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Iron-based degradative solidification/stabilization (Fe(II)-DS/S) is a treatment method that could be economically applied to smaller DNAPL-contaminated sites and to those sites with impermeable soils. Reductive dechlorination is achieved by compounds that are formed by reaction of ferrous iron with components of Portland cement or with defined chemicals (FeCl3 + Ca(OH)2). These dechlorinating agents can effectively degrade chlorinated hydrocarbons (PCE, TCE, and 1,1,1-TCA) that are dissolved in aqueous solution. This research investigated the application of Fe(II)-DS/S to remove chlorinated hydrocarbons that are present as DNAPLs in source zones and to compared the reactivity of ferrous iron in different mixtures, including the conventional mixture with cement (Fe(II)+C) and an iron-solid mixture (ISM) that was synthesized without the addition of cement. The modified first-order model, which the rate was proportional to the concentration of target in the aqueous phase and it was also nearly constant when DNAPL was present, was developed to describe dechlorination kinetics. The modified second-order model assumed that the rate was proportional to the product of the concentration of target in the aqueous phase and the concentration of reductive capacity of the solid reductant. The modified first-order model was used to describe degradation of target compounds with ISM, and the modified second-order model was used to describe removals for TCE and 1,1,1-TCA with Fe(II)+C. Results of experiments on PCE dechlorination with ISM indicated that the increase of Fe(II) in ISM increased rate constants and decreased the solubility of targets. The half-life was increased with increasing total PCE concentration. The product analysis implied that degradation of PCE with ISM was via a combination of the hydrogenolysis and β-elimination pathways. A comparison of the types of targets and reductants indicated that Fe(II)+C had better reactivity for chlorinated ethenes (PCE and TCE) than ISM. However, ISM could dechlorinate a chlorinated ethane (1,1,1-TCA) as rapidly as Fe(II)+10%C. The ratio of [RC]o/[Fe(II)]o implied that Fe(II) in Fe(II)+C was more involved in reducing chlorinated ethenes than was Fe(II) in ISM. Dechlorination of a DNAPL mixture followed the same order of reactivity as with individual DNAPLs with both reductants.

This study aims to investigate the fate of polychlorinated biphenyls (PCBs) in sediments via using an anaerobic dechlorination model (ADM). PCBs are ubiquitous environmental pollutants, accumulated mostly in aquatic sediments. Significant attention was placed on the anaerobic dechlorination of PCBs since this process leads to the conversion of highly-chlorinated biphenyls to lower chlorinated ones, resulting in less toxic and more biodegradable congeners. An ADM was developed previously for the identification and quantification of anaerobic dechlorination pathways. In the present study, this model was improved and applied to laboratory and environmental sediment PCB data from Baltimore Harbor (BH), Maryland, USA, where PCB contamination has been recorded. The laboratory PCB data was from a 500 day microcosm study conducted with BH sediments which was used to validate the model, as well as to gather information on dominant dechlorination pathways affecting the sediments. ADM predicted the laboratory PCB data almost perfectly and subsequently very well predicted the environmental sediment PCB profiles. A complete identification and quantification of the anaerobic dechlorination pathways occurring in the BH sediments is achieved with this study for the first time. The significant similarity between the sediment sample PCB profiles and the model predicted profiles reveals that the BH sediments have undergone anaerobic dechlorination via a combination of previously identified dechlorination activities (N, P, M) with selective pathways. Model findings are consistent with microbial analysis of the sediments. Better understanding of anaerobic dechlorination mechanisms should aid in predicting natural attenuation of PCBs or developing bioremediation strategies for contaminated sites.

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Naturally occurring bacterial populations are capable of detoxifying chlorinated compounds and immobilizing the radionuclide uranium via reductive processes. This study addressed the following three knowledge gaps in the fields of chlorinated solvent and uranium bioremediation, 1) the risks and benefits of coupling bioremediation with thermal treatment for clean-up of chlorinated ethene-contaminated sites, 2) the accuracy of available techniques for the monitoring of chlorinated solvent bioremediation, and 3) the role of gram positive Desulfitobacterium spp. in uranium immobilization. Experiments demonstrated that thermal treatment increases electron donor availability, but the increased electron donor was not used to fuel reductive dechlorination and was actually consumed for methanogenesis. Two approaches for monitoring chlorinated solvent bioremediation were investigated, molecular techniques and compound-specific isotope analysis (CSIA). Results demonstrated that while Dehalococcoides (Dhc) gene expression was up-regulated under conditions inhibitory to dechlorination, the isotope effects associated with dechlorination reactions catalayzed by Dhc populations in consortia and in pure cultures were similar. U(VI) reduction by multiple Desulfitobacterium isolates was demonstrated. Interestingly, while almost all U(VI)-reducing populations have been reported to produce uraninite (UO2), the product of U(VI) reduction by Desulfitobacterium isolates was a unique form of insoluble mononuclear U(IV).

