techniques, the development of resistance by microorganisms with such conventional treatments of antibiotics is inevitable and poses a new threat. Various researches have taken place in the past few decades to provide clean drinking water. Photocatalysis is considered to be a promising viable alternative for the existing methods to solve the menace of water pollution. It is an advanced oxidation process where the reactive oxygen species are generated by using nanomaterials that can cause degradation of chemicals and pathogens. Particularly, photocatalysis using semiconductors and their composites have been tested for their use in the destruction of contaminants. Several methods have been used in the synthesis of nanomaterials and the variations in their morphologies have resulted in different applications such as photocatalysis and electrocatalysis. Among all semiconductors, TiO2 has been widely used in this application owing to their non-toxicity and abundance in availability. However, TiO2 can be activated only in the presence of UV light. Therefore, the formation of heterojunctions, doping of metals/no- metals in TiO2 has enabled the activation of TiO2 in the visible region. The former approach has also been studied with ceria and silver salts combination. Besides conventional metal oxides, other transitional metal oxides such as copper oxide and bismuth oxide have also been studied owing to its conducting property and facile growth on substrates respectively for enhanced photocatalysis. All the above tweaking has enabled efficient charge separation, band gap reduction, and prevention of recombination. In this thesis, all the nanomaterials and their composites have been synthesized using simple methods such as solution combustion, hydrothermal, solution co-precipitation, and chemical deposition. The primary aim of this thesis is to synthesize various effective nanomaterials with different morphologies, bandgap engineered nanocomposites, metal or non-metal doped metal oxides for efficient waste water treatment of dyes, antibiotics, phenols, and bacteria. Besides, relying on photocatalytic ability, the photoconductivity and intrinsic conducting properties of nanomaterials were exploited to perform photoelectrocatalysis that enhances the rate of decontamination to several orders than photocatalysis. In addition to focusing on increasing the rate of degradation, the main drawback of photocatalysis which is catalyst retrieval has been overcome using conducting substrates and nanomaterial coated substrates for efficient photocatalytic and photoelectrocatalytic decontamination of waste water. All the structural, morphological, chemical and optical properties were thoroughly studied using various characterization techniques such as XRD, SEM, TEM, XPS, UV-DRS, PL respectively. The rate kinetics of dye, antibiotic and phenol degradation was examined. Experimental data was tested with the proposed model in the case of photoelectrocatalytic degradation. The photocatalysts were also studied for its reusability for many cycles. All the proposed works have analyzed the reason for the enhanced activity by performing scavenger reactions to determine the responsible reactive oxygen species. Thus, this thesis exhibits a thorough understanding of how to design and engineer nanomaterials for photocatalytic and photoelectrocatalytic water remediation. The following are the chapters discussed in this thesis. Chapter 1 discusses the drawbacks associated with the current waste water treatment methods and the possibilities of photocatalysis to replace the existing treatments. The advantages of certain transition metals, conventional methods of synthesis and various other properties of the nanomaterials have been discussed. Chapter 2 explains the synthesis of TiO2 nanobelts using combustion synthesized TiO2 under UV and solar irradiation. The catalyst has been characterized for its structural, morphological, chemical and optical properties. The degradation of anionic and cationic dyes and their activity against E.coli bacteria have been evaluated. The efficiency of this catalyst has been compared with commercial Degussa P25. This study shows the morphological influence of nanomaterials on photocatalytic activity. Chapter 3 describes the synthesis of Ag3PO4 impregnated combustion synthesized TiO2 nanobelts using