ABSTRACT The purpose of this research was to investigate the modified photocatalyst(TiO2) from the heterogeneous photocatalysis of perchloroethylene(PCE) products distribution by different operating conditions using near UV/TiO2 hope that could enhance the PCE¡¦s conversion and mineralization rate and explore the reaction pathways.The modified photocatalyst of this research was completed with Ag/TiO2¡BAu/TiO2¡BPt/TiO2¡BWO3/TiO2 and AC/TiO2. The added species except activied carbon was 10 % weight of photocatalyst(TiO2) others the noble metal (sillver¡Bgold and platinum) and tungsten oxide(WO3) were 0.5 % weight of TiO2. Then the experiments were conducted by varying relative humidity(R.H.=0~60 %), oxygen concentration(0~21 %), and retention time(0.38~0.89 sec). Glass beds coated with modified Degussa P-25 anatase TiO2 were filled in a Pyrex glass reactor. TiO2 was illuminated by four 10 watts ultraviolet(UV) lamps. Results from QA/QC experiments indicated that PCE could not be photodegradated by near UV of wavelength 365 nm. However, It can be decomposed quickly through heterogeneous photocatalysis. And it also find that no modified photocatalyst would be envenomed in photoactivied continuance test. The best PCE conversion and mineralization rate of modified photocatalyst were WO3/TiO2 and AC/TiO2. The modified photocatalyst Ag/TiO2 were the same as TiO2 but Au/TiO2 and Pt/TiO2 were worse to TiO2. The highest converstion rate of PCE could top to 99.5 %¡F The experiment showed that PCE was decomposed as oxygen concentration and retention time increased. But a higher concentration of oxygen was not efficient on the increase of PCE conversion. The conversion ratio of PCE could be inhibited at higher relative humidities. The end products observed from UV/TiO2 heterogeneous photocatalytic reactions included CHCl3, CCl4, C2HCl5, C2Cl6, COCl2, CCl3CClO, Cl2, HCl, CO, and CO2. The major chlorinated compound was Cl2 when the photocatalytic reactions proceed at higher oxygen concentration and less humid conditions. As water vapor existed, the major chlorinated compound became HCl. The major product was CO2 during the entire experimental process of heterogeneous photocatalytic reactions.

Tetrachloroethylene (PCE) is a contaminant that has been frequently detected in ground water, surface water, air and soil. Advanced reduction processes (ARP) make up a set of wastewater treatment technologies that have been proposed recently. This project has conducted research on degrading PCE with an ARP that combines dithionite and ultraviolet activation. The purpose of the project is to provide knowledge for the development of potential wastewater treatment technologies. Several control experiments (blank control, reagent control and UV control) were conducted to prove the feasibility of applying the dithionite/UV ARP to degrade PCE. ARP degradation of PCE was studied under different pH (5, 7, 8, 9) and light intensities (2, 4, 7.3 mW/cm2). The results showed that the fastest degradation was observed at pH 7 and that degradation becomes faster at higher light intensities. Combining dithionite and UV light resulted in a faster degradation of PCE than only using UV light to photolyze PCE.

A laboratory study was conducted to assess the relationship between degree of volatile organic compound (VOC) mass removal from soil and heating duration, initial dense non-aqueous phase liquid (DNAPL) saturation, and grain size. The relationship between post-remedy sampling temperature and VOC soil concentration was examined. Soil contained in glass jars was spiked with DNAPL phase tetrachloroethylene (PCE), saturated, and placed in an oven for a specified period of time. The soil temperature at the centre of each jar was monitored during heating. Upon removal from the oven, each jar was immediately capped with an air tight seal and placed into an ice bath until the soil temperature had cooled to the desired sampling temperature. The jar caps were subsequently removed and the soil was sampled using a coring tool and immersed into pre-weighed vials containing methanol. PCE in soil samples was quantified using purge-and-trap with gas chromatography/mass spectrometry. Soil temperature increased steadily from ambient until reaching a plateau at 89 ºC ± 4 ºC due to co-boiling of DNAPL phase PCE and water. A linear relationship was found between the length of the co-boiling plateau and the initial PCE saturation. Co-boiling continued until DNAPL phase PCE had been depleted, at which time the soil temperature increased to the boiling point of water and remained constant while remaining pore water was removed. PCE soil concentrations decreased rapidly in the early stages of heating, but leveled off between 9.0 and 19 ppb soon after the soil became dried out. Analysis of the sensitivity to initial PCE saturation data revealed that the concentration of PCE in post-remedy samples increased with increasing initial saturation. Results of the sensitivity to grain size tests showed a decreasing trend between PCE soil concentration and decreasing sand grain size while temperature at sampling was not found to affect the amount of PCE quantified post-thermal remedy. Soil temperature at the centre of each jar during cooling was measured and an analytical solution was fit to the recorded data. From this data, the thermal diffusivity of the soil was approximated and was found to range from 1.4 x 10-7 to 1.8 x 10-7 m2/s. / Thesis (Master, Civil Engineering) -- Queen's University, 2007-12-11 10:12:50.564

