Many nitroaromatic compounds (NACs) are considered toxic and potential carcinogens. The purpose of this study was to develop an integrated reductive/oxidative process for treating NAC contaminated waters. The process consists of the combination of zero-valent manganese or iron and a hydroxyl radical based treatment technique. Corrosion promoters were added to the contaminated water to minimize passivation of the metallic species. Water contaminated with 2,4-dinitrotoluen (DNT) was treated with the integrated process using a recirculating batch reactor. It was demonstrated that addition of corrosion promoters to the contaminated water enhanced the rate of reaction of 2,4-DNT with zero-valent iron or manganese. Results showed that iron provided greater reduction of 2,4-DNT than manganese. Chemical oxidation was used to mineralize the reduction products. The degree of mineralization was measured analyzing the samples for total organic carbon and nitrates. A proposed reaction and corrosion mechanisms and rate expressions were developed during the course of the study.

For centuries chemists have sought to improve humankind’s quality of life and address many of society’s most pressing needs through the development of chemical processes and synthesis of new compounds, often with phenomenal results. Unfortunately, there also are many examples where these chemicals have had unintended, detrimental consequences that are not apparent until years or decades after their initial use. There are numerous halogenated molecules in this category that are globally dispersed, resistant to natural degradation processes, bioaccumulative, and toxic to living organisms. Chemicals such as these are classified as persistent organic pollutants (POPs), and due to their negative environmental and health effects, they require safe, effective, and inexpensive means of remediation. This research focuses on the development and optimization of a reaction matrix capable of reductively dehalogenating several POPs. Initial experiments determined that powdered magnesium and 1% V/V acetic acid in absolute ethanol was the most effective system for degrading polychlorinated biphenyl (PCB), an extraordinarily recalcitrant environmental contaminant. Further studies showed that this matrix also was capable of degrading polychlorinated dibenzo-p-dioxins (PCDDs), polybrominated diphenyl ethers (PBDEs), and four organochlorine pesticides (OCPs); dieldrin, heptachlor, heptachlor epoxide, and chlordane. During this phase of testing, field samples contaminated with chlordane were washed with ethanol and this ethanol/chlordane solution was degraded using the same reaction matrix, thereby demonstrating this technology’s potential for “real-world” remediation projects. Finally, a set of experiments designed to provide some insight into the mechanism of dechlorination seems to indicate that two distinct processes are necessary for degradation to occur. First, the passivated iv outer layer of the magnesium must be removed in order to expose the zero-valent magnesium core. Next, an electron is transferred from the magnesium to the target molecule, causing the cleavage of the halide bond and the subsequent abstraction of either a hydrogen or proton from a solvent molecule. It is anticipated that an understanding of these fundamental chemical processes will allow this system to be tailored to a wide range of complex environmental media