co-precipitation technique. The activity of this material has been studied under solar light. The catalyst has been characterized for its structural, morphological, chemical and optical properties. Similar to the previous chapter, the degradation of dyes and the antibacterial activity of this catalyst has been compared with commercial Degussa P25. This study explains the importance of morphology and charge carrier facilitation in the case of heterojunction formation. Chapter 4 explains the synthesis of ceria nanoflakes by solution combustion method using ascorbic acid as fuel and PEG assisted sonochemical method. The catalyst has been characterized for its structural, morphological, chemical and optical properties. The effect of silver salts such as AgBr on ceria/Ag3PO4 under visible region for degradation of dyes and antibacterial activity has been evaluated. This work elucidates the effect of band engineering in the charge carrier dynamics between interfaces of components within the catalysts. Chapter 5 elucidates the synthesis of vanadium, nitrogen co doped TiO2 catalysts for the simultaneous degradation of microbes and antibiotics. The primary aim of this work is to understand whether interstitial or substituted doped nitrogen will be effective in the presence of vanadium. The photoactivity of this novel catalyst was studied for its synergistic degradation of antibiotics and bacteria simultaneously towards the prevention of microbial resistance towards antibiotics. Chloramphenicol and E.coli were subjected to photodegradation under visible light. Chapter 6 explains the synthesis of copper oxide based nanomaterial for antibiotic and bacterial degradation by photoelectrocatalysis. In order to enhance the rate of photodegradation, photocatalysis has been upgraded with the application of a potential to photocatalytic systems that possess better charge conducting capability. Highly network like copper oxide has been synthesized using conventional combustion synthesis method and compared with copper oxide nanorods synthesized by hydrothermal method. The rate kinetics of photocatalytic and photoelectrocatalytic degradation of antibiotics has been examined thoroughly and validated based on a cyclic network model. This work demonstrates the synergistic rate enhancing capacity upon combining photocatalysis and electrocatalysis. Chapter 7 discusses the fabrication of Cu/CuO/FTO (fluorine doped tin oxide) based substrates for bacterial degradation. Considering the difficulties in photocatalyst retrieval processes and realizing the importance of electrocatalysis, conducting substrates such as Cu strip, FTO were subjected to antibacterial treatment. Formation of copper oxide onto copper strip during the course of reaction forced us to develop CuO/Cu and CuO/FTO interfaces to examine the photocatalytic and photoelectrocatalytic killing of E.coli. Chapter 8 investigates the fabrication of Bi2O3/Ag based material for photocatalytic and photoelectrocatalytic degradation for phenols and substituted phenols. This work starts with fabrication of Bi2O3 working electrodes by chemical deposition. Photodegradation experiments were conducted under UV irradiation and enhancement of the rate of degradation was observed when the working electrode was deposited with silver nanoparticles via chemical reduction method. Formation of the intermediate Bi(OH)x on Bi2O3 or Bi2O3/Ag has resulted in better hydroxyl radical generation upon excitation. Similarly, surface plasmon resonance due to silver nanoparticles was found to be responsible for augmentation in degradation efficiency of phenol. Chapter 9 briefly summarizes the work and provides future directions. The research work thus attempts to design and engineer photocatalytic nanomaterials that are better than the existing materials and emphasizes the importance towards water remediation.

