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A study was conducted to evaluate the sorption characteristics of six disinfection byproducts (DBPs) on four sorbents. To investigate sorption of volatile organic compounds (VOCs), specially designed experimental batch and continuous flow modules were developed. The investigated compounds included: chloroform, 1,2-dichloroethane (DCE), trichloroethylene (TCE), bromodichloromethane (BDCM), methyl tertiary butyl ether (MTBE), bromate and bromide ions. Sorbents used included light weight aggregate (LWA), an inorganic porous material with unique surface characteristics, Amberlite® XAD-16, a weakly basic anion exchange resin, Amberjet®, a strongly basic anion exchange resin, and granular activated carbon (GAC). Batch experiments were conducted on spiked Milli-Q® and lake water matrices. Results indicate considerable sorption of TCE (68.9%), slight sorption of bromate ions (19%) and no appreciable sorption for the other test compounds on LWA. The sorption of TCE increased to 75.3% in experiments utilizing smaller LWA particle size. LWA could be a viable medium for removal of TCE from contaminated surface or groundwater sites. Amberlite® was found unsuitable for use due to its physical characteristics, and its inability to efficiently remove any of the test compounds. Amberjet® showed an excellent ability to remove the inorganic anions (>99%), and BDCM (96.9%) from aqueous solutions but with considerable elevation of pH. Continuous flow experiments evaluated GAC and Amberjet® with spiked Milli-Q® and tap water matrices. The tested organic compounds were sorbed in the order of their hydrophobicity. Slight elevation of pH was observed during continuous flow experiments, making Amberjet® a viable option for removal of BDCM, bromate and bromide ions from water. The continuous flow experiments showed that GAC is an excellent medium for removal of the tested VOCs and bromate ion. Each of the test compounds showed different breakthrough and saturation points. The unique design of the continuous flow apparatus used in the study proved to be highly beneficial to assess removal of volatile organic compounds from aqueous solutions.

Functionalized silica materials are synthesized for various environmental applications. The overall objective is functionalization with sulfur-containing moieties for mercury sorption and as a platform for nanoparticle synthesis. The first objective is quantifying this functionalization for various silica platforms. The second objective is development of effective mercury sorbents, for both aqueous mercury and elemental mercury vapor. Third, those sorbents are incorporated into mixed matrix membranes (MMM) for aqueous mercury sorption. Fourth, functionalized silica materials are developed as platforms for the synthesis of reactive metal nanoparticles (NP) for the degradation of trichloroethylene. Thiol-functionalized silica is used as a sorbent for aqueous mercury, and a novel functionalized material (thiol-functionalized silica shell surrounding a carbon core) has been developed for this application. Total capacity and kinetics of aqueous mercury sorption were determined. The silica-coated carbon was functionalized with thiol and sulfonate moieties for regeneration under mild conditions. Finally, the sorbent particles were incorporated into polysulfone to form a mixed matrix membrane (MMM) for toxic metal capture under convective-flow conditions. High loadings (up to 50% particles, base particles of ~80 nm) were achieved in the MMM. The particles are well-dispersed which can lower mass transfer resistance to the sorption sites. The MMM also imparts several practical advantages such as ease of sorbent handling. Silica functionalized with tetrasulfide silane is used for mercury vapor sorption. Sorption kinetics and dynamic capacity depend upon pore structures of the functionalized material. The particles are thermally stable and exhibit a glass transition in the tetrasulfide silane coating, with high total sorption capacity achieved by addition of copper sulfate. Temperature effects on mercury sorption indicate a chemisorptive mechanism. Silica particles functionalized with sulfonate moieties were used as a platform for the synthesis of dispersed iron nanoparticles. These NP are applied for degradation of trichloroethylene (TCE), a persistent, toxic, and widespread pollutant. The particles were stabilized against agglomeration. Natural product reducing agents, such as ascorbic acid, adsorb to the particle surface and can protect against oxidation. These particles were demonstrated for the reductive as well as oxidative degradation of TCE.

