Zero valent iron (ZVI) has demonstrated its reactivity and effectiveness for in-situ groundwater and soil remediation. The potential of the high reducing activity of nanoscale ZVI (nZVI) for environmental decontamination has attracted more attentions in recent years, as nZVI may be injected with water to the pollution sites for in-situ remediation. However, rapid oxidation and instant agglomeration of nZVI make it difficult for large-scale engineering application. Effort has been made to improve the stability and mobility of nZVI for effective in-situ remediation. In the present study, a novel Ca-based surface coating method has been developed for protection of nZVI and enhancement of its transport in environmental applications. A simple thermal deposition method was employed to coat a Ca-based layer on the surface of micro- or nano- ZVI particles in water or methanol environment. According to microscopic observations, Ca(OH)2 nano-layer was formed on the ZVI surface. A clear core-shell structure was observed for the coated nZVI/Ca(OH)2 particles based on the TEM observations. The Ca(OH)2 coating layer had a thickness about one fifth of the nZVI diameter and the Ca to Fe ratio was below 0.2. With the Ca(OH)2 shell, nZVI particles can be effectively protected against corrosion according to the standard natural spray corrosion tests. Thus, the Ca(OH)2 coating layer is able to greatly improve the stability of nZVI during storage, transportation and application. In addition, based on the result of the dissolution tests, the Ca(OH)2 shell could be readily dissolved in water with a low Ca content or a low ionic strength. After dissolution of the Ca(OH)2 shell, the reactivity of nZVI was found to be at the similar level as bare nZVI, which could remove Cr(VI) from water by more than 90% in about 20 min. The pseudo-first order rate constants for Cr(VI) reduction by bare nZVI and nZVI/ Ca(OH)2 after shell dissolution were 0.064 and 0.072 min-1, respectively. Moreover, the Ca(OH)2 coating shell would not only function as a protection layer but also improve the mobility of nZVI particles in in-situ applications. The aggregation and sedimentation of nZVI/Ca(OH)2 particles became considerably slower compared to bare nZVI without the coating. Clean-bed water filtration tests were conducted with sand and glass columns to evaluate the mobility and transport of nZVI in porous media. The results show that bare nZVI in the particle suspension deposited mostly at the top of the filters with little penetration. In comparison, the nZVI/Ca(OH)2 particles were able to penetrate through the filter media during the filtration process, and the dark iron particles could fill up the entire filter columns. The penetration rate increased from nearly 0 m/hr for bare nZVI to 0.43 m/hr for nZVI/Ca(OH)2 through the filter media. The Ca-based coating materials are known as of low cost and environmentally friendly. Thus, the new coating method developed in this study provides a cost-effective means for both the protection of nZVI and improvement of its transport and delivery in porous media for environmental decontamination. / published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

Multicomponent nonaqueous phase liquids (NAPL) contaminating the subsurface can significantly inhibit remediation. One method of enhancing the rate of remediation of NAPL constituents, compared to pump-and-treat, involves source zone treatment with enhanced solubilization agents (ESAs) including cyclodextrins. Equilibrium cyclodextrin enhanced solubilization of simple 1, 2, and 3 component NAPL mixtures was examined to evaluate the applicability of Raoult's Law. The results suggest that Raoult's Law may be used to estimate equilibrium and early-time dynamic concentrations in contact with ideal NAPL mixtures, and Raoult's Law may be used to estimate cyclodextrin enhanced groundwater concentrations for ideal NAPL mixtures. Solubility enhancement of NAPL compounds was dependent on the cyclodextrin concentration and independent of NAPL composition. Column experiments and numerical modeling were used to evaluate the dissolution behavior of the NAPL mixtures in water and a cyclodextrin solution to estimate mass transfer rates. The aqueous multicomponent dissolution followed Raoult's Law, and the model-estimated lumped rate coefficients were independent of the NAPL composition. Addition of the cyclodextrin enhanced the dissolution and removal of compounds from residual NAPL due to an increase in the driving force (i.e. concentration gradient) and the mass transfer coefficient. The model results suggest that Raoult's Law is applicable for ideal NAPL mixture dissolution in water, but potential nonideality was observed and caused the model simulation to deviate from the dissolution behavior for NAPL mixture cyclodextrin experiments. The cyclodextrin dissolution experiments were less rate-limited than aqueous dissolution, and the mass transfer coefficients were quantified with the model. The results of the model suggest that NAPL mixture nonideality and intra-NAPL diffusion may also impact enhanced dissolution behavior. Additionally, the importance of NAPL mixture characterization was illustrated by evaluation of a mixture of PCE (tetrachloroethene) and diesel fuel collected from a site in Tucson, Arizona. A sample from the site was used to create mixtures with increasing PCE in the NAPL. Chemical evaluation of the complex NAPL was conducted, and physical property and phase partitioning testing was performed, which demonstrated the effect of NAPL composition on its distribution, interphase mass transfer, and potential mobilization.

