Application of iron-based nanostructures to contaminant remediation

This thesis focuses on the synthesis and applications of nanoscale zero valent iron (nZVI) in the environmental remediation of contaminants. The polyvalent characteristics of this nanomaterial are evaluated in this work with the study of its application in a wide range of contaminants: heavy metals and pesticides in water medium, and malodorous sulfur compounds present in air streams. Moreover, a novel method of synthesis of encapsulated nZVI from a waste material is presented, which meets the principles of green chemistry and at the same time represents a low-cost method of obtaining nZVI with improved characteristics. Chapter 1 describes the current state of the topics that will be discussed in the rest of the thesis. Specifically, the different mechanisms of contaminant remediation by nZVI are discussed, a summary of the current synthesis methods is presented and the principal modifications of nZVI to improve its characteristics are described. Finally, the limitations of the current techniques are assessed, which will be the starting point of the thesis. In Chapter 2, the application of nZVI to heavy metal removal during long time periods is explored. The contaminants studied are Zn, Cd, Ni, Cu and Cr, which are the most common heavy metals found in ground and wastewater. A delivery-effect of the heavy metal ions that had already been attached to nZVI surface is observed after long reaction times, which is a consequence of the nZVI aging and oxidation. The conditions that influence the delivery-effect are assessed and possible solutions to this detected problem are presented. In Chapter 3, nZVI is applied to the removal of sulfur-based odorous compounds in air streams. The compounds studied are hydrogen sulfide and dimethyl disulfide (DMDS), which are commonly found in wastewater treatment plants. Both nZVI loading and pH are varied to assess their influence on the process. Bimetallic nanoscale particles of Cu/Fe, Ni/Fe and Pd/Fe are synthesized in order to improve the DMDS abatement by the nZVI. The advantages of this new method for odor removal are discussed at the look of the experimental results. Lastly, a pilot scale test was performed in a wastewater treatment plant in order to test the effectiveness of the nZVI in a real application. The nZVI were applied in a scrubber to eliminate the sulfurous compounds from the pre-treatment area of the wastewater treatment plant. Chapter 4 deals with the application of nZVI to the oxidation of non-biodegradable pollutants by the Fenton reaction. Specifically, the effect of pH on the degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) is studied. The advantages of using nZVI as a Fenton reagent compared to homogeneous Fenton are described. Furthermore, the addition of UV-light to the process is investigated. Finally, the main degradation intermediates of the reaction are identified and a degradation mechanism is accordingly proposed. In Chapter 5, the presence of polychlorinated dioxins and furans (PCDD/Fs) in the nZVI surface is addressed. Studies have shown that nZVI enhances the formation of such chlorinated compounds during thermal processes, but it is unclear which the origin of the compounds is. It has been suggested that nZVI could possess impurities such as PCDD/Fs in its surface. Therefore, the concentration of PCDD/Fs in both commercial and laboratory-synthesized nanoparticles is analyzed. PCDD/Fs pattern and WHO-TEQ concentrations are also obtained. As an outcome of the results obtained in this chapter, a recommendation for preventing the PCDD/Fs presence in nZVI is given. Chapter 6 is dedicated to the synthesis of carbon-encapsulated nanoparticles using hydrothermal carbonization (HTC) of an agricultural waste, particularly, olive mill wastewater (OMW). This novel method, in addition to meet the green chemistry principles, makes profit of the high polyphenol content of OMW to maximize the fraction of incorporated iron into the nZVI. Moreover, the carbon layer surrounding the nZVI protects it against oxidation and avoids its aggregation. Several HTC conditions are explored to study their implications in the characteristics of the material obtained. A deep characterization of the encapsulated nZVI is also presented in this chapter. In Chapter 7, the applications of the encapsulated nZVI synthesized in Chapter 6 are explored and compared for the same contaminants that have been studied in the previous chapters. Then, the advantages of encapsulated nZVI in comparison with common nZVI are discussed at the end of the chapter, and an estimation of the synthesis costs with this method is addressed. Lastly, in Chapter 8, the main conclusions of the thesis are summarized and suggestions for future work are presented