Dissertations / Theses on the topic 'Groundwater In situ remediation. Oxidation'

In situ chemical oxidation (ISCO) is a leading-edge technology for soil and groundwater remediation, and involves injecting a chemical oxidant (e. g. , permanganate, hydrogen peroxide, or persulfate) into the subsurface to deplete contaminant mass through oxidation. Since the delivery of the chosen oxidant to the target treatment zone must occur in situ, the interaction between the injected oxidant and the aquifer material is a key controlling factor for a successful ISCO application. While many published ISCO studies have focused on the interaction between an oxidant and target contaminants, many questions still remain on the interaction between a potential oxidant and the aquifer material. Through a series of bench-scale experiments with aquifer materials collected from 10 sites throughout North America, the research presented in this thesis provides insight into the interaction between these aquifer materials and two widely used ISCO oxidants; permanganate and hydrogen peroxide. <br /><br /> The investigation into the interaction between aquifer materials and permanganate consisted of three series of bench-scale experiments: (1) long-term batch experiments which were used to investigate permanganate consumption in response to fundamental geochemical properties of the aquifer materials, (2) short-term batch experiments which were designed to yield kinetic data that describe the behavior of permanganate in the presence of various aquifer materials, and (3) column experiments which were used to investigate permanganate transport in a system that mimics the subsurface environment. The long-term experiments which involved more than 180 batch reactors monitored for ~300 days showed that the unproductive permanganate consumption by aquifer materials or natural oxidant demand (NOD) is strongly affected by the initial permanganate concentration, permanganate to solid mass ratio, and the reductive components associated with each aquifer material. This consumption cannot be represented by an instantaneous reaction process but is kinetically controlled by at least a fast and slow reactive component. Accordingly, an empirical expression for permanganate NOD in terms of aquifer material properties, and a hypothetical kinetic model consisting of two reaction components were developed. In addition, a fast and economical permanganate NOD estimation procedure based on a permanganate COD test was developed and tested. The investigation into short-term permanganate consumption (time scale of hours) was based on the theoretical derivation of the stoichiometric reaction of permanganate with bulk aquifer material reductive components, and consisted of excess permanganate mass experiments and excess aquifer material mass experiments. The results demonstrated that permanganate consumption by aquifer materials can be characterized by a very fast reaction on the order of minutes to hours, confirming the existence of the fast reaction component of the hypothetical kinetic model used to describe the long-term permanganate NOD observations. A typical experimental column trial consisted of flushing an aquifer-material packed column with the permanganate source solution until sufficient permanganate breakthrough was observed. The permanganate column results indicated the presence of a fast and slow consumption rate consistent with the long-term batch test data, and an intermediate consumption rate affecting the shape of the rising limb of the breakthrough curve. Finally, a comparison of the experimental results between batch and column systems indicated that permanganate NOD was significantly overestimated by the batch experiments; however, permanganate consumption displayed some similarity between the batch and column systems and hence an empirical expression was developed to predict permanganate consumption in physically representative column systems from batch reactor data. <br /><br /> The interaction between hydrogen peroxide and aquifer materials was also investigated with both batch and column experiments. A series of batch experiments consisting of a mixture of 2% hydrogen peroxide and 15 g of aquifer materials was used to capture the overall hydrogen peroxide behavior in the presence of various aquifer materials. The results indicated that the decomposition of hydrogen peroxide in the presence of various aquifer materials followed a first-order rate law, and was strongly affected by the content of amorphous transition metals (i. e. , Fe and Mn). Although hydrogen peroxide decomposition is related to the total organic carbon (TOC) content of natural aquifer materials, the results from a two-week long exposure to hydrogen peroxide suggests that not all forms of natural organic matter contributed to this decomposition. A multiple linear regression analysis was used to generate predictive relationships to estimate hydrogen peroxide decomposition rate coefficients based on various aquifer material properties. The enhanced stability of hydrogen peroxide was investigated under six scenarios with the addition of chelating reagents. The impact of a new green chelating reagent, S,S'-ethylenediaminedisuccinate (EDDS), on the stability of hydrogen peroxide in the presence of aquifer materials was experimentally examined and compared to that of the traditional and widely used chelating reagent, Ethylenediaminetetraacetic (EDTA). The results demonstrated that EDDS was able to significantly increase the stability of hydrogen peroxide, especially for aquifer materials with low TOC contents and/or high dissolvable Fe and Mn contents. Finally, to complement and expand the findings from the batch experiments, column experiments were conducted with aquifer materials from five representative sites. Each column was flushed with two types of source solutions (with or without EDDS addition) at two flow rates. The column experiments showed that the use of EDDS resulted in an earlier breakthrough and a higher stable concentration of hydrogen peroxide relative to the case without the addition of EDDS. The hydrogen peroxide decomposition rate coefficients generated from the column data were significantly higher than those generated from the batch test data and no correlation between hydrogen peroxide decomposition coefficients obtained from column and batch experiments was observed. Based on the column experimental results, a one-dimensional transport model was also calibrated to capture the hydrogen peroxide breakthrough process. <br /><br /> Data from bench-scale tests are routinely used to support both ISCO design and site screening, and therefore the findings from this study can be used as guidance on the utility of these tests to generate reliable and useful information. In general, the behavior of both permanganate and hydrogen peroxide in the presence of aquifer materials in batch and the column systems clearly indicates that the use of batch test data for ISCO system design is questionable since column experiments are believed to mimic in situ conditions better since column systems provide more realistic aquifer material contact. Thus the scaling relationships developed in this study provide meaningful tools to transfer information obtained from batch systems, which are widely employed in most bench-scale studies, to column systems.

The public water supply in Germany is mainly based on groundwater, and great care is taken to protect these water resources. A major challenge is, however, the remediation of polluted aquifers. Such is the case at a former gas works site in Karlsruhe, Germany. The "Gaswerk Ost" of the local gas and water supply company, the Stadtwerke Karlsruhe, was in operation for nearly 80 years until it was closed down in 1965. Unwanted by-products from the gas production still contaminate the soil and groundwater of this site. The main contaminants are benzene and polynuclear aromatic hydrocarbons (PAH) such as acenaph-thene, acenaphthylene, fluorene and fluoranthene. For remediation a novel passive methodology was planned. It was decided to install a funnel and gate system to purify the contaminated groundwater in situ by letting it pass through subterranean activated carbon reactors located downstream of the polluted site. During the construction of the remediation system a further pollutant, vinyl chloride (VC), was detected in the groundwater, a substance which could not be removed adequately by the technology employed. The objective of this research project was to find out whether the PAH and vinyl chloride could be removed from the groundwater by UV irradiation prior to the activated carbon filtration. Investigations consisted of two parts: laboratory experiments were conducted to prove the general degradability of the pollutants and field experiments were earned out to confirm these results on a pilot scale. In addition to sole UV irradiation, ozonation and advanced oxidation processes (AOPs) such as UV/aeration, UV/hydrogen peroxide and UV/ozone were performed in the laboratory to generate highly reactive hydroxyl radicals. For the contaminants present at the gas works site, the individual molar absorption coefficients were determined at 254 nm to estimate the degradation performance by direct photolysis at the main emission line of the UV lamps used for the irradiation experiments. It could be shown that all investigated substances were degradable in model test solutions prepared with reverse osmosis water, the degradation of PAH being significantly better than that of benzene and VC depending on the absorption of UV light of the individual substances. During the irradiation of acenaphthene the detection of by-products with an aromatic character showed that no complete mineralisation could, however, be achieved in an acceptable period of time. Degradation experiments performed in tap water as well as in groundwater showed slower degradation behaviour due to the high carbonate and bicarbonate concentrations and a high organic carbon content, mainly resulting from humic substances in the case of groundwater. The high iron concentration of the reduced groundwater led to an increase in turbidity during irradiation, since iron II was oxidised to iron III. In contrast to UV irradiation only, better results were achieved with combined treatment methods and with ozonation. For all methods tested in the laboratory the "Electrical Energy per Order of Magnitude" (EEO) was calculated from the degradation data, ozonation being most efficient for all investigated substances with regard to the energy consumption. On the basis of the laboratory findings it was decided to perform not only UV experiments at the gas works site but to extend the in-situ investigation programme by including ozonation. With UV irradiation the concentrations of the PAH acenaphthylene, fluorene, fluoranthene and pyrene could be reduced by nearly 90%. The total efficiency of UV irradiation in this specific groundwater was, however, unsatisfactory because the main contaminant acenaph-thene was removed by only 50% to a concentration of approximately 35 g/l (remediation target value = 0.2 g/l) although 1.33 kWh per m3 were applied with four lamp modules, each containing six lamps. In contrast to this, ozonation resulted in a complete elimination of VC and PAH as well as nearly 90% removal of benzene, thus confirming the laboratory findings. As almost all contaminants could be removed by ozonation only, combined UV/ozone treatment was not applied in situ. Ozonation technology was found to be the most favourable method for the removal of contaminants present at the former gas works site in Karlsrahe based on its practicability, economic advantages and high efficiency.

The natural attenuation of groundwater pesticides by biological degradation, is widely accepted to occur at concentrations > 1 mg 1-1. However from observations of groundwater monitoring data it can be indicated that the occurrence of pesticides in groundwater is primarily at trace μg 1-1 concentrations, with 45 % of UK groundwater samples that failed the EC Drinking Water Directives PV of 0.1 μg 1-1 between 1995 – 2000, accounting for an average concentration of 64 μg 1-1. However, there are limited directed studies of in situ biological degradation of pesticides at μg concentrations. Therefore, this work was designed provided an insight as to whether any prevalent microbial adaptation can occur to degrade atrazine at μg 1-1 concentrations in groundwater. Laboratory batch studies were performed using a groundwater exposed to 0.2 μg 1-1 of the herbicide atrazine, for an excess of 10 years. Bacterial enrichment using a glucose minimal salts medium resulted in no biological degradation of atrazine, when amended at concentrations between 10 μg to 50 mg 1-1. Batch studies using the atrazine degrader Pseudomonas sp. Strain ADP as a positive control, indicated a capability to degrade atrazine within sterilised groundwater, at 50 mg 1-1 (0.92 mg 1-1 day-1) and 1 mg 1-1 (0.14 mg 1-1 day-1), but no degradation of atrazine at 100 or 10 μg 1-1. Therefore, biological degradation of trace μg 1-1 concentrations of atrazine by groundwater in situ bacteria does not readily occur. It is expected that changes in atrazine groundwater concentrations, are resulting purely from dilution, sorption or chemical degradation. Consequently, it cannot be assumed that microbial adaptation can occur to degrade atrazine at μg 1-1 concentrations in groundwaters even if in situ bioaugmentation methods are applied.

