The photocatalytic reduction of NO3- to N2 with ilmenite (FeTiO3): Effects of groundwater matrix.

This work analyzes the role of natural groundwater, as well as the effect of HCO3-, Ca2+, Mg2+, K+, SO42- and Cl- concentrations, upon the photocatalytic nitrate reduction using ilmenite as catalyst and oxalic acid as hole scavenger. The nitrate removal and the selectivity towards N2 are significantly limited compared to previous experiments using ultrapure water matrix. Calcium (Ca2+), bicarbonate (HCO3-) as well as pH are claimed as the major controlling factors related to the process yield. Thus, Ca2+ promotes the formation of insoluble oxalate microcrystals, reducing the amount of hole scavenger available. The presence of HCO3- leads to a steeply increase in the pH value, favoring the adsorption onto the ilmenite surface of ions OH-instead of NO3-, NO2- and C2O42. The aforementioned issues are overcome by working with C2O42-/NO3- ratio well above the stoichiometric one, that also maintains the pH value in an acid range. A completed depletion of the starting NO3-, the no detection of either NO2- or NH4+ in the aqueous phase, and a selectivity towards N2 above 95% were achieved using two times the stoichiometric dose.

Evaluation of photoassisted treatments for norfloxacin removal in water using mesoporous Fe2O3-TiO2 materials.

We report the synthesis of mesoporous TiO2 and mesoporous Fe2O3-TiO2 catalysts by using a structure-directing-surfactant method, their characterization and their employment as photocatalysts for norfloxacin degradation in aqueous solution. The main findings show that in the presence of both O2 and H2O2, Fe-containing mesoporous titania (Fe2O3-TiO2), with iron percentages between 1 and 3 wt%, exhibited norfloxacin degradation rates more than 60% greater than otherwise identical mesoporous titania without iron. Furthermore, the activity of the mesoporous composite catalysts also exceeds that of titania when illuminated with 405 nm light-emitting diodes. Iron loading improved the photocatalytic activity for norfloxacin degradation with values of apparent reaction rate constants of 0.037 min-1 and 0.076 min-1 with 1 and 3 surface wt.% of iron, respectively. An optimum of activity was found with the 3 wt% Fe2O3-TiO2 catalyst. Under these conditions, 10 mg/L of norfloxacin is reacted essentially to completion and 90% of total organic carbon conversion was obtained within 120 min of reaction. This higher organic carbon conversion degree was reached due to the photo-oxidation of short-chain organic acids. The high activity of the as-synthesized mesoporous composites is attributed to the additional iron phase which led to the different reactions for H2O2 decomposition, but also due to the improvement in light absorbance. Finally, the activity of the most active catalyst was found to be stable over multiple sequential runs, which was related to a negligible amount of iron leaching (<0.1%) from these materials.

Landfill leachate treatment by sequential combination of activated persulfate and Fenton oxidation.

This work assesses the feasibility of sequential persulfate and Fenton oxidation for the decolorization and mineralization of landfill leachate (5600 mg L-1 TOC; pH0: 8.6) in a continuous batch-recirculation system. Firstly, it was analyzed the role of the operational conditions upon the persulfate activation evaluating the effects of electrolysis, ilmenite (FeTiO3) as a source of Fe(II) and UV-LED (at 365 nm). The studied variables include current density (j) (50-200 mA cm-2), persulfate dose (46.8-234 mM) and mineral concentration (500-1500 mg L-1). The increase in j enhanced the hypochlorite generation and PS conversion to SO4- and, consequently, decolorization efficiency increasing the penetration of light through the solution and the photoreduction of Fe(III) to Fe(II) in the FeTiO3 surface. The combined electrolysis/FeTiO3/UV-LED showed synergetic effect compared to the individual processes, achieving mineralization around 53% under the optimum operating conditions (1 g L-1 of FeTiO3, using 234 mM of PS at 200 mA cm-2 under UV-LED radiation). The subsequent Fenton oxidation once the pH decreased up to around 3, led to overall mineralization above 90% after 480 min, confirming the suitability of this combined treatment to deal with recalcitrant and highly colored effluents.

Nanoscale Fe/Ag particles activated persulfate: optimization using response surface methodology.

This work studied the bimetallic nanoparticles Fe-Ag (nZVI-Ag) activated persulfate (PS) in aqueous solution using response surface methodology. The Box-Behnken design (BBD) was employed to optimize three parameters (nZVI-Ag dose, reaction temperature, and PS concentration) using 4-chlorophenol (4-CP) as the target pollutant. The synthesis of nZVI-Ag particles was carried out through a reduction of FeCl2 with NaBH4 followed by reductive deposition of Ag. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area. The BBD was considered a satisfactory model to optimize the process. Confirmatory tests were carried out using predicted and experimental values under the optimal conditions (50 mg L-1 nZVI-Ag, 21 mM PS at 57 °C) and the complete removal of 4-CP achieved experimentally was successfully predicted by the model, whereas the mineralization degree predicted (90%) was slightly overestimated against the measured data (83%).

