Chemical reduction of hexavalent chromium (VI) in soil slurry by nano zero valent iron

The increasing industrial development of recent decades has lead to the production of increasing quantities of waste containing heavy metals, elements often harmful to the environment, which in the past were not properly disposed of, thus inducing soil and groundwater pollution. In particular, chromium (Cr) and its derivatives are largely used in industries such as textiles, electronics, metallurgy, tanneries. Consequently, large quantities of this element were released into the environment due to leakage or incorrect disposal. Chromium is a transition element present in nature in three stable forms: metallic Cr, trivalent Cr(III) and hexavalent Cr(VI). Metallic Chromium is rarely found in nature, mainly as natural chrome metallic inclusions in diamonds, fragments of as meteorites and metal alloys in fluvial deposits. The trivalent form is characterized by a relatively low toxicity, while the hexavalent chromium present in different compounds of industrial origin, is considered highly toxic towards the respiratory system and carcinogenic. In the present work, lab experiments of Cr(VI) contaminated soil clean-up by chemical reduction with nanoparticles of zero valent iron (nZVI) are presented and discussed. The aim of the work was to optimize the main operative parameters of the reduction process (pH, nZVI concentration, liquid/solid ratio). Cr(VI) reduction using nZVI was found to obey a pseudo-first-order kinetic: the kinetic constant depended upon the nZVI: Cr(VI) ratio. The use of nZVI in combination with sodium dithionite was also studied, by performing tests in batch conditions at pH = 1.3, in order to assess the optimal ratio between nZVI and Cr(VI), and between dithionite and Cr(VI). The results obtained showed an increase of Cr(VI) reduction rate with respect to the tests carried only with nZVI: for long treatment times, up to 24 hours, an almost total removal of Cr(VI) was achieved when a large excess of reagents was used

Manganese-containing mixed oxide electrodes as anode materials for degradation of model organic pollutants

Mixed oxide thin film electrodes have been prepared by thermal decomposition from alcoholic solution on Pt substrate. In particular, three different anodes have been obtained by co-deposition of Ru (Ruthenium) and Mn (Manganese) oxides, Ru, Mn and Cu (Copper) oxides and co-deposition of Ru, Mn and Co (Cobalt) oxides. The electrochemical behaviour of the prepared electrodes was evaluated by potentiodynamic polarization curves and cyclic voltammetry tests. We also tested and compared their oxidizing ability in the degradation of aqueous solutions containing methyl orange as model compound and small amount of chloride. Galvanostatic experiments were conducted in a membrane-free reactor. The treatment extent was assessed by detection of color and TOC decay. The electrogeneration of active chlorine, chlorate and perchlorate was also monitored. The preliminary results show that ternary oxides coated electrodes exhibit enhanced electrocatalytic activity without producing undesired chlorinated by-products

Shortcut Biological Nitrogen Removal (SBNR) in an MFC anode chamber under microaerobic conditions. The effect of C/N ratio and kinetic study

In this work, the feasibility of the Shortcut Biological Nitrogen Removal (SBNR) in the anodic chamber of a Microbial Fuel Cell (MFC) was investigated. Thirty day experiments were carried out using synthetic wastewaters with a Total Organic Carbon vs. nitrogen ratio (TOC/N) ranging from 0.1 to 1. Ammonium, nitrite, nitrate, pH, and TOC were daily monitored. Results showed that microaerobic conditions in the anodic chamber favored the development of nitritation reaction, due to oxygen transfer from the cathodic chamber through the membrane. Nitritation was found to depend on TOC/N ratio: at TOC/N equal to 0.1 an ammonium removal efficiency of up to 76% was observed. Once the oxygen supply to the cathodic chamber was stopped, denitritation occurred, favored by an increase of the TOC/N ratio: a nitrite removal of 80.3% was achieved at TOC/N equal to 0.75. The presence of nitrogen species strongly affected the potential of the electrochemical system: in the nitritation step, the Open Circuit Voltage (OCV) decreased from 180 mV to 21 mV with the decrease of the TOC/N ratio in the investigated range. Lower OCV values were observed in the denitritation steps since the organic carbon acted as the energy source for the conversion of nitrite to nitrogen gas. A kinetic analysis was also performed. Monod and Blackman models described the ammonium and the organic carbon removal processes well during the nitritation step, respectively, while Blackman-Blackman fitted experimental results of the denitritation step better

Shortcut biological nitrogen removal (SBNR) in microbial fuel cells (MFCs)

Microbial Fuel Cells (MFCs) represent nowadays a promising technology for the treatment of industrial wastewater. In this work the Shortcut Nitritation/Denitritation process in H-type MFC was investigated. The cell was fed by sodium acetate and fumaric acid, as organic carbon source, and ammonium sulphate, sodium nitrite and sodium nitrate as nitrogen source. Anaerobic digestion supernatant (digestate) was used as bacterial source. Batch tests were performed at a TOC/N ratio of 0.35, and Total Organic Carbon (TOC), pH and Open Circuit Voltage (OCV) were daily monitored. High organic carbon removal (up to 85%) in short time (within 6 days) were achieved. The nitritation proved to be independent of organic carbon amount and composition: an ammonium content reduction of about 45% was observed. Regarding the denitritation step, an almost quantitative removal of nitrite and nitrate was observed when fumaric acid was used as a carbon source

Photolysis of in-situ electrogenerated hydrogen peroxide for the degradation of emerging pollutants