Die vorliegende Arbeit entstand im Rahmen einer pilotmaßstäblichen Boden- und Grundwassersanierung am Industriestandort „Hydrierwerk Zeitz“. Auf dem Gelände einer ehemaligen Benzolproduktionsanlage wurden großflächige Kontaminationen von Boden und Grundwasser festgestellt. Mittels moderner Erkundungstechnik konnten die Haupteintragsbereiche des dominierenden Schadstoffes Benzol erkundet und eingegrenzt werden. Verschiedene Arten von Grundwasser-, Boden- und Bodenluftbeprobungen sowie geophysikalische Verfahren erlaubten eine exakte Lokalisation des Schadstoffquellbereiches sowie der sich hieraus ausbildenden Schadstofffahne. Ziel der am Standort durchgeführten Pilotsanierungen war die Beseitigung der Schadstoffquelle, um eine weitere Nachlieferung in die Schadstofffahne zu unterbinden. Der Schadstoffquellbereich der hier behandelten Pilotsanierung war auf eine Kubatur von ca. 15 x 9 x 11 Kubikmeter begrenzt. Als Hauptkontaminant lag mit einem Anteil von 98% Benzol vor. Weiterhin wurden Toluol, Ethylbenzol sowie Xylol in geringen Mengen angetroffen. Aufgrund der hochvolatilen Eigenschaften des vorliegenden Hauptkontaminanten Benzol wurde am Standort eine thermische Sanierung der gesättigten sowie ungesättigten Zone durchgeführt, die eine Extraktion von rund 8 Tonnen Benzol erzielte. Im Zentrum der Sanierungskubatur wurde mit Hilfe von drei Injektions¬brunnen ein Dampf-Luft-Gemisch injiziert und eine Zieltemperatur im aus¬gewiesenen Sanierungsbereich von 85 ˚C erreicht. Diese Temperatur übersteigt den Siedepunkt von Benzol (80,1 ˚C) und führt zu einem vollständigen Übergang des Schadstoffes in die Gasphase. Durch sechs das Sanierungsfeld eingrenzende Extraktionsbrunnen wurde der Schadstoff dem Untergrund entzogen und an der Oberfläche durch eine thermische Nachverbrennungsanlage geleitet. Eine Problematik dieser Sanierungstechnik ist die exakte Lokalisation der sich im Untergrund ausbreitenden Front des Sanierungsmittels. Aufgrund von Inhomogenitäten in gesättigter und ungesättigter Zone kommt es zur Ausbildung von präferentiellen Fließpfaden. Diese Strukturen verhindern eine radialsymmetrische Ausbreitung des Sanierungsmittels und sorgen dafür, dass zum Teil große Bereiche der Sanierungskubatur nicht abgereinigt werden. Weiterhin findet ein sehr großer Energieverlust durch teilweises Austreten des Dampf-Luft-Gemisches in Bereiche außerhalb der Sanierungskubatur statt. Eines der Hauptziele dieser Arbeit war daher die Durchführung eines geoelektrischen Monitorings, das es erlaubte, durch Messung von elektrischen Widerstandsänderungen im Untergrund Position und Lage des Sanierungsmittels zu bestimmen und solche Bereiche zu lokalisieren, die keine Abreinigung erfuhren. Weiterhin konnten durch dieses Monitoring präferentielle Fließpfade erkundet werden, die zu Energieverlusten von über 60% im Verlauf der Sanierung führten. Als innovatives Verfahren wurde am Sanierungsstandort ein 3-dimensionales geoelektrisches Monitoring durchgeführt; ein Verfahren, das Messungen an Oberflächenelektroden mit Messungen an im Untergrund eingebrachten Bohrlochelektroden verknüpft. Mit diesem Verfahren konnten hochaufgelöste 3-dimensionale Abbildungen erstellt werden, die die Ausbreitung des injizierten Sanierungsmittels im Verlauf der Sanierung abbildeten. Um eine in dieser Auflösung vergleichbare Abbildung der Temperaturbereiche im Untergrund durch Messungen mit fest installierten Temperaturmessketten zu erlangen, wäre eine unverhältnismäßig große Menge an Sensoren notwendig gewesen. Somit war die Entwicklung eines geoelektrischen Monitoringsystems die einzige Möglichkeit, den Sanierungsverlauf so zu verfolgen, dass während des Betriebes Optimierungsmaßnahmen durchgeführt werden konnten. Abschließend konnte das Sanierungsverfahren in Kombination mit Temperaturmessungen außerhalb des Sanierungsbereiches bewertet und Erkenntnisse für Verbesserungen bei zukünftigen Anwendungen gewonnen werden. / The work presented here was carried out within a pilot scale soil- and groundwater remediation project at the former industrial area „Hydrogenation plant Zeitz”. Beneath a former benzene production facility a large scale contamination of soil and groundwater was found. Using modern exploration technologies main spill and infiltration zones for the principal contaminant benzene as well as residual or floating phases could be identified. A variety of methods for sampling of groundwater, soil and soil-air, as well as different geophysical methods allowed for the exact localisation of the contaminant source zone and the contaminant plume emerging from the source zone. The objective of the pilot remediation was the (partial) removal of the contaminant source to prevent further supply to the contaminant plume. The source area of this pilot remediation was limited to a cubature of about 15 x 9 x 11 meters. Benzene