Fenton-dependent recovery of carbon initially saturated with one of several chlorinated aliphatic contaminants was studied in batch and continuous-flow reactors. A specialty carbon, URV-MOD 1 (Calgon) was employed to minimize non-productive H2O2 demand - that which does not yield hydroxyl or superoxide radicals.Enhancement of PCE degradation kinetics by ferric iron addition is limited by iron solubility, even at relatively low pH. Quinone addition increased the pseudo-first-order rate constant for PCE loss temporarily. Only copper addition sustainably enhanced the specific rate of PCE loss. For copper-to-iron molar ratios of 0.25 to 5, the pseudo-first-order rate constant for PCE transformation was increased by a factor of 3.5. It is apparent that the effect of copper addition on Fenton-dependent reaction rates is complex, and involves a shift in chemical mechanism, as indicated by the differing slopes in the Arrhenius plot (with and without copper).A mathematical model was developed to evaluate the effect of operational parameters ([Fe(III)]T:[H2O2]o ratio and pH) on degradation kinetics and optimize the PCE degradation process in homogeneous reaction mixtures. The model simulated experimental degradation of the organic target in a homogeneous Fenton-reaction system. The model requires further refinement to simulate Fenton's systems in which ions in solution (such as sulfate and chloride) play significant roles.In continuous-flow reactors, Fenton's reagents were cycled through spent GAC in columns to degrade one of seven chlorinated compounds tested. The contaminant with the weakest adsorption characteristics, methylene chloride, was 99% lost from the carbon surface during a 14-hour regeneration period. At the field site, the GAC was saturated with gases containing TCE and PCE from a soil vapor extraction (SVE) system. In the field, up to 95% of the sorbed TCE was removed from GAC during regeneration periods of 50-60 hours. Recovery of PCE-loaded GAC was significantly slower. Column experiments show that there is minimal loss of carbon adsorption capacity during Fenton treatment and that the rate of GAC regeneration is compound specific. Scoping-level cost estimates indicated that field use of Fenton regeneration is not cost effective without optimization and/or iron surface amendments, except in the case of the most soluble VOCs.

"A one dimensional, multiple reaction pathway model of the dechlorination reactions of trichloroethylene (TCE) and tetrachloroethylene (PCE) as these species pass through a zero valent iron permeable reactive barrier (PRB) was produced. Three different types of rate equations were tested; first order, surface controlled with interspecies competition, and surface controlled with inter and intra species competition. The first order rate equations predicted the most accurate results when compared to actual data from permeable reactive barriers. Sensitivity analysis shows that the most important variable in determining TCE concentration in the barrier is the first order rate constant for the degradation of TCE. The velocity of the water through the barrier is the second most important variable determining TCE concentration. For PCE the concentration in the barrier is most sensitive to the velocity of the water and to the first order degradation rate constant for the PCE to dichloroacetylene reaction. Overall, zero valent iron barriers are more effective for the treatment of TCE than PCE. "

Groundwater parameter analysis, microcosm experiments, and microcosms modeling were undertaken to assess the potential of Monitored Natural Attenuation as a remediation strategy at Site 12 at the Naval Amphibious Base (NAB) Little Creek. Site 12 was contaminated with PCE waste disposed by a former dry cleaning facility. In the groundwater analysis, contaminant characteristics and redox indicators were evaluated to assess the reductive dechlorination potential of Site 12. The results of the groundwater analysis indicated that Site 12 exhibited sulfate-reducing and methanogenic conditions which provide the required environment for reductive dechlorination. However, Site 12 only demonstrated partial reductive dechlorination to cis-1,2-DCE and possible anaerobic oxidation of cis-1,2-DCE and VC to CO₂. Microcosms were designed to further evaluate the extent of microbial degradation of the chlorinated ethenes at Site 12 and to provide concentration versus time data for the estimation of chlorinated ethenes' biodegradation rates. The extent of degradation in the microcosms was consistent with the groundwater data. However, ethene production was not observed and the quantity of TCE measured for two of the microcosms differed substantially when compared to the groundwater data. The microcosm model used SEAM3D to simulate the results of the microcosm experiments (concentration versus time data) to estimate the biodegradation rates of PCE and its daughter products. The SEAM3D reductive dechlorination package, based on Monod kinetics, predicted for the MLS12-Shallow microcosm maximum specific utilization rates for PCE, TCE, cis-1,2-DCE and VC at 0.4, 0.42, 0.05, and 0.25 day⁻¹, respectively and half saturation coefficients for PCE, TCE, cis-1,2-DCE and VC at 0.41, 0.01, 0.07, and 0.02 mg/L, respectively. The results of this study suggest that while the groundwater environment provides the necessary conditions for reductive dechlorination, Site 12 is not an efficient system for reductive dechlorination. This lack of efficiency may stem from sparse microbial populations capable of reducing cis-1,2-DCE or the system may contain levels of PCE which inhibit the further reduction of cis-1,2-DCE. Based on the observed inhibitory relationship between PCE and cis-1,2-DCE and VC production, source removal would reduce the PCE levels and encourage further reductive dechlorination at Site 12. Therefore, the recommended first step for a monitered natural attenuation-based remediation strategy at Site 12 should be source removal. / Master of Science

