The purpose of this thesis was to investigate the potential ability of nano-scale zerovalent iron (nZVI) to remediate multiple metal contaminants, specifically in the context of mine tailings. The project began by adopting techniques reported on by investigators researching the remediation effectiveness on metal contaminants of nZVI within the framework of civil engineering applications, such as groundwater treatment (Karabelli et al, 2008). This phase of the project saw the treatment of laboratory prepared samples of copper contaminated waters (at 10, 30, 50 and 100 ppm) by the addition of unstabilized nZVI. Results showed that all but the 100 ppm samples were effectively cleared of nearly all metal contamination following treatment additions of 1 mL nZVI to 50 mL of sample water. The second phase of the project sought to expand on this success by subjecting laboratory prepared water samples containing multiple metal contaminants to the same dose on nZVI. A collection of metal contaminants, known as the Arctic Suite, containing arsenic, cadmium, cobalt, chromium, nickel, lead and zinc, was made up as contaminated waters (at 1, 3, 5, and 10 ppm concentrations) and was tested for nZVI remediation. Results showed that only the 10 ppm samples were not effectively remediated and furthermore showed preferential treatment of arsenic, chromium and lead instead of an even distribution of treatment amongst all metal contaminants present. The final phase of the project saw the testing of contaminated waters produced from five mine tailings, acquired from separate sources, by the same dose of nZVI as in the first two phases of the project. Results showed that where contaminant metals were present some remediation effect did occur. However, an inability to produce highly contaminated leachates from the mine tailings meant that no trends in nZVI remediation effectiveness could be determined with any certainty. / Thesis (Master, Mining Engineering) -- Queen's University, 2011-09-01 11:04:28.869

Trichloroethylene (TCE) is one of the most common groundwater pollutants in the United States and is a suspected carcinogen. The United States Environmental Protection Agency (EPA) estimated that between 9% and 34% of the drinking water sources in the United States may contain TCE, and have set a maximum contaminant level of 5 ìg/L for drinking water. Traditional treatment technologies such as granular activated carbon and air stripping have only had marginal success at removing TCE from contaminated sites. Chemical oxidation processes have provided a promising alternative to traditional treatment methods. The objective of this research was to examine the conditions under which zero valent iron (Fe0) activates persulfate anions to produce sulfate free radicals, a powerful oxidant used for destroying organic contaminants in water. With batch experiments, it was found that persulfate activated by zero valent iron removed TCE more effectively than persulfate oxidation activated by ferrous iron. This laboratory study also investigated the influence of pH (from 2 to 10) on TCE removal. TCE was prepared in purified water and a fixed persulfate/TCE molar ratio was employed in all tests. The results indicated that this reaction occurred over a wide range of pH values. The production and destruction of daughter products cis 1,2 dichloroethylene and vinyl chloride were observed. The effect of persulfate dose on this reaction was also studied. Results showed that a molar ratio of 10/1/1 (persulfate/ZVI/TCE) yielded over 95 percent TCE destruction. Increasing the persulfate dose resulted in greater TCE destruction as well as destruction of the daughter products. Kinetic experiments at a molar ratio of 10/1/1 (persulfate/ZVI/TCE) show that approximately 90 percent of the TCE was destroyed in less than 15 minutes.

Thesis (Ph. D.)--Auburn University. / Abstract. Vita. Includes bibliographical references (p. 153-170).

Uranium contamination of groundwater from mining and milling operations is an environmental concern. Reductive precipitation of soluble and mobile hexavalent uranium (U(VI)) contamination to insoluble and immobile tetravalent uranium (U(IV)) constitutes the most promising remediation approach for uranium in groundwater. Previous research has shown that many microorganisms are able to catalyze this reaction in the presence of suitable electron-donors. The purpose of this work is to explore lowcost, effective alternatives for biologically catalyzed reductive precipitation of U(VI). Methanogenic granular sludge from anaerobic reactors treating industrial wastewaters was tested for its ability to support U(VI)-reduction. Due to their high microbial diversity, methanogenic granules displayed intrinsic activity towards U(VI)-reduction. Endogenous substrates from the slow decomposition of sludge biomass provided electron-equivalents to support efficient U(VI)-reduction without external electrondonors. Continuous columns with methanogenic granules also demonstrated sustained reduction for one year at high uranium loading rates. One column fed with ethanol, only enabled a short-term enhancement in the uranium removal efficiency, and no enhancement over the long term compared to the endogenous column. Nitrate, a common co-contaminant of uranium, remobilized previously deposited biogenic U(IV). U(VI) also caused inhibition to denitrification. An enrichment culture (EC) was developed from a zero-valent iron (Fe⁰)/sand packed-bed bioreactor. During 28 months, the EC enhanced U(VI)-reduction rates by Fe⁰ compared with abiotic Fe⁰ controls. Additional experiments indicated that the EC prevented the passivation of Fe⁰ surfaces through the use of cathodic H₂ for the reduction of Fe(III) in passivating corrosion mineral phases (e.g. magnetite) to Fe²⁺. This contributed to the formation of secondary minerals more enriched with Fe(II), which are known to be chemically reactive with U(VI). To determine the toxicity of U(VI) to different populations present in uranium contaminated sites, including methanogens, denitrifiers and uranium-reducers, experiments were carried out with anaerobic mixed cultures at increasing U(VI) concentrations. Significant inhibition to the presence of U(VI) was observed for methanogens and denitrifiers. On the other hand uranium-reducing microorganisms were tolerant to high U(VI) concentrations. The results of this dissertation indicate that direct microbial reduction of U(VI) and microbially enhanced reduction of U(VI) by Fe⁰ are promising approaches for uranium bioremediation.