as the main contaminant was assessed with a share of 98%. Additionally low concentrations of toluene, ethylbenzene, as well as xylols were found. Since the main contaminant benzene is characterised by high volatility, a thermal remediation approach for the saturated as well as unsaturated zone was conducted at the site which allowed for the extraction of about 8 t of benzene. By the help of three wells a steam-air-mixture was injected into the central section of the remediation cubature and a target temperature of 85 ˚C was reached. This temperature exceeds the boiling point of benzene (80.1 ˚C) and leads to a complete volatilisation of the contaminant. Six extraction wells surrounding the remediation cubature removed the contaminant from the subsurface and delivered it to a catalytic combustion system. The exact localisation of the spreading steam front in the subsurface is the main problem of this remediation approach. Preferential flow paths develop due to inhomogeneities in the saturated and vadose zone of the subsurface. These structures inhibit a radial-symmetric spreading of the steam-air-mixture and, hence, prevent the remediation of large sections of the cubature. Additionally a very high loss of energy into sections outside the target area takes place. To overcome this problem, it was one of the main objectives of this work to perform a geoelectrical monitoring of the remediation approach which allowed the localisation of the steam-air-mixture by measuring electrical resistivity distributions in the sub¬surface. In addition, the development of preferential flow paths which led to energy losses of over 60% during the remediation could be explored. As an innovative concept for this remediation method a 3-dimensional geoelectrical monitoring was conducted; a procedure that combines measurements at surface electrodes with measurements at borehole electrodes installed in the subsurface. With this method a high resolution 3-dimensional imaging could be established which displays the spreading of the steam-air-front during the remediation process. To achieve such an imaging with comparable resolution with standard temperature sensors installed in the subsurface, an unreasonable number of these sensors would have been necessary. The development of the geoelectrical monitoring system was the only approach that allowed the observation of the treatment process as well as optimisation of the remediation system during active remediation. Ultimately the remediation procedure could be evaluated with additional measurements outside the remediation zone and information for the enhancement of further applications could be obtained.

Η ρύπανση του εδάφους από βιομηχανικά και αστικά απόβλητα αποτελεί παγκοσμίως ένα από τα σημαντικότερα περιβαλλοντικά προβλήματα. Ανάμεσα στους πιο επικίνδυνους ρύπους συγκαταλέγονται και οι υδρογονάνθρακες πετρελαιοειδών. Αναπόφευκτη συνέπεια της διαφυγής των υγρών ρύπων στο έδαφος είναι η μεταφορά τους προς στην ακόρεστη ζώνη του εδάφους μέσω μιας σειράς διεργασιών (ροή, διαλυτοποίηση, εξάτμιση, διασπορά, ρόφηση, κτλ) και η ρύπανση των υποκείμενων ταμιευτήρων υπογείων υδάτων. Οι πλέον κλασσικές μέθοδοι απομακρυσμένης (ex situ) απορρύπανσης εδαφών περιλαμβάνουν εκσκαφή και μεταφορά του εδάφους σε κατάλληλους χώρους (π.χ. αποτεφρωτήρες, βιο-σωροί, κλπ). Τα τελευταία χρόνια έχει αναπτυχθεί έντονο ενδιαφέρον για την ανάπτυξη και εφαρμογή τεχνολογιών επιτόπιας απορρύπανσης των εδαφών (in situ soil remediation) με χαμηλό κόστος και ελάχιστο περιβαλλοντικό αποτύπωμα. Στην παρούσα εργασία μελετώνται δύο σχετικά νέες μέθοδοι επιτόπιας απορρύπανσης: α) ο βιοαερισμός και, β) η έγχυση ατμού. Και στις δύο περιπτώσεις, για να αυξηθεί η ακτίνα δράσης της απορρύπανσης, το έδαφος διεγέρθηκε με την δημιουργία οριζόντιων υδραυλικών ρωγμών που λειτουργούν ως οριζόντια φρεάτια διαβίβασης και εξαγωγής ρευστών. Το πεδίο μελέτης είναι ένα πρώην στρατιωτικό αεροδρόμιο της Βόρειο-Δυτικής Πολωνίας, το Kluczewo, το οποίο έχει ρυπανθεί εκτεταμένα με κηροζίνη για μεγάλο χρονικό διάστημα (1935-1992). Το έδαφος της περιοχής αυτής παρουσιάζει ρωγμές ενώ η πορώδης μήτρα έχει σχετικά χαμηλή διαπερατότητα. Οι ίδιες γεωλογικές συνθήκες επικρατούν σε μεγάλο μέρος του υπεδάφους της Βόρειας Ευρώπης. Λόγω της ισχυρά ετερογενούς φύσης αυτών των εδαφών από την κλίμακα των πόρων στην κλίμακα του πεδίου και της