This research is about the development of a photocatalytic reactor design, Honeycomb, for in-situ groundwater remediation. Photocatalysis, typically a pseudo first order advanced oxidation process, is initiated via the illumination of UVA light on the catalyst, i.e. titanium dioxide (TiO2). In the presence of oxygen, highly reactive oxidising agents are generated such as superoxide (O2-), hydroxyl (OH.-) radicals, and holes (hvb+) on the catalyst surface which can oxidise a wide range of organic compounds. The target contaminant is methyl tert butyl ether (MTBE), a popular gasoline additive in the past three decades, which gives the water an unpleasant taste and odour at 20 μg L-1, making it undrinkable. This research consists of three major parts, i.e. (i) establishing a suitable catalyst immobilisation procedure, (ii) characterisation and evaluation of reactor models and (iii) scale up studies in a sand tank. TiO2 does not attach well onto many surfaces. Therefore, the first step was to determine a suitable immobilisation procedure by preparing TiO2 films using several potential procedures and testing them under the same conditions, at small scale. The coatings were evaluated in terms of photocatalytic activity and adhesion. The photocatalytic activity of the coatings was tested using methylene blue dye (MB), which is a photocatalytic indicator. A hybrid coating, which comprises a sol gel solution enriched with Aeroxide TiO2 P25 powder, on woven fibreglass exhibited the best adhesion and photocatalytic activity among samples evaluated. Thus, it was used to produce immobilised catalyst for this research. Consequently, the immobilisation procedure was scaled up to synthesize TiO2 coatings for the potential photocatalytic reactor design. The photocatalytic activity of the coatings produced from the scaled up immobilisation procedure were reasonably comparable to that produced at small scale. Due to the UVA irradiation and mass transfer limitations, photocatalytic reactors are typically compact in order to maximise their efficiency to accommodate high flows, particularly in water and wastewater treatment. In the case of groundwater, however, the treatment area can span up to meters in width and depth. Groundwater flow is significantly lower than that of water treatment, as the reactor design does not need to be compact. Considering both factors, a photocatalytic reactor design of hexagonal cross-section (Honeycomb) was proposed, in which the structures can be arranged adjacent to each other forming a honeycomb. A model was constructed and tested in a 4 L column (cylindrical) reactor, using the MB test to characterise the reactor performance and operating conditions. This was followed by a hydraulic performance study, which encompasses single and double pass flow studies. The single pass flow study involves the photocatalytic oxidation (PCO) of MB and MTBE, while the double pass flow study was focused on the PCO of MTBE only. The double pass can simulate two serially connected reactors. Single pass flow studies found that the critical hydraulic residence time (HRT) for the PCO of MB and MTBE is approximately 1 day, achieving up to 84 % MTBE removal. Critical HRT refers to the minimum average duration for a batch of contaminant remaining in the reactor in order to maintain the potential efficiency of the reactor. Double pass studies showed the reactor can achieve up to 95 % MTBE removal in 48 hours, and that reactor performance in the field of serially connected reactors can be estimated by sequential order of single pass removal efficiency. In groundwater, there are likely to be other impurities present and the effects of groundwater constituents on the reactor efficiency were studied. The MTBE PCO rate is affected by the presence of organic compounds and dissolved ions mainly due to the competition for hydroxyl radicals and the deactivation of catalyst surface via adsorption of the more strongly adsorbed organic molecules and ions. Despite the presence of organic compounds and dissolved ions, the reactor achieved about 80 % MTBE removal in 48 hours. A double pass flow study showed that the overall efficiency of the photocatalytic reactor in the field can be estimated via sequential order of its efficiency in a single pass flow study using the actual groundwater sample in the laboratory. A sand tank was designed for the simulation of the clean up of an MTBE plume from a point source leakage using the 200 mm i.d. Honeycomb I prototype. Honeycomb I achieved up to 88.1 % MTBE removal when the contaminated groundwater flowed through (single pass) at 14.6 cm d-1. The critical HRT for Honeycomb I was also approximately 1 day, similar to that in the column reactor. The response of MTBE removal efficiency towards flow obtained in the column reactor and sand tank was generic, indicating that the reactor efficiency can be obtained via testing of the model in the column reactor. The presence of toluene, ethylbenzene and o-xylene (TEo-X) decreased the MTBE removal efficiency in both the sand tank and column reactor. The same set of catalyst and 15 W Philips Cleo UVA fluorescent lamp was operated for a total of about 582 h (24 d) out of the cumulative 1039 h (43 d) sand tank experiments, achieving an overall MTBE removal efficiency of about 76.2 %. The experiments in the column reactor and sand tank exhibited the reliability of the immobilised catalyst produced in this research. This research demonstrates the potential of Honeycomb for in-situ groundwater remediation and also proposes its fabrication and installation options in the field.

Permeable reactive biobarrier (PRBB) is a flow-through zone where microorganisms degrade contaminants in groundwater. Discontinuous presence of contaminants in groundwater causes performance loss of a PRBB in removing the target contaminant. A novel enricher reactor (ER) - PRBB system was developed to treat groundwater with contaminants that reappear after an absence period. ER is an offline reactor for enriching contaminant degraders, which were used for augmenting PRBB to maintain its performance after a period of contaminant absence. The ER-PRBB concept was initially applied to remove benzene that reappeared after absence periods of 10 and 25 days. PRBBs without ER augmentation experienced performance losses of up to 15% higher than ER-PRBBs. The role of inducer compounds in the ER to enrich bacteria that can degrade a mixture of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated with an objective to minimize the use of toxic chemicals as inducers. Three inducer types were studied: individual BTEX compounds, BTEX mixture, and benzoate (a non toxic and a common intermediate for BTEX biodegradation). Complete BTEX removal was observed for degraders enriched on all three inducer types; however, the removal rates were dependent on the inducer type. Degraders enriched on toluene and BTEX had the highest degradation rates for BTEX of 0.006 to 0.014 day-1 and 0.006 to 0.012 day-1, respectively, while degraders enriched on benzoate showed the lowest degradation rates of 0.004 to 0.009 day-1. The ER-PRBB technique was finally applied to address the performance loss of a PRBB due to inhibition interactions among BTEX, when the mixture reappeared after a 10 day absence period. The ER-PRBBs experienced minimal to no performance loss, while PRBBs without ER augmentation experienced performance losses between 11% and 35%. Presence of ethanol during the BTEX absence period increased the performance loss of PRBB for benzene removal. PRBBs augmented with degraders enriched on toluene alone overcame the inhibition interaction between benzene and toluene indicating that toluene can be used as a single effective inducer in an ER. The ER-PRBB was demonstrated to be a promising remediation technique and has potential for applications to a wide range of organic contaminants.

During the construction of the new urban area in the north-eastern part of Stockholm, Stockholm Royal Seaport, groundwater with extremely elevated levels of the carcinogenic aromatic hydrocarbon benzene was discovered in the area Hjorthagen. Such a contamination can be remediated in-situ by the use of chemical oxidation and biodegradation. Due to the fact that many factors such as contaminant composition, groundwater characteristics and temperature vary between sites, smaller bench scale studies are usually conducted before the full scale remediation on site. Little published research exists on the ability of these remediation techniques in areas with lower groundwater temperature such as Stockholm, why the need of a bench-scale study in this case is even larger. The objective of this master thesis is to, out of three investigated remediation agents, find the most suitable one for remediation of the benzene-contaminated groundwater in Hjorthagen. This was made in the form of a bench-scale study and the techniques studied were chemical oxidation, for which the two agents hydrogen peroxide (uncatalyzed and catalyzed in the form of Fenton’s reagent) and persulfate (activated with iron (II)) were used, and biological degradation by the use of a calcium peroxide-based compound. The study showed that the benzene-contaminated groundwater was best remediated with Fenton’s reagent, which was able to degrade the benzene with great success.

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO<br>CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>O impacto dos pesticidas sobre a qualidade das águas subterrâneas tem sido objeto de preocupação de cientistas e autoridades públicas do nosso planeta. O uso intensivo de pesticidas na agricultura e a alta persistência de muitos deles tem requerido um rigoroso controle para evitar possíveis contaminações das águas subterrâneas e superficiais. O herbicida atrazina é um poluente freqüentemente encontrado nas águas subterrâneas em muitos países e foi selecionado para este estudo. O objetivo principal deste trabalho foi avaliar a efetividade, em escala de laboratório, da remediação de águas subterrâneas contaminadas com atrazina a partir do tratamento com ozônio produzido eletroquimicamente in situ. O anodo de β-PbO2 foi empregado na produção do ozônio por via eletroquímica e foi obtido por eletrodeposição sobre um substrato de titânio. A análise do depósito de PbO2 pela técnica de difração de raios-X confirmou apenas a presença das fases α e β do PbO2 e apontou a fase β como a principal. Foi comprovado que o aumento da corrente elétrica aumenta a taxa de produção de ozônio. Taxas de produção de O3 de 4,4; 19,5 e 39,1 mg h(-1) foram obtidas a partir de valores de densidades de correntes de 0,5, 1,0 e 1,5 kA m(-2),respectivamente. Os experimentos de degradação em batelada de uma solução de atrazina com concentração igual a 1 mg L(-1) para densidades de corrente de 0,5, 1 e 1,5 kA m(−2) mostraram que, com o aumento da densidade da corrente ocorreu um acréscimo na taxa de degradação da atrazina. Isto indica que o maior poder de oxidação do anodo, na medida em que se incrementa a corrente aplicada, é devido à maior eletrogeração dos oxidantes O3/.OH. A partir da análise cinética dos resultados obtidos nos experimentos de degradação foram obtidas boas correlações lineares quando os dados foram ajustados seguindo um modelo de pseudo-primeira ordem. As constantes cinéticas de pseudo- primeira ordem calculadas foram 6,2×10(−3), 8,8×10(−3) e 1,21×10(−2) min (−1) para 0,5, 1 e 1,5 kA m(−2), respectivamente. Os experimentos de degradação de atrazina em fluxo contínuo foram realizados numa coluna de acrílico de forma cilíndrica (26 cm x 4cm DI) preenchida com areia lavada, simulando o material do aqüífero, contendo um anodo de Ti/β-PbO2 e um catodo de Ti/RuO2. Durante os experimentos houve uma diminuição progressiva da concentração de atrazina no efluente de saída da coluna. Após 8 horas, as concentrações de atrazina na saída da coluna foram 75% e 80% menores do que a concentração de atrazina na entrada da coluna quando se aplicaram correntes de 0,4 e 0,6 A, respectivamente. Estes resultados confirmam a potencial aplicação deste tipo de estratégia de controle de plumas de contaminação e proporciona as bases para o desenvolvimento futuro desta técnica de remediação de aqüíferos.<br>The impact of pesticides on the quality of groundwater has been the subject of scientific and public health concerns in the entire planet, especially in areas where groundwater is mainly used for human consumption. The intensive use of pesticides in agriculture and the high persistence of several of these chemicals have required a rigorous control of possible environmental contaminations, especially of drinking water sources. The herbicide atrazine is frequently detected in natural waters of many countries and was selected for investigation. A laboratory scale study on the evaluation of the effectiveness of remediation of atrazine in groundwater utilizing in situ electrochemical generated ozone was conducted. β-PbO2 was used as anode for ozone generation. β-PbO2 electrodes were prepared by electrodeposition on Ti plates. X-ray diffraction analysis confirmed that the deposit contained only the α and β PbO2 with the β phase prevailing. The electrochemical ozone production increases with incrementing the current density. The rate of ozone production during the electrolysis was 4.4, 19.5 and 39.1 mg h-1 for current densities of 0.5, 1.0 and 1.50 kAm(-2), respectively. In the experiments of atrazine degradation by electrochemically generated ozone a difference in atrazine degradation was found when the applied current density was varied. The results evidenced that the atrazine degradation rates increased with augmenting the current density. This is indicative of a greater oxidation ability of the anode with increasing the current applied due to the production of more electrogenerated active oxidant (O3/.OH). The kinetic analysis of the above results related to different reaction orders gave good linear correlations when the data was fitted with a pseudo first-order reaction rate equation. The pseudo first-order rate constants obtained were 6.2×10(−3), 8.8×10(−3), and 1.21×10(−2) min(−1) for 0.5, 0.1, and 1.5 kA m(−2), respectively. The acrylic column (26 cm x 4 cm ID) used in flow degradation experiments was packed with clean sand and contained a single set of electrodes. Two expanded titanium mesh coated with β-PbO2 and RuO2 served as anode and cathode, respectively. During the experiments the atrazine effluent concentration progressively diminished. After 8 hours of electrolysis the effluent atrazine concentration was reduced by 75% and 80% applying current densities of 0.4 and 0.6, respectively. These results confirm the potential applicability of this type of groundwater plume control strategy. The study constitutes a foundation to the future developing of this aquifer remediation technique.