The disposal of combustible wastes by incineration is a controversial issue that is strongly debated by both scientists and environmental activists due to the resulting emissions of noxious compounds, including (inter alia) polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), heavy metals and acid gases like sulfur dioxide. Currently available air pollution control devices are capable of effectively cleaning flue gases, and PCDD/F emissions to air from modern municipal solid waste (MSW) incinerators are low. However, the PCDD and PCDF end up in ash fractions that, in Sweden, are usually deposited in landfills. The European Union has recently set a maximum permitted total concentration of 15 µg TEQ/kg for PCDD/F species in waste. Fly ash from municipal solid waste (MSW) incineration containing PCDD/Fs at concentrations above this limit will have to be remediated to avoid disposing of them in landfills; an expensive and environmentally unfriendly option. Therefore, effective, reliable and cost-effective methods for degrading PCDD/F in fly ash are required, and a better understanding of the behavior of PCDDs and PCDFs during thermal treatment will be needed to develop them. In the studies this thesis is based upon both the formation and degradation of PCDDs and PCDFs in ashes from MSW incineration were studied. The main findings of the investigations regarding PCCD/F formation were: - The concentrations of PCDD and PCDF in fly ash increased with reductions in the temperature in the post-combustion zone. - The homologue profile in the ash changed when the temperature in the post-combustion zone changed. - The final amounts of PCDD and PCDF present were affected by their rates of both formation and degradation, and the mechanisms involved differ between PCDDs and PCDFs. The main findings from the degradation studies were: - The chemical composition of ash has a major impact on the degradation potential of PCDD and PCDF. - The presence of oxygen during thermal treatment can enhance the degradation of PCDD and PCDF. - Thermal treatment is a viable option for degrading PCDD and PCDF in ashes from MSW. - Shifts in chlorination degree occur during thermal treatment. - Rapid heat transfer into the ash is a key factor for ensuring fast degradation of PCDD and PCDF. - Degradation of other chlorinated organic compounds, e.g. PCB and HCB, also occurs during thermal treatment of ash. - Reductions in levels of PCDD and PCDF were not solely due to their desorption to the gas phase. - Differences between the behavior of 2378-substituted congeners of PCDD and PCDF and the other congeners during thermal treatment were observed. - Differences in isomer patterns of both PCDD and PCDF were observed between the ash and gas phases after thermal treatment at both 300 and 500 oC. Overall, the results show that the formation and degradation mechanisms of PCDDs differ substantially from those of PCDFs. Thus these groups of compounds should be separately considered in attempts to identify ways to reduce their concentrations.

Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It’s revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of PAA as a polyelectrolyte offers an excellent platform for the immobilization of metal nanoparticles (NPs) applied for degradation of toxic chlorinated organics with significantly increased longevity and stability. The advantage of using temperature and pH responsive polymers/hydrogels also includes the high reactivity and effectiveness in dechlorination. Further advancement on the PVDF functionalization involved the alkaline treatment to create partially defluorinated membrane (Def-PVDF) with conjugated double bounds allowing for the covalent attachment of different polymers. The PAA-Def-PVDF membrane shows pH responsive behavior on both the hydraulic permeability and solute retention. The sponge-like PVDF (SPVDF) membranes by phase inversion were developed through casting PVDF solution on polyester backing. The SPVDF membrane was demonstrated to have 4 times more surface area than commercial PVDF MF membrane, allowing for enhanced nanoparticles loading for chloro-organics degradation. The advanced functionalization method and process were also validated to be able to be scaled-up through the evaluation of full-scale functionalized membrane provided by Ultura Inc. California, USA. Nanofiltration (NF) between UF and RO presents selectivity controlled by both steric and electrostatic repulsions, which are widely used to reject charged species, particularly multivalent ions. In this work, selective permeation of CaCl2 and high sucrose retention are obtained through the modification of nanofiltration membranes with lower charge compared to commercial nanofiltration membrane. The membrane module also shows high stability with constant water permeability in a long-term (two months) test. Extended Nernst-Planck equation were further used to evaluate the experimental results and it fits well.

Detoxification of chlorinated organic compound is an important and urgent issue in water remediation nowadays. Trichloroethylene (TCE), as a model compound in this study, has been proved to be degraded effectively by bimetallic nanoparticles (NPs) in solution phase. In this study, Fe/Pd bimetallic NPs were synthesized in poly (acrylic acid) (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes. TCE dechlorination with these bimetallic NPs was conducted under different pH values and different metal loadings to study the role of corrosion on reaction rates. One-dimensional mathematical model with pseudo first-order reaction kinetic was introduced to discuss the TCE dechlorination profile in membrane system. Reduction reaction in pores is affected by several parameters including NP loading and size, TCE diffusivity, void volume fraction and surface-area-based reaction rates. This model result indicated that modification is needed to correct the reaction rate obtained from bulk solution in order to represent the actual efficiency of NPs on reduction reaction. In addition, TCE dechlorination mainly occurred near NPs’ surface. Second part of model indicated that reduction mechanism with TCE adsorption-desorption behavior could be used to discuss dechlorination with a high TCE concentration.