δημιουργίας προτιμητέων μονοπατιών ροής, είναι αρκετά δύσκολο να σχεδιαστούν αποδοτικές μέθοδοι απορρύπανσης. Κύριος στόχος της εργασίας είναι η αξιολόγηση της απόδοσης των δύο μεθόδων απορρύπανσης μετά την εφαρμογή τους στην ακόρεστη ζώνη ετερογενούς εδάφους που έχει ρυπανθεί εκτενώς με υδρογονάνθρακες πετρελαιοειδών (κηροζίνη). Για να προσδιοριστεί η απόδοση κάθε μεθόδου, συλλέχθηκαν δείγματα εδάφους από ένα μεγάλο αριθμό σημείων και πραγματοποιήθηκαν χημικές αναλύσεις μέτρησης της συγκέντρωσης και της σύστασης των υδρογονανθράκων με GC-MS και GC-FID. Προκειμένου να διευκρινιστoύν καλύτερα οι κύριοι μηχανισμοί απομάκρυνσης του ρύπου και να εκτιμηθεί η αποδοτικότητα της έγχυσης ατμού και του βιοαερισμού, διεξήχθησαν πειράματα έγχυσης ατμού και βιοαερισμού και σε εργαστηριακή κλίμακα (oρθογώνιο κελί από PMMA με διαστάσεις 55 cm x 50 cm x 12 cm και υπό ακόρεστες συνθήκες). Λόγω των ετερογενειών της πορώδους δομής, στον βιοαερισμό ο κύριος μηχανισμός απομάκρυνσης ρύπου ήταν η εξάτμιση των υδρογονανθράκων και η σχετικά γρήγορη μεταφορά των ατμών μέσω διάχυσης και λόγω της μεγάλης βαθμίδας συγκέντρωσης από την μικροπορώδη μήτρα προς μονοπάτια προτιμητέας ροής (preferential flow paths) αέρα (αερισμός). Αντιστοίχως, λόγω της χαμηλής διαπερατότητας του εδάφους, στην περίπτωση της έγχυσης ατμού ο κύριος μηχανισμός απομάκρυνσης των ημι-πτητικών και μη πτητικών συστατικών ήταν η απόσταξη ατμού (δηλαδή η μείωση του σημείου ζέσεως των υδρογονανθράκων λόγω της παρουσίας μη αναμίξιμης υδατικής φάσης). Η σύγκριση των δύο μεθόδων απορρύπανσης με διάνοιξη οριζόντιων υδραυλικών ρωγμών έδειξε ότι και οι δύο μέθοδοι είναι αρκετά αποδοτικές όσον αφορά στη μείωση της μάζας του ρύπου (~72%) σε ισχυρά ετερογενή εδάφη με ρωγμές. Η έγχυση ατμού όμως είναι πολύ πιο γρήγορη (3 μήνες) από το βιοαερισμό (12 μήνες) αλλά ταυτόχρονα και αρκετά πιο ακριβή από αυτόν (14-25%). Όσον αφορά το ποσοστό μείωσης επικινδυνότητας του υπολειπόμενου ρύπου, ο βιοαερισμός δίνει με μεγάλη διαφορά καλύτερα αποτελέσματα (93%) από ότι η έγχυση ατμού (8-68%) όπου παρατηρείται και μεγάλη διακύμανση τιμών. / Soil contamination by industrial and urban wastes is nowadays one of the most important pollution problems worldwide. The petroleum hydrocarbons are included in the list of toxic pollutants that have contaminated extensive areas all over the world. An inevitable consequence of liquid pollutants release on the ground is their transport by a variety of mechanisms (e.g. gravity flow, dissolution, volatilization, dispersion, sorption, etc) in the unsaturated zone of soil, and subsequent pollution of the underlying aquifers. Conventional methods of ex-situ soil remediation are the soil excavation and its transportation in appropriate places (e.g. incinerator, bio-piles, etc). During the last years, there is a growing interest for the development and application of low-cost and sustainable (low environmental impact) in-situ soil remediation technologies. In the present work, two relatively new in-situ remediation technologies, bioventing and steam injection, were tested on the vadose zone of a low permeability and fractured glacial till sediment that was contaminated by jet fuel. The experimental site is situated in an abandoned military airport (Kluczewo) in North-Western Poland. The area was polluted extensively by jet fuel over a long period (1935-1992). The geological characterization revealed the existence of vertical desiccation fractures at the upper layers and horizontal/sub-horizontal tectonic fractures at the deeper ones, and a relatively low permeability and heterogeneous micro-porous matrix. The same geologic conditions dominate in a major part of the subsurface in Northern and Central Europe. Due to the multi-scale heterogeneities, ranging from the pore-scale to the field-scale, and the creation of preferential flow paths in such soils, it is very difficult to design successful remediation strategies based on vertical wells. For this reason, in both field experiments (bioventing and steam injection), the soil was stimulated by opening hydraulic fractures which acted as horizontal wells of fluid injection/extraction, and enhanced the influence radius of remediation. The main goal of the work is to evaluate, under field conditions, steam injection and bioventing as sustainable and efficient technologies for the removal of petroleum