Freshwater is a scarce resource, threatened by an ongoing pollution, global climate change and industrialization. Among other freshwater sources, groundwater is by far the most important source of usable freshwater but due to the intrinsic nature of aquifers; low flow rates and a complex matrix compared to superficial waters, attempts to remove contaminants are more complex and slow. The aim of this thesis is to increase the knowledge of two remediation technologies: first, nitrate and nitrite removal based on natural occurring bioremediation and second, the production, reactivity and agglomeration of nano Zero Valent Iron (nZVI) particles. Natural occurring denitrification is a promising and partially implemented remediation approach but concerns about its performance out of the lab are justified. The following studies were carried out: evaluation of denitrification potential of wetlands from two sites in Denmark, soil characteristics and composition impact on denitrification highlighting the role and vertical distribution of organic matter, assessment of the Dissimilatory Nitrate Reduction to Ammonium (DNRA) importance as a denitrification competitor and effect of the seasonal variations. Regarding seasonal fluctuations, results showed that Heterotrophic Denitrification (HD) is an Arrhenius temperature dependant process. Although, observing that HD is a very resilient process, being dominant under all tested conditions, the importance of DNRA arose in dried and frozen soils, in addition a nitrite increase was observed. Concerning to organic matter studies, heterotrophic denitrification was only present in a very narrow superficial zone where Organic Matter (OM) was abundant. DOC and LOI could not express by themselves an absolute correlation with HD, however high amounts of DOC ensured enough quantity and quality of OM. DNRA was important only in the very superficial samples where an excessive content of OM could trigger it. On the other hand, nZVI is a very promising in situ new technology which can achieve the degradation of a broad range of contaminants, some being reluctant to previous remediation and bioremediation approaches. The purpose is to help to overcome some of the challenges that limit a widespread implementation of this technique, such as: the lack of a cost -effective- straightforward production method, uncertainness on the reactivity governing factors including the passivating oxide shell in commercial particles and the agglomeration driving factors. After replicating the previous milling methods in literature (where the iron ductility if using inert media was an insurmountable barrier to reach a nanoscale size), the need to break the iron flakes was stated. Several approaches were tested, finally the addition of micronized alumina produced nanoscale particles. Abrasion of the grinding media and breakage of flakes were the main mechanisms for the nZVI production. The physicochemical properties of the obtained particles were: a mean particle diameter of 0.16 µm (by SEM) and a specific surface area of 29.6 m2·g-1 and a reactivity toward Cr (VI), trichloroethylene and tetrachloroethylene higher than commercial nZVIs. In reference to the work performed assessing the effect of a passivation oxide layer on a commercial nZVI (NANOFER STAR, nanoIron s.r.o.) it was concluded that the oxide shield of surface-passivated nZVI particles significantly decreases the performance. A process to weaken the oxide shield was tested, it consisted in exposing the passivated nZVI to water for 36 hours at w iron / w water concentration of 0.2, just before the reaction with the pollutants. The results show that this activation process increases the effectiveness of the remediation and simplifies the overall handling of the nZVI.<br>L'aigua dolça és un recurs escàs, amenaçat per una creixent contaminació, el canvi climàtic i la industrialització. Entre totes les fonts d'aigua dolça, l'aigua subterrània n¿és la font més important, però a causa de la naturalesa intrínseca dels aqüífers: baixos cabals i una matriu complexa, els intents d'eliminar-ne els contaminants són més complexos i lents. L'objectiu d'aquesta tesi és incrementar el coneixement de dues tecnologies de remediació d'aigües subterrànies. L'eliminació de nitrats i nitrits en base a la bioremediació natural i, en segon lloc, del nano Zero Valent (nZVI) referent a la seva: producció, reactivitat i aglomeració. La desnitrificació natural és una aproximació prometedora i parcialment implementada, però les inquietuds sobre el seu rendiment fora del laboratori estan justificades. Es varen realitzar els següents estudis: avaluació del potencial de desnitrificació en dos aiguamolls de Dinamarca, l'impacte de la composició del sòl i les seves característiques sobre la desnitrificació, avaluació de la importància de la reducció dissimilatòria de nitrat a amoni (DNRA) competidora de la desnitrificació i l'efecte de les variacions estacionals. Pel que fa a les fluctuacions estacionals, els resultats van mostrar que la desnitrificació heterotròfica (HD) és un procés dependent de la temperatura i pot ser modelat per Arrhenius. Encara que, es va observar que la HD és un procés molt resilient, sent dominant en totes les condicions assajades, la importància de la DNRA va ser important en els sòls assecats i congelats, on a més es va observar un augment de nitrit. En referència als estudis de la matèria orgànica del sòl, la HD només va ser present en una zona superficial molt estreta on la matèria orgànica (OM) era abundant. El carboni orgànic dissolt (DOC) i els sòlids volàtils (LOI) no van mostrar una correlació absoluta amb HD, tot i que quantitats elevades de DOC van assegurar suficient quantitat i qualitat de OM. La DNRA va ser important només en les mostres molt superficials on un contingut molt alt de OM podria provocar-la. D'altra banda, el nZVI és una nova tecnologia in situ molt prometedora que pot assolir la degradació d'una àmplia gamma de contaminants, alguns sent refractaris als enfocaments previs de remediació i bioremediació. L'objectiu és ajudar a superar alguns dels desafiaments que limiten una aplicació generalitzada d'aquesta tècnica, com ara: la manca d'un mètode econòmic de producció, la incertesa sobre els factors que en governen la reactivitat incloent la capa d'òxid superficial de passivació en les partícules comercials i els factors que regeixen l'aglomeració. Després de replicar els mètodes de mòlta anteriors trobats a la bibliografia (on la ductilitat de ferro si s'usa un mitjà de mòlta inert és un obstacle infranquejable per a assolir una mida nanomètrica), es va imposar la necessitat de trencar els flocs de ferro. Es van assajar diverses aproximacions, finalment l'addició de partícules micromètriques d'alúmina va produir satisfactòriament nZVI. L'abrasió de les boles de mòlta i el trencament dels flocs van ser els principals mecanismes de producció de nZVI. Les partícules obtingudes es varen caracteritzar per: un diàmetre mitjà de 0,16 µm (SEM) i una superfície específica de 29,6 m2·g-1 i una reactivitat vers Cr (VI), tricloroetilè i tetracloroetilè molt superior als nZVI comercials. El treball realitzat per avaluar l'efecte de la capa d'òxid de passivació en un nZVI comercial (NANOFER STAR, nanoIron s.r.o.) va concloure que el blindatge superficial d'òxid en les partícules de nZVI passivades disminueix significativament el seu rendiment. Es va assajar un procés per afeblir l'escut d'òxid, consistent en exposar el nZVI passivat a l'aigua durant 36 hores a una concentració per pes de ferro / aigua de 0,2, just abans de la reacció amb els contaminants. Els resultats mostren que aquest procés d'activació augmenta l'eficàcia de la remediació i simplifica la manipulació del nZVI.

Thesis (M.S. in environmental engineering)--Washington State University, December 2008.<br>Title from PDF title page (viewed on Apr. 17, 2009). "Department of Civil and Environmental Engineering." Includes bibliographical references (p. 15-18).

The Monument Valley UMTRA Site is a former uranium mining site that is located in Cane Valley, Arizona. The mining that occurred there from 1943 to 1968 created a groundwater contaminant plume that consists of nitrate, sulfate, and uranium. There are only a few viable methods for remediation of these types of contaminants occurring in large, deep plumes. Monitored natural attenuation is a popular approach because it is a green and low-cost alternative. However, it is often ineffective without some form of supplemental enhancement. In-situ biosequestration is one method of enhanced attenuation, which involves injecting an electron- donating substrate that will promote microbial activity and sequester contaminants by bioprecipitation, biomineralization, and enhanced adsorption. Prior tests conducted at the Monument Valley site in the center of the plume using ethanol as the electron donor proved effective in the treatment of nitrate, sulfate, and uranium. Subsequent pilot scale tests are being conducted in the source zone of the Monument Valley Site to further investigate the feasibility and effectiveness of using in-situ biosequestration for treatment of uranium contaminated groundwater. The preliminary results of these tests are discussed.

<p> During <i>in situ</i> remediation of contaminated groundwater, a treatment chemical is injected into the contaminated groundwater to degrade a contaminant through chemical reaction that occurs in the subsurface. Reactions and subsequent contaminant degradation occur only where the treatment chemical contacts the contaminant long enough to complete degradation reactions. Traditional <i> in situ</i> groundwater remediation relies on background groundwater flow to spread an injected treatment chemical into a plume of contaminated groundwater. </p><p> Engineered Injection and Extraction (EIE), in which time-varying induced flow fields are used to actively spread the treatment chemical into the contaminant plume, has been developed to increase contact between the contaminant and treatment chemical, thereby enhancing contaminant degradation. EIE has been investigated for contaminants degrading through irreversible, bimolecular reaction with a treatment chemical, but has not been investigated for a contaminant governed by complex biogeochemical processes. Uranium fate and transport in subsurface environments is governed by adsorption, oxidation reduction, solution, and solid-phase interactions with naturally occurring solution species, microbial communities, minerals and aquifer media. Uranium primarily occurs in aqueous, mobile U(VI) complexes in the environment but can be reduced to sparingly soluble, immobile U(IV) solid-phase complexes by native dissimilatory metal reducing bacteria. </p><p> This work investigates the ability of EIE to promote subsurface delivery of an acetate-amended treatment solution throughout a plume of uranium-contaminated groundwater to promote <i>in situ</i> growth of native microbial communities to immobilize uranium. Simulations in this investigation are conducted using a semi-synthetic flow and reactive transport model based on physical and biogeochemical conditions from two uranium contaminated sites: the Naturita Uranium Mill Tailings Remedial Action (UMTRA) Project site in southwestern Colorado and the Old Rifle UMTRA Project site in western Colorado.</p><p>

Fractured rock formations represent a valuable source of groundwater and can be highly susceptible to contamination by dense, non-aqueous phase liquids (DNAPLs). The goal of this research is to evaluate the effectiveness of three accepted remediation technologies for addressing DNAPL contamination in fractured rock environments. The technologies under investigation in this study are chemical oxidation, bioremediation, and surfactant flushing. Numerical simulations were employed to examine the performance of each of these technologies at the field scale. The numerical model DNAPL3D-RX, a finite difference multiphase flow-dissolution-aqueous transport code that incorporates RT3D for multiple species reactions, was modified to simulate fractured rock environments. A gridding routine was developed to allow the model to accurately capture DNAPL migration in fractures and aqueous phase diffusion gradients in the matrix while retaining overall model efficiency. Reaction kinetics code subroutines were developed for each technology so as to ensure the key processes were accounted for in the simulations. The three remedial approaches were systematically evaluated via simulations in two-dimensional domains characterized by heterogeneous orthogonal fracture networks parameterized to be representative of sandstone, granite, and shale. Each simulation included a DNAPL release at the water table, redistribution to pools and residual, followed by 20 years of ‘ageing’ under ambient gradient conditions. Suites of simulations for each technology examined a variety of operational issues including the influence of DNAPL type and remedial fluid injection protocol. Performance metrics included changes in mass flux exiting, mass destruction in the matrix versus the fractures, and percentage of injected remedial fluid interacting with the target contaminant. The effectiveness of the three remediation technologies covered a wide range; the mass of contaminants destroyed were found to range from 15% to 99.5% of the initial mass present. Effectiveness of each technology was found to depend on a variety of critical factors particular to each approach. For example, in-situ chemical oxidation was found to be limited by the organic material present in the matrix of the rocks, while the efficiency of enhanced bioremediation was found to be related to factors such as the location of indigenous bacteria present in the domain and rate of bioremediation. In the chemical oxidation study, the efficiency of oxidant consumption was observed to be poor across the suite of scenarios, with greater than 90% of the injected permanganate consumed by natural oxidant demand. This study further revealed that the same factors that contributed to forward diffusion of contaminants prior to treatment are critical to this remediation method as they can determine the extent of contaminant destruction during the injection period. Bioremediation in fractured rock was demonstrated to produce relatively good results under robust first-order decay rates and active microorganisms throughout the fractures and matrix. It was demonstrated that under ideal conditions, of the total initial mass present, up to 3/4 could be reduced to ethene, indicating bioremediation may be a promising treatment approach due to the effective penetration of electron donor into the matrix during the treatment period and the ongoing treatment that occurs after injection ceases. However, when indigenous bacteria was assumed to exist only within the fractured walls of sandstone, it was found that under the same conditions, the rate of dechlorination was 200 times less than the Base Case. Since the majority of the mass resided in the matrix, lack of bioremediation in the matrix significantly reduced the effectiveness of treatment. Surfactant treatment with Tween-80 was proven to be a relatively effective technique in enhanced solubilisation of DNAPL from the fractures within the domain. However, by comparing the aqueous and sorbed mass at the start and end of the Treatment stage, it is revealed that surfactant treatment is not efficient in removing these masses that reside within the matrix. Furthermore, DNAPLs identified in dead end vertical fractures were found to remain in the domain by the end of the simulations across all scenarios studied; indicating that the injected surfactant experiences difficulty in accessing DNAPLs entrapped in dead end fractures. Altogether, the results underscore the challenge of restoring fractured rock aquifers due to the field scale limitations on sufficient contact between remedial fluids and in situ contaminants in all but the most ideal circumstances.