The analyses of benthonic foraminifera in surface sediments for two-years (Oct. 2007-August 2009) and cores from Halifax Harbour (HH) were essential for short-term monitoring, and reference environment reconstruction for the remediation that started in 2008. The distribution of foraminifera in the surface sediments indicates a lateral environmental variation and positive correlation to the pollution rate in HH as the environmental purity increases seawards. The treated area, Inner Harbour, recorded a rapid environmental recovery during treatment period (2008), and reverted to its former characteristics after treatment stopped (early 2009). This recovery represented by an increase in both diversity (from <12 to >20 species) and abundance (from 120–880 to 1350-1750 individuals). Additionally, the assemblage during that period witnessed a decrease in opportunistic species (<50%), shell deformities (<11%), and inner linings (17%), and a significant increase in calcareous species. The assemblage in pre-impact environment, as inferred from cores, has a high diversity (>30 species) and abundance (>4000 individuals), a dominant calcareous record (>60%), and lower deformities (3-4%). The gradual environmental degradation due to organic enrichment in the harbour caused an increasing foraminiferal decimation to reach dramatic levels with the huge growth of Halifax city since late 1950s. This decimation led to dominance of opportunistic species (e.g., agglutinated forms such as Eggerella advena, and Reophax scottii), abundance of shell deformities, and complete absence of calcareous tests, leaving only their inner linings. Analysis of benthonic foraminifera in two cores from Sydney Harbour (SH) helped to compare contamination types in both areas (domestic in HH vs. industrial in SH). The domestic pollution in HH developed an agglutinated assemblage with low diversity, low abundance, and high ratios of inner linings. In SH the assemblage showed higher diversity (>22 species) and abundance (>4000 individuals), dominant calcareous record (>50%), and low inner linings (<10%) together with some species that had never been observed in such cold waters in Nova Scotia (Ammonia beccarii).

The Redwater Production Area (RPA) is an established oil field located north of Edmonton in central Alberta. Recent assessments indicate that substantial amounts of hydrocarbon contaminated soil exist in the RPA as a result of the use of flare pits, ecological ponds, product spills and pipeline leaks. Alternative remedial technologies may reduce the quantity, cost, and ultimately the long-term liabilities associated with the current practice of landfill disposal. The purpose of this thesis is to assess the viability of accelerated biopile soil treatment as a remedial methodology in the rehabilitation of contaminated soil in the RPA. The thesis includes a literature search, a bench scale treatability and pilot biopile experiment and concludes with a summary of the viability of biopiling to be employed as part of a multi-year/multi-site remedial initiative. Construction of the Redwater Soil Treatment Facility began in 2008 with treatment and recycling operations commencing in early 2009.

Mathematical modelling was utilized to evaluate trichloroethylene (TCE) and tetrachloroethylene (PCE) dense non-aqueous phase liquid (DNAPL) source zone remediation in the subsurface environment. Semi-analytical solutions were derived, tested, and employed to evaluate the benefits of source zone concentration reduction and solute degradation mechanisms on the evolution of plumes in porous media and fractured rock domains. Simulations of treatment in complex DNAPL source zones using different remedial technologies were completed with a numerical model that was developed, tested, calibrated, and applied to nine idealized heterogeneous porous media sites. Analytical modelling revealed that, in domains dominated by matrix diffusion, aggressive and moderate source zone concentration reduction may have similar effects on the leading edge of the plume. The tailing (near source) edge of the plume may be more responsive to aggressive concentration reduction, particularly when diffusion processes are negligible. Both the near-field (near-source) and far-field plume responses were strongly influenced by the matrix decay half-life for both transient and steady-state conditions. The degradative capacity of the matrix largely dictated plume extent and life-span for the fractured bedrock site considered here. Numerical simulations of in situ source zone treatment with chemical oxidation (ISCO), enhanced bioremediation (ISEB), and surfactants (SEAR) were compared and contrasted. Treatment efficacy was site specific, with benefits observed at some sites, and detrimental impacts observed at others. Each technology demonstrated some degree of performance enhancement relative to dissolution only (no treatment). The maximum DNAPL mass depletion enhancement factors for ISCO, ISEB and SEAR, were 1.44, 2.91, and 2.70 after 10 years, respectively. Similarly, the maximum boundary mass flux enhancement factors for ISCO, ISEB and SEAR were 9.78, 3.32, and 3.97, respectively. While notable enhancements were observed for many sites during active treatment, the long-term performance of pre-maturely terminated ISCO and ISEB, and to a lesser degree SEAR, was similar to dissolution. Overall, the partial depletion of DNAPL mass from source zones produced on-going persistent boundary mass flux signatures. Only the complete removal of DNAPL mass, which was attained for one site with SEAR, successfully eliminated downgradient boundary mass flux. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2009-05-21 08:55:04.491

No description available.