hydrocarbons from highly heterogeneous soils. In order to determine the efficiency of each remediation method, soil samples were collected from twelve wells and seven depths, and placed inside specific flasks pre-filled with dichloromethane (DCM). After the accelerated extraction of non-aqueous phase liquid (NAPL) from the soil and its dissolution in DCM, the composition and concentration of hydrocarbons (NAPL) was performed by using GC-MS and GC-FID. In order to clarify the main NAPL removal mechanisms and evaluate the effectiveness of steam injection and bioventing, lab-scale experiments were also conducted in soil tanks by using synthetic NAPL (PMMA cell with 55 cm x 50 cm x 12 cm dimensions) and keep the conditions comparable to the field ones. Due to pore structure heterogeneities, the main NAPL removal mechanism in bioventing was the volatilization of hydrocarbons and the fast vapour transfer through diffusion (due to the high concentration gradient) from the porous matrix to the high hydraulic conductivity preferential flow paths of injected air (ventilation). Respectively, due to the low soil permeability, in steam injection the main removal mechanism of semi- and non-volatile substances was steam distillation (namely the reduction of NAPL compounds bubble point because of the coexistence of immiscible water). The comparison of the two remediation technologies, steam injection and bioventing, indicate that both methods are efficient with respect to the reduction of the pollutant mass (~72%) in highly heterogeneous and fractured soils. With respect to cost issues, steam injection albeit faster, is 14-25% more expensive than bioventing. Finally, concerning the risks associated with the reduction of residual NAPL in groundwater, bioventing was more effective (~93%) than steam injection (8-68%).

This thesis is dedicated to the degradation of reinforced concrete structures, their causes and consequences of the waveforms. This thesis describes how the protection of concrete structures against these negative effects. The practical part of the work was focused on the development of new types of repair materials with added value in the form of corrosion inhibitor. In this part of the work was done adhesive bridge and development of repair materials for hand and machine application.

Die vorliegende Arbeit entstand im Rahmen einer pilotmaßstäblichen Boden- und Grundwassersanierung am Industriestandort „Hydrierwerk Zeitz“. Auf dem Gelände einer ehemaligen Benzolproduktionsanlage wurden großflächige Kontaminationen von Boden und Grundwasser festgestellt. Mittels moderner Erkundungstechnik konnten die Haupteintragsbereiche des dominierenden Schadstoffes Benzol erkundet und eingegrenzt werden. Verschiedene Arten von Grundwasser-, Boden- und Bodenluftbeprobungen sowie geophysikalische Verfahren erlaubten eine exakte Lokalisation des Schadstoffquellbereiches sowie der sich hieraus ausbildenden Schadstofffahne. Ziel der am Standort durchgeführten Pilotsanierungen war die Beseitigung der Schadstoffquelle, um eine weitere Nachlieferung in die Schadstofffahne zu unterbinden. Der Schadstoffquellbereich der hier behandelten Pilotsanierung war auf eine Kubatur von ca. 15 x 9 x 11 Kubikmeter begrenzt. Als Hauptkontaminant lag mit einem Anteil von 98% Benzol vor. Weiterhin wurden Toluol, Ethylbenzol sowie Xylol in geringen Mengen angetroffen. Aufgrund der hochvolatilen Eigenschaften des vorliegenden Hauptkontaminanten Benzol wurde am Standort eine thermische Sanierung der gesättigten sowie ungesättigten Zone durchgeführt, die eine Extraktion von rund 8 Tonnen Benzol erzielte. Im Zentrum der Sanierungskubatur wurde mit Hilfe von drei Injektions¬brunnen ein Dampf-Luft-Gemisch injiziert und eine Zieltemperatur im aus¬gewiesenen Sanierungsbereich von 85 ˚C erreicht. Diese Temperatur übersteigt den Siedepunkt von Benzol (80,1 ˚C) und führt zu einem vollständigen Übergang des Schadstoffes in die Gasphase. Durch sechs das Sanierungsfeld eingrenzende Extraktionsbrunnen wurde der Schadstoff dem Untergrund entzogen und an der Oberfläche durch eine thermische Nachverbrennungsanlage geleitet. Eine Problematik dieser Sanierungstechnik ist die exakte Lokalisation der sich im Untergrund ausbreitenden Front des Sanierungsmittels. Aufgrund von Inhomogenitäten in gesättigter und ungesättigter Zone kommt es zur Ausbildung von