In situ chemical oxidation is a promising technology for the remediation of persistent subsurface contamination. Increasingly, the persulfate ion is being studied for use in these systems, both on its own as a strong oxidant and as the precursor to the even more reactive sulfate radical. Persulfate has been shown to treat a wide range of contaminants, from traditional Superfund contaminants such as chlorinated solvents to emerging pharmaceutical contaminants. Additionally, persulfate ISCO can be tailored to site and pollutant specific characteristics based on the method of persulfate activation (e.g., energy and catalysis activation) to the sulfate radical. Thermal activation of persulfate is particularly promising because it can be easily controlled, requires no additional reagents, and commonly creates only non-toxic end products. While persulfate in-situ chemical oxidation technology is being commercially used, a mechanistic study of the physical and chemical processes controlling the effectiveness of this remedial approach is not well documented in the literature. Published work characterizing persulfate ISCO largely focuses on reactions in aqueous, batch systems, which fail to provide crucial design data when working with ever transient, multi-phase groundwater systems. The purpose of this research was twofold. Initial studies characterized the overall transport behavior of unactivated and thermally-activated persulfate (20, 60, and 90°C) in one-dimensional soil column systems packed with a natural sandy porous media. This necessitated the development of a flow-through, temperature-controlled, continuous-injection system for the delivery of heat-activated persulfate. Finally, as a proof of concept, experiments were conducted to investigate persulfate ISCO as a remedial approach for residual-phase trichloroethylene (TCE), a commonly detected, persistent subsurface contaminant. At all activation temperatures investigated, persulfate exhibited ideal transport behavior with negligible differences in the observed breakthrough curves of persulfate ion and nonreactive tracers in miscible displacement experiments. Additionally, moment analysis of the breakthrough curves measured for persulfate ion in solution indicated negligible interaction of persulfate with the sandy material under steady-state flow (average retardation factor equaled 1.00 ± 0.021). Persulfate ISCO for residual-phase trichloroethylene (TCE) was characterized at two flow rates, 0.2 mL/min and 0.5 mL/min, resulting in two degrees of apparent persulfate activation, 39.5% and 24.6%, respectively. Both ISCO soil column systems showed an initial, long-term plateau in effluent concentrations measured for TCE indicating steady-state dissolution of pure phase TCE. Effluent concentrations of TCE began decreasing after 75 and 100 pore volumes (normalized for the residual fraction of TCE in individual soil columns) in the 39.5% and 24.6% activated persulfate columns as compared to 110 pore volumes in the control study (flushed with electrolyte only). Pseudo first-order rate constants for the decreasing TCE concentrations were calculated using log-linear regression analysis. The measured reaction rate constants for the control, the 0.2 mL/min (39.5% activation) study, and the 0.5 mL/min (24.6% activation) study equaled 0.044, 0.063, and 0.083 hr-1, respectively. Additionally, moment analysis of the complete dissolution of TCE in the persulfate/activated persulfate remediation systems indicated approximately 33% degradation/oxidation of TCE mass present. As shown by this and other work, persulfate has enormous potential as a subsurface remediation technology. A more thorough understanding of the physical and chemical mechanisms controlling the behavior and application of persulfate in the subsurface, especially under transient conditions, is necessary for the growth of this technology. By characterizing heat-activated persulfate under dynamic conditions, describing the overall transport of persulfate/activated persulfate in a natural porous media, as well as a proof of concept for the ISCO treatment of a residual nonaqueous phase liquid, this work aids in improving the implementation of persulfate ISCO systems.

Este trabalho apresenta os resultados obtidos no processo de remediação de uma área impactada pelo composto tetracloroeteno através do emprego da tecnologia de oxidação química in situ (ISCO). O teste de bancada realizado em uma amostra de água subterrânea da área de estudo tratada com uma solução de 5% de permanganato de potássio resultou em um percentual de remoção da massa de tetracloroeteno e seus produtos de degradação natural (tricloroeteno, dicloroeteno e cloreto de vinila) superior a 99%. Ao todo, foram injetados em subsuperfície 2950 kg de permanganato de potássio a uma concentração de 6% para o tratamento de 20000 m³ de um aqüífero impactado pelo composto tetracloroeteno e os seus produtos de degradação natural. A injeção de permanganato potássio resultou na destruição de aproximadamente 70% das concentrações de tetracloroeteno e seus produtos de degradação natural na área alvo de remediação dentro de um período de 30 dias após o término da aplicação do oxidante em subsuperfície, comprovando a eficiência do processo de oxidação química in situ para o tratamento de águas subterrâneas impactadas pelo composto tetracloroeteno.<br>This work presents the results obtained during the remediation process of an area impacted by the compound tetrachloroethene applying the technology of in situ chemical oxidation (ISCO). The bench test performed in a groundwater sample from the study area treated with a 5% potassium permanganate solution resulted in a percentage removal of tetrachloroethene mass and its natural degradation products (trichloroethene, dichloroethene and vinyl chloride) superior than 99%. In total, it was injected in the subsurface 2950 kg of potassium permanganate with a concentration of 6% in order to treat 20000 m³ of an aquifer impacted by the compound tetrachloroethene and its natural degradation products. The potassium permanganate injection resulted in the destruction of approximately 70% of the tetrachloroethene concentration and its natural degradation products in the target area within a period of 30 days after finishing the oxidant application in the subsurface, confirming the efficiency of the in situ chemical oxidation process for treating groundwater impacted by tetrachloroethene.

The Swedish mining industry has changed from the historical situation with several smaller mines to the present situation with a few, bigger mines. This results in presence of abandoned mines around Sweden. Remediation of mines is regulated by legislation and the present demands are considerably higher than it was some decades ago.  The Storliden mine was a Zink- and Coppermine active between 2001-2008. Storliden is located in Malå municipality, Västerbotten county, and is included in the Skellefte district, known for its sulfide mineralizations.  The ore was broken underground with a technique called cut and fill mining. It was estimated that the ore was to be consumed in 2007, but due to rising ore prices, the mine was operated until 2008. Remediation was done through backfilling the mine with waste rock from Storliden and Boliden’s mines Renström, Kedträsk, and Kankberg. Also, tailings, concrete, and sludge from the sedimentation basins were backfilled. Today, the mine is filled with water.  High Arsenic concentrations in water is a serious health issue in parts of the world. Bangladesh is perhaps the most common example where Arsenic in groundwater has caused health problems for millions of people. In Sweden, the Skellefte field is known for its elevated Arsenic concentrations in the bedrock, related to sulfide mineralizations. Studies confirm a correlation between Arsenic-bearing bedrock and elevated concentrations in water.  This thesis work has been conducted together with the consultant company Golder Associates (Golder) in Luleå. Golder has performed environmental investigations in the Storliden area during the period 2018-2020. Installation and sampling of groundwater wells were included in this investigation. High concentrations of Arsenic was found in some of the groundwater wells. This thesis aims to review potential sources of Arsenic and their potential significance. The purposes are to be fulfilled by evaluating and interpreting the results from the sampling, Piper diagrams, ratios, and modeling in the program PHREEQC.  The results indicate that the presence of Arsenopyrite in the bedrock is the most likely source of the elevated concentrations of Arsenic in deep groundwater. Oxidation of Arsenopyrite is likely caused by mainly dissolved oxygen in groundwater. Further, the water quality differs from different depths, indicating that deep groundwater and water flow from the mine via the ramp do not have any immediate connection. It is likely that remains of tailings on the industrial area cause low pH and leaching of metals locally.  High concentrations of Arsenic can occur very locally, highlighting the importance of conducting sampling of groundwater used as drinking water in areas where sulfide mineralizations are confirmed or suspected. Further, a relation between the time that water is in contact with the bedrock/mineralization and the concentration of Arsenic is stated. Higher concentration HCO3- tends to correlate with elevated Arsenic concentration.<br>Sveriges gruvindustri har förändrats i snabb takt, från ett flertal mindre gruvor till dagens läge med ett mindre antal större gruvor. Detta resulterar i förekomst av nedlagda gruvor runt om i Sverige. Efterbehandling av gruvor regleras genom lagstiftning, och kraven idag är betydligt högre än för bara något decennium sedan.   Storlidengruvan var en zink- och koppargruva verksam mellan 2001–2008. Storliden ligger i Malå kommun och området ingår i Skelleftefältet, känt för sina sulfidmineraliseringar. Malmen bröts i en underjordsgruva med så kallad igensättningsbrytning, dvs. tomrum har succesivt fyllts ut med material under driften. Malmen beräknades vara förbrukad 2007, men när malmpriset ökade kunde gruvan leva vidare till 2008. Efterbehandlingen innebar att fylla igen gruvan med gråberg från Storliden men också gråberg från Bolidens gruvor Renström, Kedträsk och Kankberg. Dessutom användes anrikningssand, cement och slam från sedimentationsbassängerna för att fylla igen gruvan. Länshållning av gruvan upphörde och idag är gruvan vattenfylld. Höga arsenikhalter i vatten är ett hälsoproblem i delar av världen. Det kanske vanligaste exemplet är Bangladesh, där arsenik i grundvatten har orsakat hälsoproblem för miljontals människor. I Sverige är Skelleftefältet utmärkande för den höga arsenikhalten i berggrunden. Naturlig arsenikhalt i borrade brunnar har undersökts i flera studier som visar ett samband mellan arsenikhaltig berggrund och förhöjda halter i vatten.  Examensarbetet har utförts tillsammans med konsultföretaget Golder Associates i Luleå. Golder har fått i uppdrag att utföra miljötekniska undersökningar i Storlidenområdet, bland annat ingick installation och provtagning av grundvattenrör. Denna provtagning skedde under perioden 2018–2020. I några av grundvattenrören påträffades förhöjda halter av arsenik. Detta examensarbete syftar till att utreda förekomsten av Arsenik i grundvattnet, undersöka vilka källor som kan vara orsaken till arsenikhalterna samt källornas förväntade betydelse. Detta har gjorts genom att utvärdera och tolka resultaten från provtagningarna samt användningen av Piper-diagram, geokemiska kvoter och geokemisk modellering i programmet PHREEQC. Resultaten indikerar att förekomst av arsenikkis som mineralisering i berggrunden är den mest troliga källan till de förhöjda halterna av arsenik i djupt grundvatten. Oxidationen av arsenikkis sker troligtvis främst av löst syre i grundvattnet. Vidare skiljer sig vattenkvalitén åt från olika djup och delar av området som provtagits, dvs. det verkar inte finnas någon omedelbar koppling mellan djupt grundvatten och vatten som kommer via rampen som leder till gruvan. Det är troligt att rester av anrikningssand på industriområdet orsakar lågt pH och metallutlakning lokalt.  Höga arsenikhalter kan förekomma lokalt, vilket understryker vikten av att utföra provtagning av grundvatten som används för dricksvatten i områden där misstänkt eller konstaterade sulfidmineraliseringar förekommer, eftersom arsenik annars kan vara en mycket skadlig ”diffus” förorening. Vidare konstateras också samband mellan den tid som vatten är i kontakt med mineralisering och arsenikhalt. Högre halt HCO3- tenderar att korrelera med förhöjd arsenikhalt

Recentemente, o uso de persulfato em processo de oxidação química in situ em áreas contaminadas por compostos orgânicos ganhou notoriedade. Contudo, a matriz sólida do solo pode interagir com o persulfato, favorecendo a formação de radicais livres, evitando o acesso do oxidante até o contaminante devido a oxidação de compostos reduzidos presentes no solo ou ainda pela alteração das propriedades hidráulicas do solo. Essa pesquisa teve como objetivos avaliar se as interações entre a solução de persulfato com três solos brasileiros poderiam eventualmente interferir sua capacidade de oxidação bem como se a interação entre eles poderia alterar as propriedades hidráulicas do solo. Para isso, foram realizados ensaios de oxidação do Latossolo Vermelho (LV), Latossolo Vermelho Amarelo (LVA) e Neossolo Quartzarênico (NQ) com solução de persulfato (1g/L e 14g/L) por meio de ensaios de batelada, bem como a oxidação do LV por solução de persulfato (9g/L e 14g/L) em colunas indeformadas. Os resultados mostraram que o decaimento do persulfato seguiu modelo de primeira ordem e o consumo do oxidante não foi finito. A maior constante da taxa de reação (kobs) foi observada para o reator com LV. Essa maior interação foi decorrente da diferença na composição mineralógica e área específica. A caulinita, a gibbsita e os óxidos de ferro apresentaram maior interação com o persulfato. A redução do pH da solução dos reatores causou a lixiviação do alumínio e do ferro devido a dissolução dos minerais. O ferro mobilizado pode ter participado como catalisador da reação, favorecendo a formação de radicais livres, mas foi o principal responsável pelo consumo do oxidante. Parte do ferro oxidado pode ter sido precipitado como óxido cristalino favorecendo a obstrução dos poros. Devido à maior relação entre massa de persulfato e massa de solo, a constante kobs obtida no ensaio com coluna foi 23 vezes maior do que a obtida no ensaio de batelada, mesmo utilizando concentração 1,5 vezes menor no ensaio com coluna. Houve redução na condutividade hidráulica do solo e o fluxo da água mostrou-se heterogêneo após a oxidação devido a mudanças na estrutura dos minerais. Para a remediação de áreas com predomínio de solos tropicais, especialmente do LV, pode ocorrer a formação de radicais livres, mas pode haver um consumo acentuado e não finito do oxidante. Verifica-se que o pH da solução não deve ser inferior a 5 afim de evitar a mobilização de metais para a água subterrânea e eventual obstrução dos poros por meio da desagregação dos grãos de argila.<br>Recently the persulfate application for in situ chemical oxidation at areas contaminated by organic compounds gained notoriety. However, the persulfate can interact with the solid matrix of the soil favoring the formation of free radicals, avoiding the oxidant access to the contaminant due to the oxidation of reduced compounds present in the soil or by changing the hydraulic properties of the soil. This research aimed to evaluate if the interactions between the persulfate solutions and three Brazilian tropical soils could eventually interfere on the persulfate oxidation capacity and if the interaction between them could modify the hydraulic properties of the soil. For such, oxidation tests were performed with soils: Latossolo Vermelho (LV), Latossolo Vermelho Amarelo (LVA) and Neossolo Quartzarênico (NQ) with persulfate solution (1 and 14 g/L) through batch tests and LV oxidation by persulfate solution (9 and 14 g/L) on undisturbed columns. The results showed that persulfate decay followed a first order model and oxidant consumption was not finite. The higher reaction rate coefficient (kobs) was observed in the reactor with LV. This higher interaction was due to the difference in the mineralogical composition and surface area. Kaolinite, gibbisita and iron oxides showed greater interaction with persulfate. The pH reduction on the reactor solution caused the aluminum and iron leaching due to dissolution of minerals. The mobilized iron may have participated as a reaction catalyst favoring the formation of free radicals although it was the major responsible for the oxidant consumption. Part of oxidized iron may have been precipitated as crystalline oxide favoring the clogged pores. As a consequence of the higher mass proportion between persulfate and soil, the kobs constant obtained in the column test was 23 times higher than the one observed on the batch test, even utilizing a concentration 1.5 times lower than bath test. There was a reduction in the soil hydraulic conductivity and the water flow proved to be heterogeneous after oxidation due to changes in minerals structure. For remediation purposes in areas with predominance of tropical soils, especially LV, the formation of free radicals may occur but an accented and not finite oxidant consumption may happen. It is verified that the pH solution should not be inferior than 5 to prevent the mobilization of metals to the groundwater and a possible pores clogging by the breakdown of the clay grains.

