Heterogeneous Fenton Degradation of Patulin in Apple Juice Using Carbon-Encapsulated Nano Zero-Valent Iron (CE-nZVI)

Patulin (PAT), a mycotoxin found mainly in matured apples, is produced by different species of fungi, mainly Penicillium expansum, and is found in various fruits and vegetables used to produce juice. Little focus has been placed on nano-technological methods for the mitigation of this problem. In this work, carbon-encapsulated nano-zero valent iron (CE-nZVI) particles were synthesized and used as heterogeneous Fenton agents for the degradation of PAT in apple juice. The particles were found to have a spherical shape with a diameter of 130 ± 50 nm. In a heterogeneous Fenton degradation (involving CE-nZVI) process, a concentration of 0.05 g/L CE-nZVI with 0.5 mM H2O2 was used. Since the Fenton oxidation process is pH-dependent, placebo degradation was observed at varying pH conditions with an average percentage of PAT degradation of 27.8%, 87.0%, 98.0%, and 99.75% at pH 6, 5, 4.5, and 3.5 respectively, between 1 min to 4 h in a water matrix. In a juice matrix, at the regular pH of juice (3.6), percentage PAT degradation of 72% and 89% was obtained after a 2-h treatment using heterogeneous Fenton oxidation (CE-nZVI/H2O2) systems, using 0.5 mM H2O2 and 1 mM H2O2, respectively.This work was supported by the institutions IUACA (University Institute of the Water and the Environmental Sciences) University of Alicante (UA). I would also like to thank the Beca del Convenio Fundacion Mujeres por África y Universidad de Alicante Vice-Rectorate Equality Program (UA) for funding Notemba Silwana

Green Synthesis of Thin Shell Carbon-Encapsulated Iron Nanoparticles via Hydrothermal Carbonization

Nanoscale zerovalent iron (nZVI) has proven to be a promising solution for contaminant remediation, but its application is limited due to its high cost of synthesis and instability. Encapsulating the nZVI in carbon spheres generates more stable particles with improved properties due to the adsorption capacity provided by the carbon. The aim of this work was to synthesize thin shell carbon-encapsulated iron nanoparticles (CE-nFe) through hydrothermal carbonization (HTC) using olive mill wastewater as a carbonaceous source, which is a cheaper and more sustainable method of synthesis than the current practice. With this method, a high quality nanomaterial was obtained, which displayed surface areas up to 220 m2/g and was composed of ∼4 nm iron nanoparticles spheres surrounded by a thin layer of carbon (<1 nm). The effect of HTC conditions on the nanoparticle structure and morphology was evaluated. Post-treatment of the samples under nitrogen flow at high temperatures (600–800 °C) was used to increase the ZVI content of the samples. Finally, the synthesized CE-nFe were tested for the removal of heavy metals from water. Thanks to the carbon layer, CE-nFe proved to avoid the delivery of heavy metal ions back to water, a behavior previously observed with nZVI due to its aging after long time periods.Financial support for this work was given by the University of Alicante (UAFPU2013-5791)

Nitrogen activation of carbon-encapsulated zero-valent iron nanoparticles and influence of the activation temperature on heavy metals removal

Nanoparticles of zero-valent iron (nZVI) represent a promising agent for environmental remediation. This is due to their core-shell structure which presents the characteristics of both metallic and oxidised iron, leading to sorption and reductive precipitation of metal ions. Nevertheless, nZVI application presents some limitations regarding their rapid oxidation and aggregation in the media which leads to the delivery of the ions after some hours (the "aging effect"). To address these issues, modifications of nZVI structure and synthesis methods have been developed in the last years. The aging problem was solved by using nZVI encapsulated inside carbon spheres (CE-nZVI), synthetized through Hydrothermal Carbonization (HTC). Results showed high heavy metals removal percentage. Furthermore, CE-nZVI were activated with nitrogen in order to increase the metallic iron content. The aim of this study was to test CE-nZVI post-treated with nitrogen at different temperatures in heavy metals removal, demonstrating that the influence of the temperature was negligible in nanoparticles removal efficiency.This work was financially supported by University of Milano-Bicocca fund (2016-ATESP-0597) and University of Alicante (UAFPU2013-5791)

The Effect of Different Oxygen Surface Functionalization of Carbon Nanotubes on the Electrical Resistivity and Strain Sensing Function of Cement Pastes

Different studies in the literature indicate the effectiveness of CNTs as reinforcing materials in cement–matrix composites due to their high mechanical strength. Nevertheless, their incorporation into cement presents some difficulties due to their tendency to agglomerate, yielding a non-homogeneous dispersion in the paste mix that results in a poor cement–CNTs interaction. This makes the surface modification of the CNTs by introducing functional groups on the surface necessary. In this study, three different treatments for incorporating polar oxygen functional groups onto the surface of carbon nanotubes have been carried out, with the objective of evaluating the influence of the type and oxidation degree on the mechanical and electrical properties and in strain-sensing function of cement pastes containing CNTs. One treatment is in liquid phase (surface oxidation with HNO3/H2SO4), the second is in gas phase (O3 treatment at 25 and 160 °C), and a third is a combination of gas-phase O3 treatment plus NaOH liquid phase. The electrical conductivity of cement pastes increased with O3- and O3-NaOH-treated CNTs with respect to non-treated ones. Furthermore, the oxygen functionalization treatments clearly improve the strain sensing performance of the CNT-cement pastes, particularly in terms of the accuracy of the linear correlation between the resistance and the stress, as well as the increase in the gage factor from 28 to 65. Additionally, the incorporation of either non-functionalized or functionalized CNTs did not produce any significant modification of the mechanical properties of CNTs. Therefore, the functionalization of CNTs favours the de-agglomeration of CNTs in the cement matrix and consequently, the electrical conductivity, without affecting the mechanical behaviour.This research was funded by the European Union’s Horizon 2020 Research and Innovation Programme, grant number 760940

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

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.Financial support for this work was given by the University of Alicante (UAFPU2013-5791)

Study of the presence of PCDDs/PCDFs on zero-valent iron nanoparticles

Studies show that nanoscale zero-valent iron (nZVI) particles enhance the formation of chlorinated compounds such as polychlorinated dioxins and furans (PCDD/Fs) during thermal processes. However, it is unclear whether nZVI acts as a catalyst for the formation of these compounds or contains impurities, such as PCDD/Fs, within its structure. We analyzed the presence of PCDD/Fs in nZVI particles synthesized through various production methods to elucidate this uncertainty. None of the 2,3,7,8-substituted congeners were found in the commercially-produced nZVI, but they were present in the laboratory-synthesized nZVI produced through the borohydride method, particularly in particles synthesized from iron (III) chloride rather than from iron sulfate. Total PCDD/F WHO-TEQ concentrations of up to 35 pg/g were observed in nZVI particles, with hepta- and octa-chlorinated congeners being the most abundant. The reagents used in the borohydride method were also analyzed, and our findings suggest that FeCl3 effectively contains PCDD/Fs at concentrations that could explain the concentrations observed in the nZVI product. Both FeCl3 and nZVI showed a similar PCDD/F patterns with slight differences. These results suggest that PCDD/Fs might transfer from FeCl3 to nZVI during the production method, and thus, care should be taken when employing certain nZVI for environmental remediation.We would like to acknowledge the University of Alicante (EEBB-UA2013) for financing this study