präferentiellen Fließpfaden. Diese Strukturen verhindern eine radialsymmetrische Ausbreitung des Sanierungsmittels und sorgen dafür, dass zum Teil große Bereiche der Sanierungskubatur nicht abgereinigt werden. Weiterhin findet ein sehr großer Energieverlust durch teilweises Austreten des Dampf-Luft-Gemisches in Bereiche außerhalb der Sanierungskubatur statt. Eines der Hauptziele dieser Arbeit war daher die Durchführung eines geoelektrischen Monitorings, das es erlaubte, durch Messung von elektrischen Widerstandsänderungen im Untergrund Position und Lage des Sanierungsmittels zu bestimmen und solche Bereiche zu lokalisieren, die keine Abreinigung erfuhren. Weiterhin konnten durch dieses Monitoring präferentielle Fließpfade erkundet werden, die zu Energieverlusten von über 60% im Verlauf der Sanierung führten. Als innovatives Verfahren wurde am Sanierungsstandort ein 3-dimensionales geoelektrisches Monitoring durchgeführt; ein Verfahren, das Messungen an Oberflächenelektroden mit Messungen an im Untergrund eingebrachten Bohrlochelektroden verknüpft. Mit diesem Verfahren konnten hochaufgelöste 3-dimensionale Abbildungen erstellt werden, die die Ausbreitung des injizierten Sanierungsmittels im Verlauf der Sanierung abbildeten. Um eine in dieser Auflösung vergleichbare Abbildung der Temperaturbereiche im Untergrund durch Messungen mit fest installierten Temperaturmessketten zu erlangen, wäre eine unverhältnismäßig große Menge an Sensoren notwendig gewesen. Somit war die Entwicklung eines geoelektrischen Monitoringsystems die einzige Möglichkeit, den Sanierungsverlauf so zu verfolgen, dass während des Betriebes Optimierungsmaßnahmen durchgeführt werden konnten. Abschließend konnte das Sanierungsverfahren in Kombination mit Temperaturmessungen außerhalb des Sanierungsbereiches bewertet und Erkenntnisse für Verbesserungen bei zukünftigen Anwendungen gewonnen werden. / The work presented here was carried out within a pilot scale soil- and groundwater remediation project at the former industrial area „Hydrogenation plant Zeitz”. Beneath a former benzene production facility a large scale contamination of soil and groundwater was found. Using modern exploration technologies main spill and infiltration zones for the principal contaminant benzene as well as residual or floating phases could be identified. A variety of methods for sampling of groundwater, soil and soil-air, as well as different geophysical methods allowed for the exact localisation of the contaminant source zone and the contaminant plume emerging from the source zone. The objective of the pilot remediation was the (partial) removal of the contaminant source to prevent further supply to the contaminant plume. The source area of this pilot remediation was limited to a cubature of about 15 x 9 x 11 meters. Benzene as the main contaminant was assessed with a share of 98%. Additionally low concentrations of toluene, ethylbenzene, as well as xylols were found. Since the main contaminant benzene is characterised by high volatility, a thermal remediation approach for the saturated as well as unsaturated zone was conducted at the site which allowed for the extraction of about 8 t of benzene. By the help of three wells a steam-air-mixture was injected into the central section of the remediation cubature and a target temperature of 85 ˚C was reached. This temperature exceeds the boiling point of benzene (80.1 ˚C) and leads to a complete volatilisation of the contaminant. Six extraction wells surrounding the remediation cubature removed the contaminant from the subsurface and delivered it to a catalytic combustion system. The exact localisation of the spreading steam front in the subsurface is the main problem of this remediation approach. Preferential flow paths develop due to inhomogeneities in the saturated and vadose zone of the subsurface. These structures inhibit a radial-symmetric spreading of the steam-air-mixture and, hence, prevent the remediation of large sections of the cubature. Additionally a very high loss of energy into sections outside the target area takes place. To overcome this problem, it was one of the main objectives of this work to perform a geoelectrical monitoring of the remediation approach which allowed the localisation of the steam-air-mixture by measuring electrical resistivity distributions in the sub¬surface. In addition, the