Grande parte das áreas contaminadas conhecidas atualmente advém de práticas passadas onde os cuidados com a proteção à saúde humana e ao meio ambiente eram desconhecidos ou ignorados. O uso indiscriminado de produtos solventes clorados fez com que tais compostos se tornassem uma das principais fontes de contaminação no setor industrial. Por serem compostos de alta toxicidade, quando presentes na água subterrânea, mesmo em baixas concentrações, a tornam imprópria para o consumo. Técnicas de remediação como atenuação natural, ou que envolvam bombeamento e tratamento de água subterrânea contaminada por solventes clorados, vêm sendo substituídas por metodologias químicas destrutivas, por apresentarem resultados satisfatórios em um período de tempo inferior às técnicas utilizadas anteriormente. Este trabalho objetiva apresentar os resultados obtidos em duas áreas industriais onde foram aplicadas técnicas de remediação, envolvendo a redução química in situ, através da injeção de polisulfeto de cálcio e a oxidação química in situ, com a injeção de permanganato de potássio. Em ambas as áreas, os contaminantes organoclorados são os principais compostos de interesse presentes na água subterrânea. A redução química in situ é uma metodologia que utiliza um agente químico para reduzir óxidos de ferro III, presentes naturalmente no aquífero sedimentar, e transformá-los em ferro II que, por sua vez reduzirá contaminantes organoclorados. A principal característica desta metodologia é a eliminação contígua de dois átomos de cloro das moléculas dos contaminantes, o que tende e diminuir ou eliminar o acúmulo de subprodutos tóxicos como cloreto de vinila. Na oxidação química in situ, o agente promove a transferência de elétrons, onde os íons Cl- das moléculas dos contaminantes são substituídos por H+. Devido à baixa reatividade entre o permanganato de potássio e a matriz do aquífero durante as reações de oxidação química, este oxidante pode ser transportado pelos processos advectivo e dispersivo juntamente com o fluxo da água subterrânea e persistir por um período maior de tempo, reagindo com os contaminantes orgânicos. Ensaios de bancada com solo saturado contaminado de uma das áreas de estudo mostraram excelentes resultados na utilização do polisulfeto de cálcio, mas o mesmo não foi observado no teste piloto realizado em campo. Embora tenha sido observada dispersão do produto nas proximidades de pelo menos um dos pontos onde a solução foi injetada, notou-se que não houve redução significativa dos contaminantes, evidenciando que o ferro II não foi eficaz no processo de degradação. Isto pode ter sido ocasionado por uma série fatores, como possíveis reações, características hidráulicas, ou geológicas do meio. Portanto, o prosseguimento desta metodologia como alternativa de remediação para toda a área impactada foi descontinuado, tornando necessário novos estudos para avaliar a melhor técnica aplicável na área. Quanto à área onde foi aplicada a oxidação química, a remediação foi considerada eficiente. Ao longo do período de vinte e dois meses, quando foram realizadas atividades de monitoramento da água subterrânea, observou-se a presença do permanganato de potássio nas áreas mais impactadas das plumas de contaminação, fato que permitiu o processo de transferência de elétrons e consequentemente a oxidação dos contaminantes. Vinte e dois meses após as atividades de injeção, o principal contaminante identificado na área, o 1,-1-dicloroeteno, foi detectado em apenas um ponto com concentração superior a meta de remediação obtida anteriormente à injeção. Considerando que durante a sequência das atividades relacionadas à remediação, este contaminante sofreu alterações em seus valores toxicológicos estabelecidos pela Agência de Proteção Ambiental dos Estados Unidos, e passou a ser considerado um composto não carcinogênico, todos os poços apresentaram-se com concentrações inferiores a nova meta de remediação calculada. Como efeito colateral, foi observado o aumento das concentrações de metais dissolvidos, como: alumínio, bário, cromo e ferro. Tal mobilização de metais para a água subterrânea pode ser considerada temporária. Após o total consumo do permanganato de potássio pelos contaminantes ainda presentes no meio, as características físico-químicas do aquífero retornarão à situação identificada naturalmente, permitindo a precipitação dos metais.<br>Most of the currently known contaminated areas are the result of past practices, where precautions regarding protection of human health and the environment were either unknown or ignored. The indiscriminate use of chlorinated solvents is the driving factor that has led to such compounds becoming one of the main sources of contamination in the industrial sector. Chlorinated solvents are highly toxic and, when present at even low concentrations in groundwater, they make this resource unfit for human consumption. Such remediation techniques as natural attenuation, or that involve pumping and treatment of groundwater contaminated by chlorinated solvents, are currently being replaced by destructive chemical methods, as they show satisfactory results in a shorter period of time than previously used techniques. This study has the objective of showing the results obtained at two industrial sites where remediation techniques have been used involving in-situ chemical reduction, through injection of calcium polysulfide, and in-situ chemical oxidation, with injection of potassium permanganate. At both sites, organochlorine contaminants are the main compounds of concern present in groundwater. In-situ chemical reduction is a methodology that uses a chemical agent in order to reduce iron III oxides, naturally present in the sedimentary aquifer, and transform them into iron II which, in turn, reduces the organochlorine contaminants. The principal characteristic of this methodology is that of contiguous elimination of two chlorine atoms from contaminant molecules, which tends to reduce or eliminate accumulation of such toxic byproducts as vinyl chloride. In in-situ chemical oxidation, the chemical agent brings about a transfer of electrons, where the Cl- ions of contaminant molecules are replaced by H+ ions. Due to the low degree of reactivity between potassium permanganate and the aquifer matrix during chemical oxidation reactions, this oxidizing agent can be transported via groundwater flow, by advective and dispersive processes, and persist for a longer period of time, reacting with organic contaminants. Bench tests performed with contaminated saturated soil from one of the sites under study showed excellent results through the use of calcium polysulfide; however, the same results were not observed during a pilot test performed in the field. Although product dispersion was observed in the vicinity of at least one of the points where the solution had been injected, it was found that there was no significant reduction of contaminants, showing that iron II was not effective in enhancing the degradation process. This could have been the result of a series of factors, for example, possible reactions or the hydraulic or geological characteristics of the medium. Therefore, it was decided not to continue with use of this methodology as a remediation alternative for the whole impacted area, making it necessary for further studies in order to assess the best technique applicable at the site. With respect to the site where a chemical oxidation approach was adopted, remediation was considered to be effective. Over a period of twenty-two months, during which groundwater monitoring activities were performed, the presence of potassium permanganate was observed in the most impacted areas of the contamination plumes, a fact that allowed for the electron transfer process and, consequently, contaminant oxidation. Twenty-two months after initiation of injection activities, the main contaminant identified at the site (1,1-dichloroethene) was only detected at one point at a concentration exceeding the post-remediation target value established prior to commencing these activities. Considering that, during the sequence of activities related to the remediation process, this contaminant underwent changes in its toxicological values established by the United States Environmental Protection Agency, and came to be considered a non-carcinogenic compound, all wells showed concentrations below the new calculated post-remediation target. As a collateral effect, there was found to be an increase in concentrations of such dissolved metals as aluminum, barium, chromium and iron. Such mobilization of metals to groundwater can be considered a temporary effect. Following complete consumption of potassium permanganate by contaminants still present in the medium, the physical-chemical characteristics of the aquifer will return to the situation occurring naturally, allowing for the precipitation of these metals.

Le thème principal de cette recherche est la remédiation des sols contaminés par des hydrocarbures en utilisant des traitements d'oxydation chimique à pH neutre. Les minéraux à base de fer sont susceptibles de catalyser cette réaction d'oxydation. L'étude concerne donc dans un premier temps la synthèse des minéraux réactifs contenant des espèces FeII et FeIII (la magnétite et la rouille verte) et, dans un second temps, leur utilisation pour catalyser l'oxydation chimique. Les procédés d'oxydation testés incluent l'oxydation de type « Fenton-like (FL) » et de type persulfate activé (AP). La formation de la magnétite et de la rouille verte a été étudiée par des transformations abiotiques de différents oxydes ferriques (ferrihydrite, goethite, hématite et lépidocrocite) mis en présence de cations FeII. La magnétite a été utilisée pour catalyser les oxydations (FL et AP) dans la dégradation des hydrocarbures aliphatiques et aromatiques polycycliques (HAP) à pH neutre. Une dégradation importante des hydrocarbures aliphatiques a été obtenue par ces deux oxydants, aussi bien pour des pétroles dégradés naturellement que pour un pétrole brut. L'oxydation catalysée par la magnétite a également été efficace pour la remédiation de deux sols contaminés par HAP provenant d'anciens sites de cokerie. Aucun sous-produit n'a été observé dans nos expériences d'oxydation. En revanche, une très faible dégradation des hydrocarbures a été observée lorsque les espèces FeII solubles ont été utilisées comme catalyseur. Des expériences d'oxydation ont également été réalisées en colonne. Ces études d'oxydation ont révélé l'importance du type de catalyseur utilisé pour l'oxydation, la disponibilité des HAP dans les sols et l'effet de la matrice du sol. Les résultats suggèrent que la magnétite peut être utilisée comme source de fer pour activer les deux oxydations par Fenton-like et persulfate à pH neutre. Ce travail a de fortes implications sur la remédiation par oxydation chimique in situ des sols pollués par des hydrocarbures<br>The main theme of this research is the use of reactive iron minerals in the remediation of hydrocarbon contaminated soils via chemical oxidation treatments at circumneutral pH. The contribution of this thesis is two-fold including the abiotic synthesis of mixed FeII-FeIII oxides considered as reactive iron minerals (magnetite and green rust) and their use to catalyze chemical oxidation. Oxidation methods tested in this study include Fenton-like (FL) and activated persulfate oxidation (AP). The formation of magnetite and green rust was studied by abiotic FeII-induced transformations of various ferric oxides like ferrihydrite, goethite, hematite and lepidocrocite. Then, the ability of magnetite was tested to catalyze chemical oxidation (FL and AP) for the degradation of aliphatic and polycyclic aromatic hydrocarbons (PAHs) at circumneutral pH. Significant degradation of oil hydrocarbons occurring in weathered as well as in crude oil was obtained by both oxidants. Magnetite catalyzed oxidation was also effective for remediation of two PAHs contaminated soils from ancient coking plant sites. No by-products were observed in all batch slurry oxidation systems. Very low hydrocarbon degradation was observed when soluble FeII was used as catalyst under the same experimental conditions. Magnetite also exhibited high reactivity to catalyze chemical oxidation in column experiments under flow through conditions. Oxidation studies revealed the importance of catalyst type for oxidation, PAHs availability in soils and the soil matrix effect. Results of this study suggest that magnetite can be used as iron source to activate both Fenton-like and persulfate oxidation at circumneutral pH. This study has important implications in the remediation of hydrocarbon polluted soils through in-situ chemical oxidation

碩士<br>國立臺北科技大學<br>環境規劃與管理研究所<br>94<br>This research discussed the treatment of the Fenton''s agent of the in-situ chemical oxidation (ISCO) on contaminated groundwater polluted by benzene, toluene, ethylbenzene, and xylenes (BTEX) released from gasoline. The above treatment was evaluated by virtue of the literature review, principle of remediation, removal efficiency, real remediation cases and cost in order to clearly understand its merit, constraints, the best way to implement and to provide the domestic practitioners for assessing the remediation technique considering the economic benefit and the remediation schedule. The integration of the in-situ chemical oxidation (ISCO), the air sparging (AS) and soil vapor extraction (SVE) is an innovative technology. However, as the domestic remediation cases are concerned, the local contractors use gravitational injection to inject chemical oxidants in order to save cost. The present research found that the difference of the remediation schedule between the cases treated by the integrated AS and SVE and those treated by the integrated Fenton’s agent of the ISCO, AS and SVE is not significant in the remediation site with hydraulic conductivity ≧ 10-4cm/s and benzene concentration < 750ppb in groundwater. Regarding the remediation cases of the early discovered gasoline leakage from the gas station, in order to shorten the remediation period, the polluted soil was first completely removed and exchanged, then the polluted groundwater was treated by the integrated ISCO, AS, and SVE technology. The above remediation method is deemed favorable as the economic benefit and remediation schedule are concerned. However, it should be cautious about whether or not treating the groundwater by the chemical oxidation when considering the water quality protection of the water resource and environment sensitive region.