Contaminated aquatic sediments pose health risks to fish, wildlife, and humans and can limit recreational and economic uses of surface waters. Technical and cost effective in situ approaches for sediment management and remediation have been identified as a research need. Subaqueous in situ capping is a promising remedial approach; however, little is known regarding its impact on underlying sedimentary processes and the feasibility of bioaugmented caps at sites subject to contaminated groundwater seepage. This work specifically addresses (1) the impact of capping on biogeochemical processes at the sediment-water interface, (2) the ability and degree to which indigenous sediment microorganisms colonize an overlying cap, (3) the effect of advective flow direction on redox conditions within a cap, (4) natural contaminant bioattenuation processes within capped sediment, and (5) limitations toward a functional bioreactive in situ cap. Laboratory-scale experiments with capped sediment columns demonstrated that emplacement of a sand-based in situ cap induced an upward, vertical shift of terminal electron accepting processes into the overlying cap while simultaneously conserving redox stratification. Upflow conditions simulating a groundwater seep compressed anaerobic processes towards the cap-water interface. Microorganisms indigenous to the underlying sediment colonized cap material and spatial population differences generally reflected redox stratification. Downflow of oxic surface water through the cap, simulating tidally-induced recharge, created fully oxic conditions within the cap, demonstrating that flow direction strongly contributes to redox conditions. Experiments simulating capped sediment subject to contaminated groundwater seepage revealed a reduction of natural bioattenuation processes with time, stemming from the elimination of labile organic matter deposition to the sediment and a subsequent lack of electron donor. Thus, parent contaminants within groundwater seeps will be subject to minimal biotransformations within the sediment before entering a reducing cap. A bioreactive cap, inoculated with microorganisms capable of reductive dehalogenation, was established to reductively dechlorinate tetrachloroethene present in the groundwater; however electron donor amendments to sediment effluent were required to achieve complete dechlorination of tetrachloroethene to non-toxic ethene. Results from this work improve understanding of biogeochemical and bioattenuation processes within capped aquatic sediments and should aid in the development of active capping technologies.

Hexachloro-1,3-butadiene (HCBD) is a toxic aliphatic chlorinated hydrocarbon which is widely used as a fungicide, herbicide and heat transformer fluid. HCBD is resistant to microbial degradation and, therefore, persists in aquatic and soil environments worldwide. In this thesis, the ability of non-specific bacteria from various sources to dechlorinate HCBD in the presence of either acetate or lactate (as an electron donor) and cyanocobalamin (as an electron shuttle) under different conditions was investigated. Cultivating specific populations to reduce cyanocobalamin as a method to increase HCBD dechlorination rate was investigated. Also, the factors responsible for HCBD dechlorination and the stalling of dechlorination were studied. Lastly, redox potential measurement during the microbial reductive dechlorination of HCBD for online detection of ongoing dechlorination was evaluated. Findings from the Project „« Non-specific bacteria from activated sludge, anaerobic digested effluent from municipal waste, piggery waste and sheep rumen content are able to dechlorinate HCBD in the presence of cyanocobalamin to chlorine-free C4 gases in a biochemical reaction. „« Dechlorination was equated to the formation of completely dechlorinated end-products from HCBD dechlorination. „« Methanogens were found to be involved in HCBD dechlorination. „« Mediators rather than specific bacteria were responsible for the fast dechlorination rates. Results suggest that activated sludge may release synthesized mediators into the supernatant to enable enhanced HCBD dechlorination. „« HCBD dechlorination can be monitored using oxidation reduction potential (ORP). ORP has an effect on HCBD dechlorination rate. Scientific Significance/Novelty The most significant finding from this research is that it demonstrates chlorine-free end-products in contrast with other studies in literature (Booker and Pavlosthasis, 2000; Bosma et al., 1994) where dechlorination was equated with disappearance of HCBD into bacterial biomass and the detection of partially dechlorinated gases such as trichlorobutadiene. It also shows that, in contrast to literature where specific bacteria (i.e., pure strains/cultures) were commonly used for the dechlorination of polychlorinated hydrocarbons, results from this thesis show that non-specific bacteria were able to dechlorinate HCBD in the presence of cyanocobalamin at ratesƒx sufficiently high to be considered for bioremediation projects. Moreover, results demonstrate that ORP can be used to monitor HCBD dechlorination.