The objective of this research was to evaluate the treatment efficiency of a trichloroethylene(TCE)-contaminated aqueous solution and soil by combined technologies of the emulsified nanoscale zero-valent iron slurry (ENZVIS) and electrokinetic remediation process. Nanoiron was synthesized using the chemical reduction method by industrial grade chemicals. The synthesized nanoparticles contained elemental iron and iron oxide as determined by X-ray diffractmetry(XRD). Micrographs of FE-SEM have shown that a majority of nanoiron were in the size range of 30~50 nm. The stability study of food-grade soybean oil emulsion was conducted using six non-ionic surfactants and soybean oil. The results have shown that the emulsion prepared by mixed surfactants (Span 80 and Tween 40) and soybean oil yielded a better emulsion stability. Based on the above finding, the nanoiron slurry, soybean oil and aforementioned, mixed surfactants were used to prepare ENZVIS. Degradation of TCE by ENZVIS under various operating parameters was carried out in batch experiments. The experimental results have indicated that emulsified nanoiron outperformed nanoiron in TCE dechlorination rate. ENZVIS (0.75 g-Fe0/L) degradated TCE (initial conc.= 10 mg/L) down to 45 %. An increase of the oil dosage could improve the stability of the emulsion, but yielding a negative influence on degradation of TCE. Experimental results also showed that ENZVIS could remove TCE up to 94 % when pH=6. It was also formed that a higher TCE initial concentration would result in a higher TCE removal efficiency. In addition, using ENZVIS to degraded TCE-contaminated artificial groundwater has indicated that nitrate and carbonate of groundwater will suppress nanoiron reaction with TCE. Especially, a high concentration of carbonate in the reaction system might form a passive film or precipitates on nanoiron surface. This study further evaluated the treatment efficiency of combining ENZVIS and electrokinetic technology in treating a TCE-contaminated soil. Experimental conditions were given as follows:(1) initial TCE concentration in the range of 98~118 mg/kg; (2) an electric potential gradient of 1 V/cm; (3) a daily addition of 20 mL ENZVIS; and (4) a reaction time of 10 days. Experimental results have shown that an addition of ENZVIS to the anode reservoir of strongly acidic and oxidative environment would cause nanoiron to corrode rapidly and decrease TCE removal efficiency. On the other hand, an addition of ENZVIS to the cathode reservoir would enhance the degradation of TCE therein. In summary, an addition of ENZVIS to the cathod reservoir would yield the best TCE removal efficiency.

The hybrid Zero Valent Iron (hZVI) process is a novel chemical treatment platform that has shown great potential in our previous bench-scale tests for removing selenium, mercury and other pollutants from Flue Gas Desulfurization (FGD) wastewater. This integrated treatment system employs new iron chemistry to create highly reactive mixture of Fe^0, iron oxides (FeOx) and various forms of Fe (II) for the chemical transformation and mineralization of various heavy metals in water. To further evaluate and develop the hZVI technology, a pilot-scale demonstration had been conducted to continuously treat 1-2 gpm of the FGD wastewater for five months at Plant Wansley, a coal-fired power plant of Georgia Power. This demonstrated that the scaled-up system was capable of reducing the total selenium (of which most was selenate) in the FGD wastewater from over 2500 ppb to below 10 ppb and total mercury from over 100 ppb to below 0.01 ppb. This hZVI system reduced other toxic metals like Arsenic (III and V), Chromium (VI), Cadmium (II), Lead (II) and Copper (II) from ppm level to ppb level in a very short reaction time. The chemical consumption was estimated to be approximately 0.2-0.4 kg of ZVI per 1 m^3 of FGD water treated, which suggested the process economics could be very competitive. The success of the pilot test shows that the system is scalable for commercial application. The operational experience and knowledge gained from this field test could provide guidance to further improvement of technology for full scale applications. The hZVI technology can be commercialized to provide a cost-effective and reliable solution to the FGD wastewater and other metal-contaminated waste streams in various industries. This technology has the potential to help industries meet the most stringent environmental regulations for heavy metals and nutrients in wastewater treatment.