Petroleum hydrocarbons (PHCs) such as gasoline are ubiquitous organic compounds present at contaminated sites throughout the world. Accidental spills and leakage from underground storage tanks results in the formation of PHC source zones that release hundreds of organic compounds, including the high impact, acutely toxic and highly persistent aromatics (e.g., benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene) into groundwater. Contamination by these compounds continues to persist until the PHC source zone is treated in place or removed. In situ chemical oxidation (ISCO) employing persulfate was identified as a potentially viable technology for the treatment of PHC source zones. The effectiveness and efficiency and, therefore, the overall economic feasibility of a persulfate-based ISCO treatment system depend upon the reactivity of the target organic compounds and the interaction of persulfate with aquifer media. The objective of this research was to investigate the persistence of unactivated and activated persulfate in the presence of aquifer materials, and to examine persulfate oxidation of PHC compounds at both the bench- and pilot-scales. A series of bench-scale studies were performed to estimate persulfate degradation kinetic parameters in the presence of seven well-characterized, uncontaminated aquifer materials and to quantify the changes in specific properties of these materials. Batch experiments were conducted in an experimental system containing 100 g of solids and 100 mL of persulfate solution at 1 or 20 g/L. Column experiments were designed to mimic in situ conditions with respect to oxidant to solids mass ratio and were performed in a stop-flow mode using a 1 g/L persulfate solution. The degradation of persulfate followed a first-order rate law for all aquifer materials investigated. An order of magnitude decrease in reaction rate coefficients was observed for systems that used a persulfate concentration of 20 g/L as compared to those that used 1 g/L due to ionic strength effects. As expected, the column experiments yielded higher reaction rate coefficients than batch experiments for the same persulfate concentration due to the lower oxidant to solids mass ratio. Bench-scale data was used to develop a kinetic model to estimate the kinetic response of persulfate degradation during these tests. The push-pull tests involved the injection of persulfate (1 or 20 g/L) and a conservative tracer into a hydraulically isolated portion of the sandy aquifer at CFB Borden, Canada. The kinetic model developed from the bench-scale data was able to reproduce the observed persulfate temporal profiles from these push-pull tests. This implies that persulfate degradation kinetics is scalable from bench-scale to in situ scale, and bench tests can be employed to anticipate in situ degradation. The estimated reaction rate coefficients indicate that persulfate is a persistent oxidant for the range of aquifer materials explored with half lives ranging from 2 to 600 days, and therefore in situ longevity of persulfate will permit advective and diffusive transport in the subsurface. This is critical for successful delivery of oxidant to dispersed residuals in the subsurface. Activation of persulfate is generally recommended to enhance its oxidation potential and reactivity towards organic compounds. This approach may influence the stability of persulfate-activator system in the presence of aquifer materials. A series of batch tests were performed to investigate persistence of persulfate at two concentrations (1 or 20 g/L) using three contemporary activation strategies (citric acid chelated-ferrous, peroxide and high pH ) in the presence of 4 well-characterized, uncontaminated aquifer materials. Chelation by citric acid was ineffective in controlling the interaction between persulfate and Fe(II) and a rapid loss in persulfate concentration was observed. Higher Fe(II) concentration (600 mg/L) led to greater destabilization of persulfate than lower Fe(II) concentration (150 mg/L) and the persulfate loss was stoichiometrically equivalent to the Fe(II) concentration employed. Subsequent to this rapid loss of persulfate, first-order degradation rate coefficients (kobs) were estimated which were up to 4 times higher than the unactivated case due to the interaction with Fe(III) and CA. Total oxidation strength (TOS) was measured for peroxide activation experiments and was observed to decrease rapidly at early time due peroxide degradation. This was followed by slow degradation kinetics similar to that of unactivated persulfate implying that the initial TOS degradation was peroxide dominated and the long-term kinetics were dominated by persulfate degradation. The kobs used to capture TOS degradation for later time were shown to depend upon unactivated persulfate and peroxide degradation rate coefficients, and peroxide concentration. Either a slow peroxide degradation rate and/or higher peroxide concentration allow a longer time for peroxide and persulfate to interact which led to kobs ~1 to 100 times higher than kobs for unactivated persulfate. For alkaline activation, kobs were only 1 to 4 times higher than unactivated persulfate and therefore alkaline conditions demonstrated the least impact on persulfate degradation among the various activation strategies used. For all activation trials, lower stability of persulfate was observed at 1 g/L as compared to 20 g/L due to insufficient persulfate and/or ionic strength effects. A series of batch reactor trials were designed to observe the behavior of the nine high impact gasoline compounds and the bulk PHC fraction measures subjected to various persulfate activation strategies over a 28-day period. This bench-scale treatability used unactivated persulfate (1 or 20 g/L) and activated persulfate (20 g/L). Activation employed chelated-Fe(II), peroxide, high pH or two aquifer materials as activators. No significant oxidation of the monitored compounds was observed for unactivated persulfate at 1 g/L, but 20 g/L persulfate concentration resulted in their near-complete oxidation. Oxidation rates were enhanced by 2 to 18 times by activation with peroxide or chelated-Fe(II). For alkaline activation, pH 11 trials demonstrated ~2 times higher oxidation rates than the unactivated results. For pH 13 activation the oxidation rates of benzene, toluene and ethylbenzene were reduced by 50% while for the remaining monitored compounds they were enhanced by 5 to 100%. Natural activation by both aquifer materials produced oxidation rates similar to the unactivated results, implying that either activation by minerals associated with aquifer material was not significant or that any potential activation was offset by radical scavenging from aquifer material constituents. Acid-catalyzation at pH <3 may enhance oxidation rates in weakly buffered systems. Oxidation of the monitored compounds followed first-order reaction kinetics and rate coefficients were estimated for all the trials. Overall, activated and unactivated persulfate appear to be suitable for in situ treatment of gasoline. Persulfate under unactivated or naturally activated conditions demonstrated significant destruction of gasoline compounds and showed higher persulfate persistence when in contact with aquifer solids as compared to chelated-Fe(II) or peroxide-activated persulfate systems. This observation was used as the basis for selecting unactivated sodium persulfate for a pilot-scale treatment of gasoline-contaminated source zone at CFB Borden, Canada where a ~2000 L solution of persulfate (20 g/L) was injected into a PHC source zone. Concentration of organics and inorganics were frequently monitored over a 4 month period across a 90 point monitoring fence line installed down-gradient. Treatment performance was measured by estimating organic and inorganic mass loading across the monitoring fence. Increased mass loading for sodium was observed over time as the treatment volume moved across the fence-line indicating transport of the inorganic slug created upon oxidant injection. The mass loading also increased for sulfate which is a by-product generated either due to persulfate degradation during oxidation of organic compounds or during its interaction with aquifer materials. Oxidation of organic compounds was evident from the enhanced mass loading of dissolved carbon dioxide. More importantly, a significant (45 to 86%) decrease in mass loading of monitored compounds was observed due to oxidation by injected persulfate. The cumulative mass crossing the monitoring fence-line was 20 to 50% lower than that expected without persulfate treatment. As the inorganic slug was flushed through the source zone and beyond the monitoring fence, the mass loading rate of sodium, sulfate and carbon dioxide decreased and approached background condition. Mass loading of the monitored compounds increased to within 40 to 80% of the pre-treatment conditions, suggesting partial rebound. These investigations assessed the impact of activation on persulfate persistence and treatability of gasoline and served to establish guidelines for anticipating field-scale persulfate behavior under similar conditions. In summary, unactivated persulfate is a stable oxidant in the presence of aquifer materials and its persistence depends upon TOC and Fe(Am) content of the materials, ionic strength, and aquifer to solids mass ratio. Persulfate exhibits significant destruction of gasoline compounds and can be employed for the remediation of gasoline-contaminated sites. Peroxide and chelated-Fe(II) enhance oxidation rates of these compounds, but reduce stability of the persulfate-activator system. Persulfate activation using high pH conditions does not significantly impact persulfate persistence but reduces the overall destruction of gasoline compounds. Therefore, activation imposes a trade-off between enhanced oxidation rates and reduced persulfate persistence. Kinetic model is representative of persulfate degradation at bench- and pilot-scales and can be used for estimation of in situ degradation. The quantification of oxidation rates for gasoline compounds under activated and unactivated persulfate conditions will assist decision-making for identification of appropriate remediation options when targeting contamination by gasoline or by specific high impact gasoline compounds. While persulfate oxidation resulted in partial treatment of a small gasoline source zone, aggressive persulfate load will be required during injection for a complete clean-up. Overall, persulfate-based in situ chemical oxidation was demonstrated to be an effective and a viable technology for the remediation of contaminated soil and groundwater.

Iron oxide-bearing minerals have long been recognized as an effective reactive media for arsenic-contaminated groundwater remediation. This research aimed to develop a technique that could facilitate in situ oxidative precipitation of Fe3+ in a soil (sand) media for generating a subsurface iron oxide-based reactive barrier that could immobilize arsenic (As) and other dissolved metals in groundwater. A simple in situ arsenic treatment process was successfully developed for treating contaminated rural groundwater using iron oxide-coated sand (IOCS). Using imbibition flow, the system facilitated the dispersive transport of ferrous iron (Fe2+) and oxidant solutions in porous sand to generate an overlaying blanket where the Fe2+ was oxidized and precipitated onto the surface as ferric oxide. The iron oxide (FeOx) emplacement process was significantly affected by (1) the initial surface area and surface-bound iron content of the sand, (2) the pH and solubility of the coating reagents, (3) the stability of the oxidant solution, and (4) the chemical injection schedule. In contrast to conventional excavate-and-fill treatment technologies, this technique could be used to in situ replace a fresh iron oxide blanket on the sand and rejuvenate its treatment capacity for additional arsenic removal. Several bench-scale experiments revealed that the resultant IOCS could treat arsenic-laden groundwater for extended periods of time before approaching its effective life cycle. The adsorption capacity for As(III) and As(V) was influenced by (1) the amount of iron oxide accumulated on the sand surface, (2) the system pH, and (3) competition for adsorption sites from other groundwater constituents such as silicon (Si) and total dissolved solids (TDS). Although the IOCS could be replenished several times before exhaustion, the life cycle of the FeOx reactive barrier may be limited by the gradual loss of hydraulic conductivity induced by the imminent reduction of pore space over time.

博士<br>國立臺灣大學<br>環境工程學研究所<br>100<br>The purposes of this study are to explore the applicability and relevance to implement persulfate oxidation as a remedial means for soil and groundwater contaminated by petroleum hydrocarbons in Penghu area. This study consisted of three main work tasks including two laboratory and one pilot-scale demonstrations. Prior to oxidation testings, priority heavy metals content of the testing soils collected from the project area was evaluated through bench-scale chemical oxidation experiments. As in the tests for the the study site, a gasoline service station, it was observed that at pH of groundwater less than 4.0, heavy metal as nickel was detected at a concentration of 1.19 mg/L in groundwater, exceeding the regulatory standard of 1.0 mg/L. When pH elevated to a level above 6.0, nickel concentration was declined to a concentration of 0.719 mg/L. It appeared that decrease in nickel concentration was attributed to the pH increases in groundwater; therefore, it appeared that decrease in pH in groundwater during oxidation treatment process was the main cause to trigger the increase of nickel concentration. As in the field pilot tests for power plant remediation, Results obtained from the bench- and pilot-scale tests reveal that persulfate is a more persistent oxidant than hydrogen peroxide and sulfate radical (SO4-‧) has longer reaction time than hydroxyl radical (OH-‧). Furthermore, it was observed that persulfate was subject to less impact by radical scavengers as CO32-, HCO3-, and Cl- than was hydrogen peroxide, and it thereby, had less soil oxidant demand in the aqueous system onsite. Data obtained from bench-scale experiments showed that persulfate oxidation provided better removal efficiency for petroleum hydrocarbons than Fenton-like reaction. Results of bench experiments revealed that nearly 90% of total petroleum hydrocarbons (TPHd) in the soil matrix was reduced through persulfate oxidation, as opposed to 41% through Fenton-like reaction. The subsequent pilot-scale testing showed that persulfate activated by either ferrous ion or hydrogen peroxide could effectively reduce TPHd concentration to below the regulatory standard within two weeks of testing period. In the course chemical oxidation, heat, low pH, and gas generated during oxidation process would not only enhance desorption of the contaminants but also elevate the solubility of the chemicals of concern. Persulfate oxidation in the pilot test was observed to elevate the solubility of TPHd by two orders of magnitude, from 1.34 mg/L in groundwater to 289 mg/L in leachate collected from the soil treatment cells. Statistical analysis of the pilot testing performed at a power-plant indicated that 71.7% of diesel fuel was reduced through persulfate oxidation, 23.5% of diesel fuel was recovered from leachate as free product, and less than 5% of diesel fuel remained in the soil. Nickel has poor sorption selectivity to soil as compared to other divalent metals and has strong tendency to dissolve in groundwater as pH declines, causing secondary site contamination, particularly in the area where the aquifer consists of nickel-rich soil. Therefore, treatability of chemical oxidation for groundwater remediation should be carefully evaluated and planned prior to implementation to prevent from adverse site impact.