development of preferential flow paths which led to energy losses of over 60% during the remediation could be explored. As an innovative concept for this remediation method a 3-dimensional geoelectrical monitoring was conducted; a procedure that combines measurements at surface electrodes with measurements at borehole electrodes installed in the subsurface. With this method a high resolution 3-dimensional imaging could be established which displays the spreading of the steam-air-front during the remediation process. To achieve such an imaging with comparable resolution with standard temperature sensors installed in the subsurface, an unreasonable number of these sensors would have been necessary. The development of the geoelectrical monitoring system was the only approach that allowed the observation of the treatment process as well as optimisation of the remediation system during active remediation. Ultimately the remediation procedure could be evaluated with additional measurements outside the remediation zone and information for the enhancement of further applications could be obtained.

Remediation of contaminated groundwater remains a high-priority national goal in the United States. Water is essential to life, and new sources of water are needed for an expanding population. Groundwater remediation remains a significant technical challenge despite decades of research into this field. New approaches are needed to address the most severely-polluted aquifers, and cost-effective solutions are required to meet remediation objectives that protect human health and the environment. Source reduction combined with Monitored Natural Attenuation (MNA) is a remediation strategy whereby the source of contamination is aggressively treated or removed and the residual groundwater plume depletes due to natural processes in the subsurface. The USEPA requires long-term performance monitoring of groundwater at MNA sites over the remediation timeframe, which often takes decades to complete. Presently, computational tools are lacking to adequately integrate source remediation with economic models. Furthermore, no framework has been developed to highlight the tradeoff between the degree of remediation versus the level of benefit within a cost structure. Using the Natural Attenuation Software (NAS) package developed at Virginia Tech, a set of formulae have been developed for calculating the TOR for petroleum-contaminated aquifers (specifically tracking benzene and MTBE) through statistical techniques. With the knowledge of source area residual saturation, groundwater velocity, and contaminant plume source length, the time to remediate a site contaminated with either benzene or MTBE can be determined across a range of regulatory maximum contaminant levels. After developing formulae for TOR, an integrated and interactive decision tool for framing the decision analysis component of the remediation problem was developed. While MNA can be a stand-alone groundwater remediation technology, significant benefits may be realized by layering a more traditional source zone remedial technique with MNA. Excavation and soil vapor extraction when applied to the front end of a remedial action plan can decrease the amount of time to remediation and while generally more expensive than an MNA-only approach, may accrue long-term economic advantages that would otherwise be foregone. The value of these research components can be realized within the engineering and science communities, as well as through government, business and industry, and communities where groundwater contamination and remediation are of issue. Together, these tools constitute the Sâ ªEâ ªEâ ªPâ ªAGE paradigm, founded upon the concept of sound science for an environmental engineering, effectual economics, and public policy agenda. The TOR formulation simplifies the inputs necessary to determine the number of years that an MNA strategy will require before project closure and thus reduces the specialized skills and training required to perform a numerical analysis that for one set of conditions could require many hours of simulation time. The economic decision tool, that utilizes a life cycle model to evaluate a set of feasible alternatives, highlights the tradeoffs between time and economics can be realized over the lifetime of the remedial project. / Ph. D.