"Trichloroethylene (TCE) is the most commonly found groundwater pollutant. The focus of this research was to determine the effectiveness of chemical oxidation for in-situ remediation of TCE contaminated aquifers. Analytical techniques were developed to measure the concentration of TCE and its degradation products in soil and in solution. Slurry tests were conducted to emulate in situ conditions. Various media used for the slurry tests included sand, silica and glass beads. In-situ chemical oxidation of the TCE was performed using sodium persulfate (Na2S2O8), Fenton’s reagent, Ozone and sodium persulfate activated by iron, ozone and zero valent iron. Persulfate oxidation was shown to be effective for TCE oxidation in the presence of all the media tested in slurry tests for various molar ratios of oxidant and catalyst (Fe). Approximately 75% of TCE destruction takes place in the first 5 minutes of the slurry test and 90% destruction within 24 hours. Fenton’s oxidation was tried with varying concentration of H2O2 and slurry volume. Percent removal of TCE decreased from a hydrogen peroxide concentration of 3.34% to 5% (w/v). It was found that persulfate oxidation activated by zero valent iron removed TCE more effectively than persulfate oxidation activated by ferrous iron. For persulfate oxidation activated by ozone it was found that 95% of TCE was destroyed at persulfate/TCE molar concentration of 10/1 with an initial rate constant of 0.2854/min. It was also found that increasing the amount of solids in the slurry test decreased the effectiveness of chemical oxidation. "

For this study, we revisited whether the common iron Fe mineral, magnetite Fe3O4 (s), can reduce tetrachloroethylene (PCE) and trichloroethylene (TCE) as discrepancies exist in the literature regarding rates and extent of reduction. We measured PCE and TCE reduction in batch reactors as a function of magnetite stoichiometry (x = Fe2+/Fe3+ ratio), solids loading, pH, and Fe(II) concentration. Our results show that magnetite reacts only slowly with TCE (t1/2 = 7.6 years) and is not reactive with PCE over 150 days. The addition of aqueous Fe(II) to magnetite suspensions, however, results in slow, but measurable PCE and TCE reduction under some conditions. The solubility of ferrous hydroxide, Fe(OH)2(s), appears to play an important role in whether magnetite reduces PCE and TCE. In addition, we found that Fe(OH)2(s) reduces PCE and TCE at high Fe(II) concentrations as well. At certain conditions degradation of the PCE and TCE is enhanced by an unexplored synergistic response from magnetite and ferrous hydroxide iron phases. Our work suggests that measuring dissolved Fe(II) concentration and pH may be used as indicators to predict whether PCE and TCE will be abiotically degraded by groundwater aquifer solids containing magnetite.

Recently, there has been growing interest in using transition metals (TM) for catalytic and electromagnetic applications, due to the ability of TMs to form stable compounds in multiple oxidation states. In this research, the focus has been on the synthesis and characterization of carbon-supported TM nanoparticles (NPs), specifically palladium (Pd) and gold (Au) NPs, for catalytic applications, and transition metal oxides (TMO) NPs, specifically Fe3O4 NPs for electromagnetic applications. Carbon supports have several advantages, such as enabling even distribution of particles, offering large specific surface area with excellent electron conductivity, and relative chemical inertness. In this dissertation, for catalytic applications, emphasis was on removal of trichloroethylene (TCE) from groundwater. For this application, carbon-supported Pd/Au NP catalysts were developed. Pd was chosen because it is more active, stable and selective for desired end-products, and Au has shown to be a good promotor of Pd's catalytic activity. Often, commercially available Pd-based catalysts are made using harsh chemicals, which can be harmful to the environment. Here, an environmentally friendly process with aspects of green chemistry was developed to produce carbon-supported Pd/Au NP catalysts. This process uses a combination of sonochemistry and solvothermal syntheses. The carefully designed carbon-supported Pd/Au NP catalyst material was systematically characterized, tested against TCE, and optimized for increased rate of removal of TCE. Electron microscopy and spectroscopy techniques were used to study the material including structure, configuration and oxidative state. The Pd/Au NPs were found mainly to form clusters with an aggregate-PdShellAuCore structure. Using