碩士<br>輔英科技大學<br>環境工程與科學系碩士班<br>104<br>This research adopted the In-Situ Chemical Oxidation, In-Situ Groundwater Bioremediation, Air Sparging and Soil Vapor Extraction to perform the mode field simulation test for leak sites of oil grooves from a gas station after the status of site survey. My study continuously renovated the field according to the status of site investigation and the preliminary result of simulation test, I also discussed the effect in the end after monitoring the Soil Gas and analyzing the pollutants concentration of BTEX and MTBE in the improvement period. After the time interval of location monitor process from September, 2014 to April, 2015, we immediately analyzed the concentration of pollutants and the effect of improvement. The results reveal that four methods could effectively remediated as well in this study, the improvement effect of In-Situ Chemical Oxidation decreased the concentration of benzene by monitoring from 0.334 ppm to 0.016 ppm and the removal efficiency reached 95.2%, the improvement effect of In-Situ Groundwater Bioremediation decreased the concentration of benzene by monitoring from 0.300 ppm to 0.017 ppm and the removal efficiency reached 94.3%, the improvement effects of Air Sparging and Soil Vapor Extraction decreased the concentration by monitoring from 16,900 ppm and 4,580 ppm to 49 ppm and 930 ppm, respectively. Setup problems in Soil Vapor Extraction method can be overcome with changes of method. Both the methods of In-Situ Chemical Oxidation and In-Situ Groundwater Bioremediation can achieve effectiveness by injection system of Air Sparging. It is extremely effective to reducing the time of improvement for the leak sites of oil grooves by several methods in the same time.

碩士<br>國立中興大學<br>環境工程學系所<br>100<br>This pilot-scale study was aimed to evaluate the efficacy of new stabilized nanoscale zero-valent iron (NZVI) particles in a contaminated site of groun dwater PCE that belongs to one of the dense non-aqueous phase liquids (DNAPLs). DNAPL is mostly carcinogenic or highly toxic. Once DNAPL was released into an aquifer, it could take a very long time to restore the site. Thus far, it has not been seen that a DNAPL site was successfully remediated in Taiwan. This study was carried out through the monitoring of PCE concentrations and it derivatives in wells before and after the injection of NZVI, offered by GeoNano Inc. Total 60 VOCs and Fe concentrations in groundwater were analyzed, which was then used to evaluate the influenced distance and environmental impact of NZVI. The results demonstrated that NZVI could be effective toward the degradation of targeted PCE which achieved 85% removal efficiency in 293 hours after NZVI injection. No other by-products [i.e., vinyl chloride (VC)] were obviously increased. Moreover, the influenced distance could reach more than 10 meter, and the clogging in wells was not appreciably observed.

碩士<br>國立屏東技術學院<br>環境工程技術研究所<br>84<br>Chlorophenols are common industrial chemicals. Because of high solubilities, they can spread very fast in groundwater systems. They are toxic and usually resistant to biodegradation. This study evaluated the feasibility of in-situ cheimcal oxidation of the groundwater contaminated by chlorophenols using Fenton reagent. Hydrogen peroxide and ferrous ions were added to soil microcosms to generate Fenton reaction. Chlorophenols evaluated in this study included 2- chlorophenol ,4 -chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol. A sandy soil and a silty soil were sampled from the Pingtung Country, Taiwan. Various combinations of hydrogen peroxide dosage and ferrous ion concentration were tested. The effect of nutrient salts were also examined. The results showed that H2O2 dosge and ferrous ion concentration for the best chlorophenol oxidation at natural pH were 0.05% H2O2 and 2mM Fe2(， respectively. The decrease of chlorophenols were also consistant with the increase of chloride ion in solution. However, the breakage of chlorine from chlorophenols was not 100%. The adsorption of chlorophenols plays an important role on the chemical oxidation in the soil slurry system. At low oxidation potential (low hydrogen peroxide dosage and ferrous ions) , only the chlorophenols in the soil solution were oxidized, and the adsorbed were redissolved to the solution. When high contration H2O2 and Fe2( were added, the adsorbed chlorophenols were also oxidized, and the increase of chlorophenols in soil solution was not observed.

A numerical model was utilized to assess the effects of elevated temperature on the application of in situ chemical oxidation (ISCO) and enhanced in situ bioremediation (EISB) for the subsurface remediation of trichloroethene (TCE) and tetrachloroethene (PCE). Temperature adjustment of the contaminant physicochemical properties as well as the chemical/biological reactions associated with ISCO and EISB were accounted for in the model domain. ISCO reaction rates were estimated using Arrhenius principles; microbial growth rates for EISB were estimated using non-linear fits to published literature data. The results from this study showed that temperature did provide remedial benefits to ISCO and EISB treatment during the short-term timeframe of oxidant/substrate injection. During these time periods, heated ISCO and EISB treatment exhibited greater DNAPL mass removal and mass flux reduction compared to heated abiotic dissolution. In the long term, after oxidant/substrate injection was terminated, the treatment enhancements achieved by ISCO and EISB were negated. Permeability (k) reduction due to rind formation (ISCO) and bioclogging (EISB) inhibited DNAPL dissolution and contributed to greater dissolution tailing effects. Tailing effects caused by ISCO were more severe compared to EISB since rind formation contributed to permanent k reduction; partial k recovery was observed in the EISB scenarios due to biomass decay. Even though higher temperatures were beneficial to ISCO and EISB during the short-term oxidant/substrate injection period, treatment efficacy was ultimately controlled by the detrimental by-products (rind from ISCO and biomass from EISB) formed as a result of the associative chemical/biological reactions.<br>Thesis (Master, Civil Engineering) -- Queen's University, 2014-02-10 18:59:23.177

博士<br>國立中山大學<br>環境工程研究所<br>95<br>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.

Water quality degradation is the foremost environmental issue faced by the mining industry. Negative impacts on water quality are commonly associated with unmitigated drainage emanating from sulfide-bearing mine waste deposits. These impacts stem from the liberation of acidity, sulfate, metals (e.g. Fe, Ni, Cu, Zn and Pb), and trace elements (e.g. Co, As, Cd, Sb and Tl) during the oxidation of sulfide minerals. Drainage at operational mines is commonly treated using techniques such as chemical oxidation and acid neutralization, which can succeed in achieving regulatory discharge guidelines. However, active treatment techniques are commonly burdened by high capital and operating costs. The development of passive technologies for treatment of mine drainage, which promote sulfate reduction, metal-sulfide precipitation and alkalinity production, therefore present a cost-effective alternative for managing mine drainage quality. This thesis describes laboratory and field evaluations of techniques for passive in situ treatment of acidic and neutral mine waters. Laboratory batch experiments evaluated the treatment of acid mine drainage (AMD) with mixtures of organic carbon and zero-valent iron (ZVI) for use in permeable reactive barriers (PRBs). Modest increases in sulfate-reduction rates up to 15 % were achieved by amending organic carbon mixtures with 5 to 10 % (dry wt.) ZVI. Reactive mixtures containing organic carbon supported growth of sulfate-reducing bacteria (SRB) and facilitated removal of Fe, Zn, Cd, Ni, Co and Pb. However, organic carbon was necessary to support SRB growth and sulfate reduction. Removal of Zn, Cd, Ni, Co and Pb in the absence of organic carbon is attributed to sorption and (co)precipitation reactions at the ZVI surface. Scanning electron microscopy (SEM) and X-ray absorption near-edge structure (XANES) spectroscopy confirmed the presence of secondary Fe-sulfides in mixtures containing organic carbon. The dominant reaction product in these mixtures was identified as disordered mackinawite [Fe1+xS]. The addition of ZVI to organic carbon enhanced AMD treatment over the duration of this experiment; however, long-term evaluation is required to identify optimal reactive mixtures. Field-based investigations into passive management of near-neutral pH tailings pore-water were carried out at the Greens Creek mine, located near Juneau, Alaska, USA. These studies focused on delineation of mechanisms controlling tailings pore-water chemistry, and a evaluation of the effectiveness of organic carbon amendment of tailings for passive in situ management of pore-water quality. Results demonstrate that sulfide-mineral oxidation and carbonate dissolution are the primary influences on tailings pore-water composition. Pyrite [FeS2] accounted for < 20 to > 35 wt. % of the tailings mineral assemblage, whereas dolomite [CaMg(CO3)2] and calcite [CaCO3] were present at ≤ 30 and 3 wt. %, respectively. The sulfide-mineral assemblage was dominated by pyrite; however, sphalerite [(Zn,Fe)S] and galena [PbS] were commonly observed, and tetrahedrite [(Fe,Zn,Cu,Ag)12Sb4S13], arsenopyrite [FeAsS], and chalcopyrite [CuFeS2] were present in lesser amounts. Geochemical analysis of tailings core samples generally agreed with mineralogical data. The occurrence of Cd, Cr, Co, Mo, Ni, Se, and Tl is attributed to their occurrence as impurities in primary sulfide phases. Most probable number (MPN) populations of neutrophilic sulfur-oxidizing bacteria (nSOB) and SRB were elevated at several locations within the tailings deposit. Near-neutral pH conditions dominated; however, elevated concentrations of dissolved SO4, S2O3, Fe, Zn, As, Sb, and Tl were observed within and below the oxidation zone. Field-scale experiments conducted over four years evaluated passive in situ treatment of pore-water by amending unoxidized tailings with 5 and 10 vol. % organic carbon. Field-scale cells were constructed to evaluate amendments containing differing mixtures of peat, dried spent brewing grain (SBG), and municipal biosolids (MB). Organic carbon amendment of the tailings supported the development of conditions favorable to sulfate reduction. Decreases in aqueous SO4 concentrations were observed in three cells amended with mixtures of peat, SBG, and MB. Removal of SO4 was generally accompanied by H2S production, enrichment in 34S-SO4, and increased SRB populations. Undersaturation of pore-water with respect to gypsum was observed. Sulfate reduction was sustained for the duration of the experiment in cells amended with 5 vol. % peat + SBG and 10 vol. % peat + SBG + MB. The addition of organic carbon also supported reductive dissolution of Fe(III) (oxy)hydroxides and mobilization of Fe and As. The largest increases in aqueous Fe and As concentrations were observed in cells amended with MB. Subsequent decreases in Fe and As concentrations were observed under sulfate-reducing conditions. Attenuation of Zn, Sb, and Tl accompanied SO4 removal. Mineralogical examination by SEM revealed the presence of secondary Zn-S and Fe-S precipitates on surfaces of organic carbon particles, and carbonate and aluminosilicate grains. This study demonstrates that amendment of tailings with a small and dispersed mass of organic carbon has potential to improve the quality of tailings pore water.

