Luciano Carlos

Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds.

The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25 degrees C using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta (defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 x 10(9) M(-1)s(-1). A quantitative structure-reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO* radical.

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton’s reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.

Degradation of nitroaromatic compounds by the UV–H2O2 process using polychromatic radiation sources

The UV-H2O2 process, a standard advanced oxidation process (AOP) for water treatment, has been applied to the degradation of a series of nitroaromatic compounds (nitrobenzene, 1-chloro-2,4-dinitrobenzene, 2,4-dinitrophenol, 3-nitrophenol, 4-nitrophenol and 4-chloro-3,5-dinitrobenzoic acid) using polychromatic radiation sources. The optimal concentration of hydrogen peroxide ([H2O2]OPT) leading to the fastest degradation rate of a given substrate (S) was determined experimentally and estimated using a simplified kinetic model based on the main reactions involved in the first stages of the oxidation. We have shown that, under conditions of monochromatic irradiation, the ratio ROPT (= [H2O2]OPT/[S]0) is given by a simple mathematical expression containing only a few parameters, whereas, under conditions of polychromatic irradiation, ROPT is expressed by a complex mathematical equation (involving the spectral distribution of the lamp emission and the absorption spectra of H2O2 and the substrate). Two numerical analysis procedures are proposed for obtaining the bimolecular rate constants for the reaction of hydroxyl radicals with a substrate (kS) from this equation. The rate constants, kS, determined for the substrates investigated in this work are in agreement with the expected reactivity trend, taking into account the effects of substituents on the distribution of electron density in the aromatic ring. The methods proposed in this work offer a double advantage: i) a standard AOP may be used to evaluate the rate constants of reaction of substrates with hydroxyl radicals under polychromatic as well as under monochromatic irradiation, ii) optimal amounts of additive may be obtained using only a few parameters as predictive tools.

Applications of Magnetite Nanoparticles for Heavy Metal Removal from Wastewater

Contamination of water with toxic metal ions (Hg(II), Pb(II), Cr(III), Cr(VI), Ni(II), Co(II), Cu(II), Cd(II), Ag(I), As(V) and As(III)) is becoming a severe environmental and public health problem. In order to achieve environmental detoxification, various techniques like adsorption, precipitation, ion exchange, reverse osmosis, electrochemical treatments, mem‐ brane filtration, evaporation, flotation, oxidation and biosorption processes are extensively used [3-5]. Among these, adsorption is a conventional but efficient technique to remove tox‐ ic metal ions and bacterial pathogens from water.

Nitration of nitrobenzene in Fenton's processes

Previous studies of nitrobenzene (NB) degradation by Fenton and photo-Fenton technologies have demonstrated the formation and accumulation of 1,3-dinitrobenzene (1,3-DNB) as a highly toxic reaction intermediate. In the present study, we analyze the conditions that favor 1,3-DNB formation during NB degradation by Fe(2+)/H(2)O(2), Fe(3+)/H(2)O(2), UV/Fe(3+)/H(2)O(2) or UV/H(2)O(2) processes. Nitration yields in Fenton, Fenton-like and photo-Fenton techniques were much higher than those observed in UV/H(2)O(2) systems. Besides, several tests showed that 1,3-DNB formation increases with the initial iron concentration and decreases as the initial H(2)O(2) concentration increases. In order to asses the key species involved in NB nitration mechanism, additional experiments were performed in the presence of NO(2)(-)or NO(3)(-). In dark systems, 1,3-DNB yield significantly increased with increasing [NO(2)(-)]_(0), while it was not affected by the presence of NO(3)(-). In contrast, 1,3-DNB yields were higher and more strongly affected by the additive concentration in UV/NO(3)(-) systems than in UV/HNO(2)/NO(2)(-) systems. Dark experiments performed at pH 1.5 in excess of HNO(2) along with UV/NO(3)(-) tests conducted in the presence of 2-propanol show that hydroxyl radicals play an important role in NB nitration since NB molecule does not react with the nitrating agents ONOOH, .NO or .NO(2). The results indicate that, in the experimental domain tested, the prevailing NB nitration pathway involves the reaction between the .OH-NB adduct and .NO(2) radicals.