Improving the Fenton process by visible LED irradiation.

The effect of irradiation with visible light-emitting diode (LED) light on the efficiency of Fenton oxidation is investigated using phenol as the target compound (100 mg/L). The H2O2 dose and temperature are tested as operating variables with the aim of minimizing consumption of the reagents. At 50 °C, 10 mg/L Fe2+, and 60 % of the stoichiometric H2O2 amount, phenol was completely oxidized into CO2, H2O, and short chain organic acids, with oxalic acid completely degraded. Up to 95 % mineralization was achieved. This high efficiency can be attributed to the effect of LED radiation on the quinones/Fe2+/Fe3+/H2O2 cycle, which significantly increases the reaction rate, as well as on the photodecomposition of the iron complexes formed along the oxidation process, which also enhanced mineralization.

Mineralization of naphtenic acids with thermally-activated persulfate: The important role of oxygen.

This study reports on the mineralization of model naphtenic acids (NAs) in aqueous solution by catalyst-free thermally-activated persulfate (PS) oxidation. These species are found to be pollutants in oil sands process-affected waters. The NAs tested include saturated-ring (cyclohexanecarboxylic and cyclohexanebutyric acids) and aromatic (2-naphthoic and 1,2,3,4-tetrahydro-2-naphthoic acids) structures, at 50mgL(-1)starting concentration. The effect of PS dose within a wide range (10-100% of the theoretical stoichiometric) and working temperature (40-97°C) was investigated. At 80°C and intitial pH=8 complete mineralization of the four NAs was achieved with 40-60% of the stoichiometric PS dose. This is explained because of the important contribution of oxygen, which was experimentally verified and was found to be more effective toward the NAs with a single cyclohexane ring than for the bicyclic aromatic-ring-bearing ones. The effect of chloride and bicarbonate was also checked. The former showed negative effect on the degradation rate of NAs whereas it was negligible or even positive for bicarbonate. The rate of mineralization was well described by simple pseudo-first order kinetics with values of the rate constants normalized to the PS dose within the range of 0.062-0.099h(-1). Apparent activation energy values between 93.7-105.3kJmol(-1) were obtained.

Electrochemical oxidation of landfill leachate in a flow reactor: optimization using response surface methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99% of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.

Application of intensified Fenton oxidation to the treatment of sawmill wastewater.

The application of the Fenton process for the treatment of sawmill wastewater has been investigated. The sawmill wastewater was characterized by a moderate COD load (≈3gL(-1)), high ecotoxicity (≈ 40 toxicity units) and almost negligible BOD/COD ratio (5×10(-3)) due to the presence of different fungicides such as propiconazole and 3-iodo-2-propynyl butyl carbamate, being the wastewater classified as non-biodegradable. The effect of the key Fenton variables (temperature (50-120°C), catalyst concentration (25-100 mg L(-1) Fe(3+)), H2O2 dose (1 and 2 times the stoichiometric dose) and the mode of H2O2 addition) on COD reduction and mineralization was investigated in order to fulfill the allowable local limits for industrial wastewater discharge and achieve an efficient consumption of H2O2 in short reaction times (1h). Increasing the temperature clearly improved the oxidation rate and mineralization degree, achieving 60% COD reduction and 50% mineralization at 120°C after 1h with the stoichiometric H2O2 dose and 25 mg L(-1) Fe(3+). The distribution of H2O2 in multiple additions throughout the reaction time was clearly beneficial avoiding competitive scavenging reactions and thus, achieving higher efficiencies of H2O2 consumption (XCOD ≈ 80%). The main by-products were non-toxic short-chain organic acids (acetic, oxalic and formic). Thus, the application of the Fenton process allowed reaching the local limits for industrial wastewater discharge into local sewer system at a relatively low cost.

Case study of the application of Fenton process to highly polluted wastewater from power plant.

This work investigates the application of Fenton process to the treatment of a highly polluted industrial wastewater resulting from the pipeline cleaning in a power plant. This effluent is characterized by a high chemical oxygen demand (COD>40 g/L), low biodegradability and quite a high iron concentration (around 3g/L) this coming from pipeline corrosion. The effect of the initial reaction temperature (between 50 and 90 °C) and the way of feeding H2O2 on the mineralization percentage and the efficiency of H2O2 consumption has been analyzed. With the stoichiometric amount of H2O2 relative to initial COD, fed in continuous mode, more than 90% COD reduction was achieved at 90 °C. That was accompanied by a dramatic improvement of the biodegradability. Thus, a combined treatment based on semicontinuous high-temperature Fenton oxidation (SHTF) and conventional aerobic biological treatment would allow fulfilling the COD and ecotoxicity regional limits for industrial wastewaters into de municipal sewer system. For the sake of comparison, catalytic wet air oxidation was also tested with poor results (less than 30% COD removal at 140 °C and 8 atm oxygen pressure).