state-of-the-art direct detection with electron energy loss spectroscopy, the Pd NPs were found to have an oxidative state of zero (0). The formation of the catalyst material was studied in detail by varying several synthesis parameters including type of solvent, sonication time, synthesis temperature etc. The most optimized catalyst was found remove TCE at double the rate of corresponding commercial Pd-based catalysts in a hydrogen headspace. This material was found to catalyze the removal of TCE via traditional hydrodehalogenation and shows promise for the removal of other contaminants such as trichloropropane (TCP), carbon tetrachloride (CT). This green approach to make and optimize TM materials for specific applications was extended to TMOs, specifically magnetite (Fe3O4) and further developed for the application of electromagnetism. As catalysts, Fe3O4 is used for removal of p-nitrophenol from water. However, since the carbon-supported Pd/Au material system was developed and optimized for catalysis, here, carbon-supported Fe3O4 NPs were developed for electromagnetic applications. There has been growing interest in tuning the magnetic properties of materials at room temperature with the use of external electric fields, for long-term applications in data storage and spintronic devices. While a complete reversible change of material properties has not yet been achieved, some success in partial switching has been achieved using multiferroic spinel structures such as Fe3O4. These materials experience a change in magnetic moment at room temperature when exposed to the electric fields generated by electrochemical cells such as lithium ion batteries (LIBs) and supercapacitors (SC). In the past, a 1% reversible change was observed in Fe3O4 using LIBs. Here, building on the developments from previous material system, Fe3O4 NPs were directly hybridized onto the graphene support in order to increase the observable change in magnetic moment. The material was systematically designed and tested for this application, including a study of the material formation. A simple, environmentally friendly synthesis using the solvothermal process was implemented to make the graphene-supported Fe3O4 NPs. This new material was found to produce a reversible change of up to 18% in a LIB. In order to overcome some of the difficulties of testing with a LIB, a corresponding hybrid SC was designed, built and calibrated. The graphene-supported Fe3O4 NPs were found to produce a net 2% reversibility in the SC, which has not been reported before. The results from both the LIB and SC were analyzed to better understand the mechanism of switching in a spinel ferrite such as Fe3O4, which can help optimize the material for future applications. The focus of this dissertation was on the development of a methodology for carbon-supported TM and TMO NPs for specific applications. It is envisioned that this approach and strategy will contribute towards the future optimization of similar material systems for a multitude of applications.

This research is focused on engineering submicron spherical carbon particles as effective carriers/supports for nanoscale zerovalent iron (NZVI) particles to address the in situ remediation of soil and groundwater chlorinated contaminants. Chlorinated hydrocarbons such as trichloroethylene (TCE) and tetrachloroethylene (PCE) form a class of dense non-aqueous phase liquid (DNAPL) toxic contaminants in soil and groundwater. The in situ injection of NZVI particles to reduce DNAPLs is a potentially simple, cost-effective, and environmentally benign technology that has become a preferred method in the remediation of these compounds. However, unsupported NZVI particles exhibit ferromagnetism leading to particle aggregation and loss in mobility through the subsurface. This work demonstrates two approaches to prepare carbon supported NZVI (iron-carbon composites) particles. The objective is to establish these iron-carbon composites as extremely useful materials for the environmental remediation of chlorinated hydrocarbons and suitable materials for the in situ injection technology. This research also demonstrates that it is possible to vary the placement of iron nanoparticles either on the external surface or within the interior of carbon microspheres using a one-step aerosol-based process. The simple process of modifying iron placement has significant potential applications in heterogeneous catalysis as both the iron and carbon are widely used catalysts and catalyst supports. Furthermore, the aerosol-based process is applied to prepare new class of supported