In this research, nanoscale zero-valent iron (NZVI) was synthesized using the chemical reduction method. Experimental results have revealed that nanoiron synthesized by the reagent-grade chemicals had a size range of 50-80 nm, as determined by FE SEM. BET specific surface area of thus synthesized nanoparticles was 66.34 m2/g. NZVI prepared by the industrial-grade chemicals had a broader particle size distribution (30-80 nm) and its BET specific surface area was 61.50 m2/g. Results of XRD showed that both types of NZVI were composed of iron with a poor crystallinity. Additional test results further showed that both types of NZVI had similar characteristics. NZVI prepared by the chemical reduction method tends to aggregate resulting in a significant loss in reactivity. To overcome this disadvantage, four water-soluble dispersants were used in different stages of the NZVI preparation process. Of these, Dispersant A (an anionic surfactant) has shown its superior stabilizing capability to others. An addition of 0.5 vol % Dispersant A during the nanoiron preparation process would result in a good stability of NZVI slurry (NZVIS). Degradation of trichloroethylene (TCE) by NZVIS under different atmospheres was carried out in batch experiments. Experimental results have shown that the TCE dechlorination rate increased markedly when the reaction proceeded under hydrogen gas atmosphere as compared with that of air. Methane was the primary end product with a trace amount of ethane and ethylene when the reaction was conducted under the atmosphere of H2. It was suggested that an addition of H2 to the reaction system could promote the hydrogenolysis reaction for better degradation. On the other hand, ethane was the main product when the reaction system consisted of nanoscale palladized iron and H2 atmosphere. It demonstrated that Pd-catalyzed TCE dechlorination has resulted in a direct conversion of TCE to ethane in the study. The greatest dechlorination rate was obtained when 2 g/L nanoscale palladized iron and 50 mL H2 was employed in the reaction system. Under the circumstances, the TCE (10 mg/L) removal efficiency was up to 99 % in 3 minutes. Experimental results have demonstrated that the reaction system with both nanoscale palladized iron and H2 atmosphere would promote TCE degradation rate. The culture of microorganism in soil showed minor changes to microbial community structures between the pre- and post-injection conditions. The number of microorganism colony was found to be increased after adding 1 mL NZVIS to 1 g soil. Experimental results revealed that NZVIS would not cause the inhibition or reduction of microorganism activity. Surface modification of NZVI slurry by Dispersant A could enhance its transport in saturated porous media. Sticking coefficients were determined to be 0.56 and 0.11, respectively, for bare and Dispersant A-modified NZVIS transporting in quartz sand columns. The sticking coefficient for modified NZVIS transport in soil (loamy sand) column was determined to be 0.0061. Apparently, NZVIS modified by Dispersant A would enhance the transport of NZVI in saturated porous media. The results of combining electrokinetic technology and NZVIS injection tests in horizontal soil column illustrated that the sticking coefficient was 0.00034 and the total content of iron reduced 10 wt. %. Experimental results revealed that the transport distance of NZVIS in saturated horizontal soil column would be greatly increased under electronkinetic conditions.

Thesis (Ph. D.)--Auburn University, 2007. / Abstract. Vita. Includes bibliographical references (p. 144-169).

Use of Nano Zero Valent Iron (nZVI) for treatment of different halogenated hydrocarbons, arsenic and various other contaminants has been proved successful. However, with so much diversified use of nZVI in the field and heighted attention to engineered nanoparticles, the environmental fate and impact of the nZVI remains unknown. The goal of this project was to evaluate the effects of different types of nZVI on Typha latifolia, a common wetland plant and hybrid poplar (Populous deltoids x Populous nigra), a woody plant used in phytoremediation. Plants grown hydroponically in a green house were dosed with different concentration of bare or bimetallic nZVI (with 10% nickel coating) for one to four weeks. The results showed that bare nZVI had toxic effects to Typha in higher concentrations but enhanced growth of plants at lower concentrations. Bare nZVI did not significantly affect the growth of poplars but bimetallic nZVI did impede the growth. Bimetallic nano particles were significantly more toxic and resulted in death of Typha within a week of dosing. Scanning electron microscope (SEM) clearly showed the adsorption of the nZVI on the plant root surface, confirmed by Energy dispersive x-ray (EDX) analysis. Transmission electron microscope (TEM) and Scanning Transmission electron microscope (STEM) confirmed the uptake of nZVI by poplar plant, but such internalization was not observed in case of Typha. However, uptake of the nanoparticles was only limited to the root and the translocation of particles to the shoot was not observed.

No description available.