Sustainable magnet-responsive nanomaterials for the removal of arsenic from contaminated water

In this study, chitosan and bio-based substances (BBS) obtained from composted biowaste were used as stabilizers for the synthesis of magnet-sensitive nanoparticles (NPs) via coprecipitation method. A pyrolysis treatment was carried out on both biopolymers at 550°C, and their consequent conversion into a carbon matrix was followed by means of different physicochemical characterization techniques (mainly FTIR spectroscopy and XRD), whereas magnetic properties were evaluated by magnetization curves. The prepared materials were tested in water remediation processes from arsenic (As) species (both inorganic and organic forms). These tests, explained by means of the most common adsorption models, evidenced that the best performances were reached by both materials obtained after pyrolysis treatments, pointing out the promising application of such magnet-sensitive materials as easy-recoverable tools for water purification treatments.

Humic-like substances from urban waste as auxiliaries for photo-Fenton treatment: a fluorescence EEM-PARAFAC study

In this work, analysis of excitation-emission-matrices (EEM) has been employed to gain further insight into the characterization of humic like substances (HLS) obtained from urban wastes (soluble bio-organic substances, SBOs). In particular, complexation of these substances with iron and changes along a photo-Fenton process have been studied. Recorded EEMs were decomposed by using parallel factor analysis (PARAFAC). Three fluorescent components were identified by PARAFAC modeling of the entire set of SBO solutions studied. The EEM peak locations (λex/λem) of these components were 310-330 nm/400-420 nm (C1), 340-360 nm/450-500 nm (C2), and 285 nm/335-380 nm (C3). Slight variations of the maximum position of each component with the solution pH were observed. The interaction of SBO with Fe(iii) was characterized by determining the stability constants of the components with Fe(iii) at different pH values, which were in the order of magnitude of the ones reported for humic substances and reached their highest values at pH = 5. Photochemical experiments employing SBO and Fe(iii), with and without H2O2, showed pH-dependent trends for the evolution of the modeled components, which exhibited a strong correlation with the efficiency reported for the photo-Fenton processes in the presence of SBO at different pH values.

Soybean peroxidase immobilized onto silica-coated superparamagnetic iron oxide nanoparticles: Effect of silica layer on the enzymatic activity

Peroxidase immobilization onto magnetic supports is considered an innovative strategy for the development of technologies that involves enzymes in wastewater treatment. In this work, magnetic biocatalysts were prepared by immobilization of soybean peroxidase (SBP) onto different silica-coated superparamagnetic iron oxide nanoparticles. The obtained magnetic biocatalysts were tested for the degradation of malachite green (MG), a pollutant often found in industrial wastewaters and with significant drawbacks for the human and environmental health. A deep physicochemical characterization of the materials was performed by means of X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), High Resolution-Transmission Electron Microscope (HR-TEM) and magnetization measurements among others techniques. Results showed high immobilization yield of SBP onto nanomaterials with excellent properties for magnetic recoverability. A partial loss of activity with respect to free SBP was observed, compatible with the modification of the conformational structure of the enzyme after immobilization. The structural modification depended on the amount (and thickness) of silica present in the hybrid materials and the activity yield of 43% was obtained for the best biocatalyst. Thermal stability and reusability capacity were also evaluated.

From biowaste to magnet-responsive materials for water remediation from polycyclic aromatic hydrocarbons

Composted urban biowaste-derived substances (BBS-GC) are used as carbon sources for the preparation of carbon-coated magnet-sensitive nanoparticles obtained via co-precipitation method and the subsequent thermal treatment at 550 °C under nitrogen atmosphere. A multitechnique approach has been applied to investigate the morphology, magnetic properties, phase composition, thermal stability of the obtained magnet-sensitive materials. In particular, pyrolysis-induced modifications affecting the BBS-GC/carbon shell were highlighted. The adsorption capacity of such bio-derivative magnetic materials for the removal of hydrophobic contaminants such as polycyclic aromatic hydrocarbons was evaluated in order to verify their potential application in wastewater remediation process. The promising results suggest their use as a new generation of magnet-responsive easily-recoverable adsorbents for water purification treatments.

CHAPTER 4:Food Wastes Conversion to Products for Use in Chemical and Environmental Technology, Material Science and Agriculture

Food wastes are shown as a cost-effective source of added-value products for a wide number of uses. For soluble substances isolated from municipal biowastes, the present chapter reviews work performed in the last 7 years investigating the chemical nature, the physical-chemical properties, and the performance in chemical and environmental technologies, in material chemistry and in agriculture. Very recent unpublished data are also reported to show that ongoing research is a worthwhile effort to realise the full potential of the above refuse-derived biobased products. The available data allow a viable situation to be envisioned where urban waste-treatment plant are turned into biorefinery for the production of energy, chemicals and consumer products with friendly environmental impact. The perspectives for this scenario to become real are discussed.