catalytic materials such as carbon-supported palladium nanoparticles for ex situ remediation of contaminated water. The iron-carbon composites developed in this research have multiple functionalities (a) they are reactive and function effectively in reductive dehalogenation (b) they are highly adsorptive thereby bringing the chlorinated compound to the proximity of the reactive sites and also serving as adsorption materials for decontamination (c) they are of the optimal size for transport through sediments (d) they have amphiphilic chemical functionalities that help stabilize them when they reach the DNAPL target zones. Finally, the iron-carbon composite microspheres prepared through aerosol-based process can used for in situ injection technology as the process is conductive to scale-up and the materials are environmentally benign. / acase@tulane.edu

Laboratory and modeling studies were performed with a mixed-anaerobic-culture obtained from the Evanite site in Corvallis, Oregon. The culture completely transforms trichloroethene (TCE) to cis-dichloroethene (c-DCE), vinyl chloride (VC), and finally to ethene. Acetylene inhibition studies were used to examine the culture's microbial activities. Kinetic studies determined the half-saturated constant (K[subscript s]), the maximum utilization rate (k[subscript max]X), and inhibition constants (K[subscript I]). The kinetic constants were used to model the results of inhibition studies using competitive and uncompetitive inhibition models. Acetylene was found to function as a reversible inhibitor and was used to probe the activities of reductive dechlorination. Various acetylene concentrations were used to differentiate microbial processes, including methanogenesis, acetogenesis, and halorespiration. Acetylene concentrations of 48, 192, and 12 ��M, respectively, were required to achieve 90% inhibition in the rates of methanogenesis, TCE and VC transformation. H���-dependent acetate production was not inhibited by acetylene. K[subscript s] values for TCE and VC were 12 ��M and 63 ��M, respectively. Model fitting of acetylene inhibition constants (K[subscript IC]) for TCE and VC transformations yielded the same value (0.4 ��M) for a competitive inhibition model. However, for uncompetitive inhibition the estimated K[subscript IU] for TCE to c-DCE, TCE to 1,1-DCE and VC to ethene were 13.3, 14.1 and 2.2 ��M, respectively. Competitive and uncompetitive inhibition models simulated experimental data equally well for results obtained at high TCE and VC concentrations. The models were further verified to fit transient data of acetylene inhibition at lower TCE and VC concentrations, and competitive inhibition resulted in a better fit to the experimental data. 1-chloro-1-fluoroethene (1,1-CFE) was found to track the rate of VC transformation well, since VC and 1,1-CFE had similar maximum transformation rates and K[subscript s] values. A competitive inhibition model with the measured K[subscript s] values, 63 and 87 ��M. was used to predict the rates of VC and 1,1-CFE transformation, respectively. The similar rates and results of acetylene and compound inhibition studies indicated VC and 1,1-CFE were transformed by the same enzyme. 1,1-CFE transformation by three different cultures, clearly demonstrate that 1,1-CFE was an excellent surrogate to track rates of VC transformation. / Graduation date: 2004

Isotopic methods have been developed over the last 10 years as a method for determining chemical interactions of chlorinated solvents. These methods are especially promising for. This study attempts to employ and develop compound specific isotopic analyses of TCE and cDCE, along with chemical data, to characterize the degradation of TCE in a fractured bedrock aquifers. The Smithville site is a contaminated field site with extremely high levels of TCE contamination that is currently undergoing monitored remediation. From December 2008 until April 2010 extended samples were collected from the site to provide additional data analyses including isotopic data. The redox conditions at the site are anoxic to reducing, with sulfate reduction and methanogenesis as dominant terminal electron accepting processes. Redox data indicates that well electrochemical conditions are highly variable within the site, including areas near the source zone that not very reducing. Documented changes in groundwater conditions to much more reducing environments indicate that oxidation of organic matter is occurring at the Smithville site in select wells. Chemical analyses of TCE, DCE, VC, ethene and ethane are employed determine