Heavy metal contamination of soils, sediments and groundwater presents an ongoing source of hazardous and persistent environmental pollution. How best to remediate these contaminants is the impetus of continuing research efforts. Methods include containment, ex situ and in situ techniques. A successful in situ method utilizing a combination of emulsified liquid membranes, ELM, and zero-valent metal, ZVM, and bimetals has demonstrated impressive heavy metal reduction in 100 ppm solutions of Cd, Cu, Ni, Pb, Cr and U. This promising in situ method has been employed by the Industrial Chemistry Laboratory at the University of Central Florida and it has demonstrated considerable success in treating several environmental threats. Contaminated soils, surfaces, sediments and groundwater with offending agents such as trichloroethene, polychorobiphenyls and heavy metals have been treated utilizing emulsified liquid membrane systems containing zero-valent iron or bimetal particles. In vial studies, lead spiked sediments have shown repeatable 60% removal of lead after seven days of treatment. A persistent pattern emerged at ten days whereupon remediation levels began to drop. The current study was established to determine the reason for the decline at ten days and beyond. Questions addressed: Does the formation of an impeding oxide layer diminish the remediation capacity of the iron/magnesium system? Does the emulsion reach a maximum capacity to withdraw the contaminant? Do the soil components or the soil structure interfere with the access to the contaminant? This study has yielded insight into the reasons emulsified liquid membrane systems containing zero-valent metals achieved maximum lead removal at day seven, and thereafter begin to lose their effectiveness. A three part study was implemented to address and to answer the three questions pertaining to the consistent pattern of diminishing remediation levels exhibited at day ten and beyond. Initially, from Study I results it appeared that the formation of an impeding oxide layer on the bi-metal which was inside the emulsion droplet and which plated or precipitated with the lead was not occurring at day ten. Results indicated that the iron/magnesium was still capable of removing lead. Furthermore, from Study II results the emulsion dose injected appeared adequate to remove the lead, meaning that the emulsion had not reached its maximum capacity for remediation. The emulsion dose was not a limiting factor. Lastly, Study III results seemed to indicate that the drop in remediation after day seven pertained to the soil structure. There appeared to be some merit to the idea that with aging of the sediment, the lead was diffusing and migrating to some inaccessible interior sites within the sediment particles. Additionally, indications from day ten and day fourteen delineated that a second emulsion dose injection might restore lead removal levels to approach those first observed at day seven and consequently be a useful field application. In order to explore the effectiveness of injecting a second dose of emulsion, another vial study was implemented. The typical pattern of observing sixty percent maximum lead removal at day seven was observed. In separate groups, a second injection of emulsion was added at day five, and then for another vial series, a second dose was added at day seven. The second emulsion dose treatment for either day five or day seven did not yield any increases in percent lead removal. Another theory emerged after viewing micrographs of recovered iron/magnesium compared with fresh ball-milled bimetal. In addition, scanning electron microscopy appeared to confirm the explanation that the emulsified zero-valent metal system might be compromised after day seven. This would lead to exposure of the iron/magnesium to the air and the elements. Corrosion of the bimetal might be occurring. With time, release of the plated or precipitated lead back into the sediment mixture could follow. The results of Study I had led to the conclusion that an impeding oxide layer had not formed; however, this conclusion may have been premature because the recovered iron/magnesium was exposed to lead solution in the vial study. Perhaps if the recovered iron/magnesium was inserted back into an emulsion and injected into lead spiked sediments the percent lead removed might give a more accurate picture of the iron/magnesium's capability to continue performing remediation. Remediation of sediments contaminated with lead is a complicated task because of the complex nature of sediment components. Emulsified liquid membranes utilizing zero-valent bimetals has repeatedly demonstrated impressive results at day seven; however, this treatment method is not without its limitations. Optimal results appear to be gained at day seven after emulsion injection. The bimetal and plated or precipitated lead must be removed at that point; otherwise the effective remediation of the contaminant is progressively reversed.

Polychlorinated biphenyls are a ubiquitous environmental contaminant that can be found today throughout the world in soils and sediments, lakes and rivers, and flora and fauna. PCBs have percolated throughout the food chain, so that almost every human being has a detectable amount of the contaminant within their blood stream. Existing remediation methods include incineration, dredging and landfilling, and microbial degradation, but all of these methods have drawbacks that limit their effectiveness as treatment options. Recently, the use of zero-valent metals as a means of reductive dechlorination has been explored. Using a combination of zero-valent magnesium and catalytic palladium, a successful bimetallic system capable of degrading PCBs has been created and optimized. Determining the mechanism for the reductive dechlorination has proven to be an arduous task, but experimental evidence has suggested three possible radical-type mechanisms for the use Mg/Pd specifically in methanol (as compared to aqueous systems). These possible mechanisms differ in the type of hydrogen species that replaces the chlorine atom on the PCB. Thermodynamic information has also aided in narrowing down which of the suggested pathways is most likely. It appears likely that the hydrogen involved in the dechlorination has the form of a "hydride-like" radical, which is a form of electron-rich atomic hydrogen. According to the literature, Pd catalysts create this species within the first few subsurface layers of the palladium in the presence of molecular hydrogen. Further work will be necessary to confirm that the "hydride-like" radical is actually the species involved in the dechlorination.