This study investigates the degradation of paracetamol, an emerging contaminant widely used as pain and fever reliever, by means of hydrogen peroxide either alone or in combination with UV-C photolysis. In particular, we provide a comparison between the performance of both commercial and electrogenerated H2O2 whose production has been achieved by galvanostatic electrolysis in undivided reactor with a gas diffusion cathode. The performance of the treatments has been assessed in terms of both pollutant decay and mineralization. The influence of the H2O2 to paracetamol molar ratio is discussed. The results show that the electrogenerated hydrogen peroxide, when activated by UV-C irradiation, results in faster degradation and mineralization of paracetamol. However, under the conditions adopted, complete depletion of the total organic carbon (TOC) has never been attained

Activated biochars used as adsorbents for dyes removal

Adsorption represents one of the most interesting technique for the removal of pollutants from wastewaters. Activated carbons show the best performances on this kind of processes but their high production costs limit their applications. In this context a big challenge is to find new materials having characteristic similar to those of commercial activated carbons but being environmental friendly and cheaper. In this work the adsorption efficiency of activated biochars produced from pine wood was investigated on the removal of dyes from water. An innovative method for the activation of the biochar using deep eutectic solvents (DES) was tuned and the characteristics of the obtained adsorbent material were compared with those of biochar activated with traditional method and non-activated biochar. The best adsorption capacities were obtained with the DES activated biochar, reaching a value of 480 mg/g for the methylene blue adsorption. Adsorption isotherm and kinetic models were applied to experimental data in order to understand the adsorption mechanism of the process

Use of nano zero-valent iron to reduce inorganic species electrogenerated during anodic oxidation on boron doped diamond anodes

In this paper, the solution coming from an anodic oxidation on boron doped diamond of chloride-containing solution is treated with addition of nano zero-valent iron (nZVI) to reduce the amount of chlorinated byproducts into chloride ions. The electrolyzed solutions have been obtained under galvanostatic conditions in an undivided reactor. The evolution and depletion of all the chlorinated species have been monitored by spectrophotometry and ion chromatography. The nanoscale iron particles have been synthesized in our laboratory by a fast and facile method through reaction of FeSO4 and NaBH4 solutions without addition of dispersants. The effect on the conversion yield of several operative parameters has been investigated and discussed. The preliminary results indicate that a nZVI postreatment can be considered a viable technology for the treatment of solutions containing active chlorine and chlorate. However, the reduction of perchlorate, either in mixed solutions or alone, requires too drastic conditions to be completed

The influence of heavy metals and organic matter on hexavalent chromium reduction by nano zero valent iron in soil

During the last decades great attention has been payed at evaluating the feasibility of Cr(VI) reduction in soil by nano zero valent iron (nZVI). An inhibitory effect on the Cr(VI) reduction by Fe-0 nanoparticles is generally shown in the presence of high level of heavy metals and natural organic matter in soil. Heavy metals in the environment can react with nZVI by redox reactions, precipitation/dissolution reactions, and adsorption/desorption phenomena. As a result of the presence of metals as Ni, Pb, a decrease in the rate of Cr(VI) reduction was observed. Hence, in the present study, experimental tests of Cr(VI) reduction by nZVI in the presence of selected heavy metals, such as nickel and lead, and in the presence of high level of organic matter, are presented and discussed. Results showed a decrease in the rate of Cr(VI) reduction in soil by nZVI (at a x25 stoichiometric excess) from 91% to 78%, 71% and 74% in the presence of Ni, Pb and both metals respectively. As regards the results of Cr(VI) reduction in the presence of organic matter, by using a reducing solution of nZVI (x25 stoichiometric excess) a decrease of Cr(VI) reduction yield from 91% to 12% was observed after 2 hours of treatment in a soil containing 35.71 g/kg of organic matter. Such low efficiency was attributed to the adsorption of organic matter onto Fe-0 nanoparticles surface, thus saturating the active reaction sites of Fe-0 nanoparticles. In addition, a significant reduction of the organic carbon in the treated soil was observed (up to 77.5%) caused by the degradation of organic matter and its dissolution in the liquid phase. A slight decrease of the total metal concentration in treated soil was also observed. Finally, kinetic tests show that Cr(VI) reduction using nZVI in the presence of a high concentration of organic compound obeyed a pseudo-zero-order kinetic model

The IMiDs targets IKZF-1/3 and IRF4 as novel negative regulators of NK cell-activating ligands expression in multiple myeloma

Immunomodulatory drugs (IMiDs) have potent anti-tumor activities in multiple myeloma (MM) and are able to enhance the cytotoxic function of natural killer (NK) cells, important effectors of the immune response against MM. Here, we show that these drugs can enhance the expression of the NKG2D and DNAM-1 activating receptor ligands MICA and PVR/CD155 in human MM cell lines and primary malignant plasma cells. Depletion of cereblon (CRBN) by shRNA interference strongly impaired upregulation of these ligands and, more interestingly, IMiDs/CRBN-mediated downregulation of the transcription factors Ikaros (IKZF1), Aiolos (IKZF3) and IRF4 was critical for these regulatory mechanisms. Indeed, shRNA knockdown of IKZF1 or IKZF3 expression was both necessary and sufficient for the upregulation of MICA and PVR/CD155 expression, suggesting that these transcription factors can repress these genes; accordingly, the direct interaction and the negative role of IKZF1 and IKZF3 proteins on MICA and PVR/CD155 promoters were demonstrated. Finally, MICA expression was enhanced in IRF4-silenced cells, indicating a specific suppressive role of this transcription factor on MICA gene expression in MM cells. Taken together, these findings describe novel molecular pathways involved in the regulation of MICA and PVR/CD155 gene expression and identify the transcription factors IKZF-1/IKZF-3 and IRF4 as repressors of these genes in MM cells