whether reductive dechlorination was occurring at the site. Results of field testing indicate that many wells on site, especially in the proximity of the source zone, dechlorination products were found. The isotopic data had a high range in both carbon and chlorine isotopes. Chlorine isotopic data ranges from a δ37Cl(TCE) of 1.39 to 4.69, a δ37Cl(cDCE) of 3.57 to 13.86, a δ13C(TCE) of -28.9 to -20.7, and a δ13C(cDCE) of -26.5 to -11.82. The range in values indicate varying degrees of degradation throughout the site, with the same wells grouping together. Combined chemical, redox and isotopic data shows that degradation seems to be a removal process for TCE at the Smithville site. Concentrations of chemicals created as a result of TCE degradation verify degradation, especially in wells 15S9, R7 and 17S9. Historically production of DCE in significant amounts, above 1.0 ppb, was observed to only occur after 2003. In addition to this, DCE data shows that the percentage of DCE made up of cDCE is above 96%. This indicates that microbes most likely mediate the processes that formed DCE from TCE. The linear regression of the delta-delta plot for isotopic TCE data shows line that is likely a direct function of the carbon and chlorine isotopic fractionation imparted upon the original TCE released. The slope found is consistent with data collected from other studies though cannot be applied to determining the process directly given the range of variability in isotopic field data.

Soil and groundwater at many existing and former industrial areas and disposal sites is contaminated by halogenated organic compounds that were released into the environment. Halogenated organic compounds are heavier than water. When they are released into the subsurface, they tend to adsorb onto the soils and cause the appearance of DNAPL (dense-non-aqueous phase liquid) pool. Among those halogenated organic compounds, trichloroethylene (TCE), a human carcinogen, is one of the commonly observed contaminants in groundwater. Thus, TCE was used as the target compound in this study. The objective of this study was to develop the emulsified carbon-releasing substrate and apply it as the filling material in the permeable reactive barrier to remediate TCE-contaminated groundwater. In this study, the developed emulsified carbon-releasing substrate contained soybean oil, lactate, biodegradable surfactant (Simple GreenTM and lecithin), and nutrients. Results of emulsion test show that up to 90% of the emulsified carbon-releasing substrate was distributed effectively in the soil pores. The emulsified carbon-releasing substrate was able to provide carbon for the enhancement of in situ anaerobic biodegradation for a long period of time. A pilot-scale study was operated at a TCE-contaminated site located in southern Taiwan. Emulsified carbon-releasing substrate emulsion was pressure-injected into the remediation wells. A total of 120 L of emulsified carbon-releasing substrate was injected into the test site. Based on the groundwater analytical results, dissolved oxygen, oxidation-reduction potential, and sulfate concentrations decreased after injection. However, the anaerobic degradation byproduct, acetic acid, increased after injection. Results also show that the total viable bacteria increased in the upgradient injection (remediation) well. Decrease in TCE concentration (dropped to below 0.01 mg/L) was also observed after substrate injection, and TCE degradation byproducts, cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) were also observed. Result of microbial analyses show that various TCE-degrading bacteria exist in the groundwater samples including Ralstonia sp., Clostridium sp., Uncultured Burkholderiales bacterium, Hydrogenophaga sp., Acidovorax sp., Zoogloea sp., Hydrocarboniphaga sp., Uncultured Curvibacter sp., Pseudomonas sp., Comamonas sp., Aquabacterium sp., and Variovorax strains. This reveals that the anaerobic dechlorination of TCE is a feasible technology at this site. Slug test result show that only a slight variation in soil permeability of the injection well was observed. This indicates that the substrate injection would not cause clogging of the soil pores. Results from the cost analysis show that the total cost for the test site remediation was approximately USD13,442 per year. This indicates that the developed system has the potential to be developed into an environmentally, economically, and naturally acceptable remedial technology. Knowledge obtained from this study will aid in designing a carbon-released substrate biobarrier system for site remediation.