Chlorinated solvents are among the most prevalent contaminants at Superfund sites. Perchloroethylene (PCE) and its degradative byproducts pose a particular problem because of their persistence in the subsurface and their threat to ecological health. In this study, microcosms were used to test the viability of bioaugmentation as a possible remediation strategy at a PCE contaminated site at the Naval Amphibious Base at Little Creek located in Virginia Beach, Virginia. All microcosms were created in duplicate using spatially diverse soils and the bioaugmented series innoculated with a mixed microbial culture provided by the Dr. Frank Loffler. This culture has been found to be capable of completely degrading PCE to ethene. The aqueous ethene concentration was monitored over time. It is clear from the results that bioaugmentation successfully increased the degree of reductive dechlorination over their static counterpart. Without innoculation, shallow static microcosms showed an accumulation of cis-DCE, while deep soils never showed conversion beyond TCE. Shallow bioaugmented microcosms showed the production and loss of vinyl chloride indicated probable complete conversion of PCE to ethene while deep soils showed the production of cis-DCE. These differences in dechlorination between shallow and deep soils indicate a possible disparity in reduction capacity. At day 78, microcosms were spiked with higher concentrations of PCE resulting in a reduction in dechlorination activity. Static microcosms exhibited similar degradative trends but bioaugmented batches experienced dramatic reductions in dechlorination activity indicating possible inhibition effects of native organisms due to concentration or potential toxic shock. It appears that bioaugmentation is a remediation alternative worthy of further study including possible delivery methods, toxicity or inhibition effects of concentration, and fate/transport studies. / Master of Science

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Abstract The industrial solvents tetrachloroethylene (PCE) and trichloroethylene (TCE) are among the most ubiquitous chlorinated compounds found in groundwater contamination. One potential method for managing PCE/TCE contaminated sites is the intrinsic bioremediation. Recent regulations adopted by U.S. Environmental Protection Agency allow intrinsic bioremediation to be considered as an alternative during development of corrective action plans. In some remediation cases, enhanced bioremediation are performed to accelerate the contaminant biodegradation rate. The main objective of this study was to evaluate the potential of using intrinsic and enhanced bioremediation technologies to clean up PCE/TCE contaminated aquifers. PCE/TCE bioavailability was evaluated by laboratory microcosms under four reduction/oxidation (redox) conditions including aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Acclimated bacteria, activated sludge, and aquifer sediments from a pentachlorophenol contaminated site were used as the inocula in this study. Methane, toluene, phenol, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in the cometabolism and reductive dechlorination microcosms. Results from this study show that PCE and TCE can be significantly biodegraded under reductive dechlorination and aerobic cometabolism conditions, respectively. All five carbon sources evaluated in this study can be applied as the primary substrates by microbial consortia to enhance the aerobic cometabolism of TCE. The highest TCE degradation rate [Up to 100% of TCE removal (with an initial concentration of 3.6µM)] was observed in the microcosms with toluene enrichment bacteria as the microbial inocula and toluene as the primary substrate. Under reductive dechlorination conditions, both sludge cake and cane molasses could be used as the primary substrates by microbial consortia (from activated sludge and aquifer sediments) and enhanced the biodegradation of PCE. The highest PCE degradation rate [Up to 100% of PCE removal (with an initial concentration of 17µM)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cake as the primary substrate. Except for reductive dechlorination microcosms, no significant PCE removal was observed in the microcosms prepared under iron reduction conditions. Results from this feasibility study would be useful in designing a scale-up in situ (e.g., in situ biobarrier system) or on-site bioremediation system (e.g., bioslurry reactor) for field application. Moreover, the application of non-toxic organic waste to enhance PCE/TCE biodegradation has the potential to become an environmentally and economically acceptable technology for the bioremediation of chlorinated-solvent contaminated groundwater.

This dissertation contains the results of two different projects. The first one is a study of the transport of protozoa pathogens Cryptosporidium parvum and Encephalitozoon intestinalis in soils. The aim of this project was to investigate the movement and retention mechanisms of these microorganisms in natural porous media. The work determined that in the case of C. parvum, the retention was primarily produced by straining and in the case of E. intestinalis the main retention mechanism was attachment. The results of C. parvum lysimeter experiment compared to the results from the 7 cm column experiments suggest that retention is proportional to the length of the column. The second study evaluated the Polymerase Chain Reaction (PCR) as a tool to identify dechlorinating bacteria in groundwater contaminated with chloroethenes. The target DNA regions to identify these microorganism were the 16s rDNA specific for dehalococcoides sp. and Desulfuromonas and DNA sequences coding for the reductive dehalogenase enzymes pceA, tceA, bvcA and vcrA. Bacteria able to transform PCE into DCE were detected in all groundwater samples. Bacteria able to transform VC into ethene were found only in one of the samples. This study shows that PCR analysis of 16s rDNA and reductive dehalogenase gene sequences together with microcosm results are useful tools to analyze the populations of reductive dechlorinators and their activity in a given site.