A laboratory study was conducted to bioremediate a fine textured soil contaminated with diesel. The local microorganisms were stimulated by supplying nutrients with the aid of a water table management system. A fine textured soil, contaminated for more than 20 years, with more than 6500 mg/kg of diesel was packed in fifteen columns, 2 m long and 0.2 m in diameter. Twelve out of fifteen soil columns were subjected to bioremediaton, by supplying nutrients, water and air at desired depths. Three columns were used as a control to monitor passive degradation of contaminant without intervention. / The experiment was designed to employ three different treatments in triplicates. In the first treatment, nutrients, air and water were supplied. In the second, only nutrients and water were applied and in the third, water alone was applied. These treatments were applied by two different water table management strategies. In the first, three columns were remediated by following a full column remediation strategy, while in the second, nine columns were treated in a stagewise manner, by maintaining the water table at 1 m depth from surface. (Abstract shortened by UMI.)

Chlorinated aliphatic hydrocarbons (CAH’s) are a diverse group of industrial chemicals that play a significant role as pollutants of soil and groundwater. They are recalcitrant and resist degradation in most waste treatment systems. Furthermore, physical removal techniques used for CAHs are often very expensive, labour intensive and time consuming. Microbial communities native to contaminated areas are known to participate in biodegradation of these CAHs to an extent. The main focus of this study was therefore to investigate the bioremediation of soil contaminated with a mixture of CAHs, namely carbon tetrachloride (CCl4), dichloromethane (DCM) and 1, 2 dichloroethane (1, 2-DCA). Two different laboratory-scale microcosm types, a stationary microcosm (Type S) and microcosms that received a continuous circulation of groundwater (Type C) were used to determine the effects of 3 different bioremediation approaches, viz, biostimulation, bioaugmentation and a combination of biostimulation and bioaugmentation on the degradation process. For both microcosm types, gas chromatography analysis revealed that the greatest decreases in CAH concentrations occurred in soil that was biostimulated. 1, 2-DCA was rapidly biodegraded in Type C microcosms that contained glucose, with a 57% net degradation in 15 days. Consortia comprising of aerobic Bacillus and Alcaligenes sp. were used for bioaugmenting contaminated soil. However, this approach did not promote biodegradation as significantly as biostimulation experiments. A combination of biostimulation and bioaugmentation revealed that the addition of nutrients was still unable to induce the degradative ability of the introduced microorganisms to produce degradation values comparable to those of biostimulated soil microcosms. Common intermediates of CAH metabolism viz., chloroform, dichloromethane and carbon dioxide were detected by gas chromatography/mass spectrometry. The detection of chloroform and dichloromethane is sufficient evidence to assume that anaerobic conditions had developed, and that biodegradation was occurring under oxygen-limiting or oxygen-free conditions. An aerobic environment was initially created, but soil microbial respiration had probably led to the rapid development of anaerobic conditions and in all likelihood, enhanced degradation. The prevalence of anaerobic conditions can also account for the lack of appreciable degradation by the bacterial consortium used during bioaugmentation. Phospholipid phosphate analysis was conducted and used as an indicator of microbial biomass. It was noted that phospholipid phosphates did not always correlate with the degradation of CAHs in some microcosms. In this regard, different patterns were noted for Type S and Type C microcosms. Microbial biomass patterns for Type C biostimulated and bioaugmented soil microcosms increased within the first 5 days of sampling. This could have been as a result of the larger volume of groundwater required for the circulating microcosm possibly concealing actual CAH concentrations. In contrast, in Type S microcosms, for most treatments, a sharp decline in biomass within the first week was observed. This study clearly demonstrates that the bioremediation of certain chlorinated solvents can be a function of their water solubility. It must also be emphasized that the biodegradation of some CAHs in a mixture can affect the concentrations of others present in the mixture as well, warranting further study with mixtures of CAHs. Furthermore, the development and use of bioreactors, similar to the Type C microcosm can provide novel, simple ways to hasten remediation of chlorinated solvents like 1, 2-DCA. / Thesis (M.Sc.) - University of KwaZulu-Natal, Durban, 2008.

No description available.

No description available.