碩士<br>國立中山大學<br>環境工程研究所<br>98<br>Groundwater at many existing and former industrial sites and disposal areas is contaminated by halogenated organic compounds that were released into the environment. The chlorinated solvent trichloroethylene (TCE) is one of the most ubiquitous of these compounds. In situ chemical oxidation (ISCO) has been successfully used for the removal of TCE. The objective of this study was to apply the ISCO technology to remediate TCE-contaminated groundwater. In this study, potassium permanganate (KMnO4) was used as the oxidant during the ISCO process. The study consisted bench-scale and pilot-scale experiments. In the laboratory experiments, the major controlling factors included oxidant concentrations, effects of soil oxidant demand (SOD) on oxidation efficiency, and addition of dibasic sodium phosphate on the inhibition of production of manganese dioxide (MnO2). Results show that higher molar ratios of KMnO4 to TCE corresponded with higher TCE oxidation rate under the same initial TCE concentration condition. Moreover, higher TCE concentration corresponded with higher TCE oxidation rate under the same molar ratios of KMnO4 to TCE condition. Results reveal that KMnO4 is a more stable and dispersive oxidant, which is able to disperse into the soil materials and react with organic contaminants effectively. Significant amount of MnO2 production can be effectively inhibited with the addition of Na2HPO4. Results show that the increase in the first-order decay rate was observed when the oxidant concentration was increased, and the half-life was approximately 24.3 to 251 min. However, the opposite situation was observed when the second-order decay rate was used to describe the reaction. Results from the column experiment show that the breakthrough volumes were approximately 50.4 to 5.06 pore volume (PV). Injection of KMnO4 would cause the decrease in TCE concentration through oxidation. Results also indicate that the addition of Na2HPO4 would not inhibit the TCE removal rate. In the second part of this study, a TCE-contaminated site was selected for the conduction of pilot-scale study. A total of eight remediation wells were installed for this pilot-scale study. The initial TCE concentrations of the eight wells were as follows: C1 = 0.59 mg/L, C1-E = 0.64 mg/L, C1-W = 0.61 mg/L, EW-1 = 0.65 mg/L, EW-1E = 0.62 mg/L, EW-1W = 0.57 mg/L, C2 = 0.62 mg/L, C3 = 0.35 mg/L. C1, EW-1, C2, and C3 were located along the groundwater flow direction from the upgradient (C1) to the downgradient location (C3), and the distance between each well was 3 m. C1-E and C1-W were located in lateral to C1 with a distance of 3 m to C1. EW-1E and EW-1W were in lateral to EW-1 with a distance of 3 m to EW-1. In the first test, 2,700 L of KMnO4 solution was injected into each of the three injection wells (C1, C1-E, and C1-W) with concentration of 5,000 mg/L. Three injections were performed with an interval of 6 hr between each injection. After injection, the TCE concentrations in those three wells dropped down to below detection limit (&amp;lt;0.0025 mg/L). However, no significant variations in TCE concentrations were observed in other wells. In the second test, 2,700 L of KMnO4 solution was injected into injection well (EW-1) with concentration of 5,000 mg/L. Six injections were performed with an interval of 6 hr between each injection. After injection, the TCE concentrations in the injection well dropped down to below detection limit (&amp;lt;0.0025 mg/L). TCE concentrations in (C1, C1-E, C1-W, EW-1E, EW-1W, C2, and C3) dropped to 0.35-0.49 mg/L. After injection, no significant temperature and pH variation was observed. However, increase in conductivity and oxidation-reduction potential (ORP) was observed. This indicates that the KMnO4 oxidation process is a potential method for TCE-contaminate site remediation. The groundwater conductivity increased from 500 μS/cm to 1,000 μS/cm, and ORP increased from 200 to 600 mv. Increase in KMnO4, MnO2, and total Mn was also observed in wells. Results from the slug tests show that the hydraulic conductivity remained in the range from 10-4 to 10-5 m/sec before and after the KMnO4 injection.

碩士<br>國立中山大學<br>環境工程研究所<br>99<br>The purpose of this study was to use controlled release technology combining with in situ chemical oxidation (ISCO) and permeable reactive barrier (PRB) to remediate TCE-contaminated groundwater. In this study, potassium permanganate (KMnO4) releasing material was designed for potassium permanganate release in groundwater. The components of potassium permanganate releasing material included poly (ε-caprolactone) (PCL), potassium permanganate, and starch with a weight ratio of 2:1:0.5. Approximately 63.8% (w/w) of potassium permanganate was released from the material after 76 days of operation. The released was able to oxidize contaminant in groundwater. Results from the solid oxidation demand (SOD) experiment show that the consumption rate increased with increased contaminant concentration. TCE removal efficiency increased with the increased TCE concentration. The second-order rate law can be used to simulate the TCE degradation trend. In the column experiment, results show that the released MnO4- could oxidize TCE and TCE degradation byproducts when 95.6 pore volume (PV) of contaminated groundwater was treated. More than 95% of TCE removal can be observed in the column study. Although the concentration of manganese dioxide (MnO2) began to rise after 8.8 PV of operation, TCE removal was not affected. Results also show that low level of hexavalent chromium was detected (&amp;lt; 0.05 mg/L). Results from the scanning electron microscope (SEM) and energy-dispersive spectroscope (EDX) analyses show that the amounts of manganese and potassium in the materials decreased after the releasing experiment. Results indicate that the concentration of TCE and SOD need to be analyzed before the releasing materials are applied in situ. In the practical application, the releasing materials will not become solid wastes because they are decomposed after use. If this slow-releasing technology can be combined with a permeable reactive barrier system, this technology will become a more economic and environmentally-friendly green remedial system.

Petroleum hydrocarbon (PHC) contamination poses a serious threat to aquifer systems worldwide. Accidental releases of PHCs due to gasoline spills and leakage from underground storage tanks can often result in PHC subsurface contamination. The main compounds of concern associated with gasoline spills are benzene, toluene, ethylbenzene and xylenes (BTEX), trimethylbenzenes (TMBs) and naphthalene, due to their high mobility and potential human health risks. Sodium persulphate is one of the newest oxidants to gain widespread use for in situ chemical oxidation (ISCO), however its effectiveness in treating PHCs is not fully understood. In this study, the ability to use unactivated sodium persulphate as a remediation tool in treating dissolved and residual BTEX contamination was tested during a bench-scale laboratory study and within a pilot-scale field investigation. In both cases unactivated sodium persulphate was used at a concentration of 100 g/L. A laboratory-scale degradation potential batch test was conducted to assess the efficacy of unactivated sodium persulphate to oxidize petroleum hydrocarbon contaminated groundwater in conjunction with aquifer material from a field site. Data from the control reactions indicated that persulphate was stable for the entire 35-day experimental period and that the decrease in PHC concentrations for most of the samples followed a first-order degradation. The behaviour and ability for sodium persulphate to oxidize dissolved and residual BTEX contamination was further evaluated in a controlled pilot scale field study. 200 kg of sodium persulphate was dissolved in 2000 L of water and injected into the subsurface. Electrical conductivity (EC), pH, sodium, persulphate, sulphate and BTEX concentrations were all monitored throughout the 158-day study period. Field research showed that there was a strong correlation between EC and sodium concentrations. Hence, this relationship allowed for real-time EC measurements to be used to effectively predict the extent of the injectate. Based on the calculated aqueous density of sodium persulphate at a concentration of 100g/L, predicted simulation model results and observed tracer field results, density effects were present and played a very important role in the transport of the injectate. The heterogeneous geology of the site also greatly influenced the transport of the injectate. The majority of the injectate appeared to have flowed out of the layers with higher hydraulic conductivity that intersected the upper and lower portion of the injection well’s screen length. The extent of the injected slug in the layers with lower hydraulic conductivity located in the centre portion of the injection well’s screen length was less in comparison. In general, areas with elevated tracer, persulphate and sulphate concentrations, also showed a decrease in BTEX concentration. Four main responses were observed. Group 1 consists of sampling points where tracer levels were elevated along with a corresponding short-term decrease in dissolved BTEX. Group 2 consists of sampling points where elevated tracer levels was observed along with a long-term apparent decrease in dissolved BTEX. Group 3 consists of sampling points where the tracer was elevated however dissolved BTEX levels remained essentially at background levels. And finally, group 4 consists of sampling points where the tracer was not observed to be elevated hence no decrease in dissolved BTEX was observed. Laboratory studies showed that the oxidation of BTEX compounds by unactivated sodium persulphate could be very successful. However, field study results showed that complexities such as heterogeneity of the field site and injectate density effects play a key role in the success of the remediation system.

碩士<br>國立暨南國際大學<br>土木工程學系<br>103<br>In this study, a treatment train composed of chemical oxidation and anaerobic bioremediation was applied to remediate trichloroethylene (TCE)-contaminated groundwater. Soil and groundwater collected from a TCE-contaminated site were used for batch and column experiments. The treatment train used in this study consisted of persulfate oxidation, anaerobic bioremediation reagents, and persulfate release materials. Results of batch experiments show high concentrations of TCE (50 mg/L) could be removed rapidly by 1 to 5% persulfate addition during 1 day of reaction. The addition of 0.5% persulfate could also oxidize TCE completely during a 4-day reaction. Ferrous ion-activated persulfate may cause the residual of TCE due to the rapid consumption of persulfate by ferrous ions. Significant inhibition of soil bacteria was observed with the addition of persulfate higher than 2%. Results of microcosm study reveal dechlorinating bacteria were present at the site. The addition of 0.5% the commercial anaerobic bioremediation reagent, Eco-Clean, could enhance the dechlorination of TCE effectively. No significant effects on TCE removal were observed with thepresence of high concentrations of sulfate (5%). The results show the proposed treatment train would be feasible for groundwater remediation. However, field pilot study needs to be conducted to further evaluate the effectiveness of the treatment train on field applications.

The ever-increasing detection of harmful organic and inorganic compounds in habitable areas throughout the world has led to mounting research into applications and techniques for the treatment of contaminated soils, surface and groundwaters, and chemical and industrial wastewaters. Chemical oxidation technologies, in particular Fenton-based remediation systems, have exhibited considerable potential for the effective treatment and remediation of such contaminated waters and soils. The use of Fenton-based oxidation systems for the treatment of contaminated waters and wastewaters warrants the development of kinetic models capable of accurately simulating system behaviour. In this thesis, the kinetics of Fenton-mediated oxidation systems and kinetic models based on its governing reaction mechanism are investigated in order to highlight those parameters and conditions that effect Fenton chemistry and oxidation performance, and to demonstrate the application of such kinetic models to design and improve treatment systems. Experimental and simulated data describing the oxidation of formic acid by Fenton's reagent at low pH (3 to 4) and under a variety of initial conditions, operating regimes, and solution environments supports a proposed reaction mechanism that nominates the hydroxyl radical (OH) as the active oxidizing intermediate in Fenton-based oxidation systems. Laboratory experiments demonstrate that formic acid oxidation is inhibited in the presence of oxygen, and model simulations of these systems reveals that such behaviour is due to the effect organic radical intermediates and/or by-products have in assisting or hindering the redox cycling of the catalytic iron species. The critical role that iron redox cycling plays in affecting oxidation performance is further highlighted by experimental and simulated studies at alternate pHs and using different target organics, including those that react directly with iron in a redox capacity. Experiments at pH 4 reveal an increase in the redox cycling of iron and improved oxidation performance compared to pH 3 as the higher pH favours the superoxide radical, a stronger reductant than the hydroperoxyl radical that predominates at pH 3. Other laboratory and modelling studies on the Fenton-mediated oxidation of certain aromatic compounds highlight the manner in which quinone and quinone-like compounds, being added directly or generated as oxidation by-products, can improve oxidation performance via redox reactions with iron. Further simulations reveal the type of practical design and operating information kinetic models can provide for treatment processes, though it is noted an appropriate understanding of the oxidation mechanism of the target species is necessary for the accurate application of the model.

abstract: In situ remediation of contaminated aquifers, specifically in situ bioremediation (ISB), has gained popularity over pump-and-treat operations. It represents a more sustainable approach that can also achieve complete mineralization of contaminants in the subsurface. However, the subsurface reality is very complex, characterized by hydrodynamic groundwater movement, geological heterogeneity, and mass-transfer phenomena governing contaminant transport and bioavailability. These phenomena cannot be properly studied using commonly conducted laboratory batch microcosms lacking realistic representation of the processes named above. Instead, relevant processes are better understood by using flow-through systems (sediment columns). However, flow-through column studies are typically conducted without replicates. Due to additional sources of variability (e.g., flow rate variation between columns and over time), column studies are expected to be less reproducible than simple batch microcosms. This was assessed through a comprehensive statistical analysis of results from multiple batch and column studies. Anaerobic microbial biotransformations of trichloroethene and of perchlorate were chosen as case studies. Results revealed that no statistically significant differences were found between reproducibility of batch and column studies. It has further been recognized that laboratory studies cannot accurately reproduce many phenomena encountered in the field. To overcome this limitation, a down-hole diagnostic device (in situ microcosm array - ISMA) was developed, that enables the autonomous operation of replicate flow-through sediment columns in a realistic aquifer setting. Computer-aided design (CAD), rapid prototyping, and computer numerical control (CNC) machining were used to create a tubular device enabling practitioners to conduct conventional sediment column studies in situ. A case study where two remediation strategies, monitored natural attenuation and bioaugmentation with concomitant biostimulation, were evaluated in the laboratory and in situ at a perchlorate-contaminated site. Findings demonstrate the feasibility of evaluating anaerobic bioremediation in a moderately aerobic aquifer. They further highlight the possibility of mimicking in situ remediation strategies on the small-scale in situ. The ISMA is the first device offering autonomous in situ operation of conventional flow-through sediment microcosms and producing statistically significant data through the use of multiple replicates. With its sustainable approach to treatability testing and data gathering, the ISMA represents a versatile addition to the toolbox of scientists and engineers.<br>Dissertation/Thesis<br>Ph.D. Civil and Environmental Engineering 2013