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Modified TiO 2 catalysts are of interest in environmental water remediation since they can lead to efficient electron-hole separation and greatly enhance the photocatalytic properties of TiO 2 . Reactive oxygen species (ROS), such as the superoxide radical (O 2 - ), hydroxyl radical (OH), and positive valence band holes (h + VB ), have been reported as the main oxidative species involved in photocatalytic degradation processes. In this work, the role of these species using TiO 2 , TiO 2 /Pt 0.5 wt%, and TiO 2 /Ag 10 wt% has been examined in order to clarify the oxidation pathways. For this purpose, the contribution of the main oxidative species was analyzed in the photocatalytic degradation of dichloroacetic acid (DCA) solutions using specific scavengers (benzoquinone, tert-butyl alcohol, and formic acid). Moreover, the hydroxyl radicals were quantitatively determined in order better understand the results. Regardless of the catalyst used, it is concluded that OH radicals are the major reactive species responsible for DCA degradation and no significant degradation is due to O 2 - radicals. Nevertheless, different OH generation pathways were found, depending on the nature of the catalysts. Degradation using TiO 2 was conducted mainly via OH radicals generated in the positive holes, while noble metal-doped TiO 2 catalysts generated OH radicals through the transformation of O 2 - radicals., (Copyright © 2018. Published by Elsevier B.V.)

5-Chloro-2-(2,4-dichlorophenoxy)phenol (TCS) is a persistent organic pollutant (POP) widely used in different consumer goods. Its recalcitrant nature demands the application of effective remediation technologies in order to avoid the negative environmental impact associated to the discharge of contaminated waters. Although advanced oxidation technologies have been considered the best alternative to destroy bio-recalcitrant compounds, the likely formation of high toxicity byproducts must be analysed before large-scale deployment. In this work, we aim to trace the presence of chlorinated compounds during the electro-oxidation of aqueous TCS samples. First, we analyze the influence of the initial concentration of TCS on the toxicity of the oxidation medium expressed by the International-Toxicity Equivalency Factor (I-TEF); second, we have detected the formation of intermediate organo-chlorinated compounds by GC-MS supported by HPLC and finally, we have quantified the concentration of highly-polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by HRGC-HRMS within the oxidation treatment. In those samples where TCS had been completely degraded the concentration of PCDD/Fs showed a high increase, especially when NaCl was used as electrolyte, with the initial concentration of TCS. Under these conditions the I-TEF achieved values up to 3.8 × 10 2  pg L -1 ., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The inherent resistance of perfluoroalkyl substances (PFASs) to biological degradation makes necessary to develop advanced technologies for the abatement of this group of hazardous substances. The present work investigated the photocatalytic decomposition of perfluorooctanoic acid (PFOA) using a composite catalyst based on TiO 2 and reduced graphene oxide (95% TiO 2 /5% rGO) that was synthesized using a facile hydrothermal method. The efficient photoactivity of the TiO 2 -rGO (0.1gL -1 ) composite was confirmed for PFOA (0.24mmolL -1 ) degradation that reached 93±7% after 12h of UV-vis irradiation using a medium pressure mercury lamp, a great improvement compared to the TiO 2 photocatalysis (24±11% PFOA removal) and direct photolysis (58±9%). These findings indicate that rGO provided the suited properties of TiO 2 -rGO, possibly as a result of acting as electron acceptor and avoiding the high recombination electron/hole pairs. The release of fluoride and the formation of shorter-chain perfluorocarboxilyc acids, that were progressively eliminated in a good match with the analysed reduction of total organic carbon, is consistent with a step-by-step PFOA decomposition via photogenerated hydroxyl radicals. Finally, the apparent first order rate constants of the TiO 2 -rGO UV-vis PFOA decompositions, and the intermediate perfluorcarboxylic acids were found to increase as the length of the carbon chain was shorter., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Abiotic and biotic processes can be used to remediate DDX (DDT, DDD, DDE, and DDNS) contaminated soils; these processes can be fostered using specific carbon-amendments to stimulate particular soil indigenous microbial communities to improve rates or extent of degradation. In this study, toluene and glycerol were evaluated as cosubstrates under aerobic and anoxic conditions to determine the degradation efficiencies of DDX and to elucidate possible degradation mechanisms. Slurry microcosms experiments were performed during 60 days using pretreated soil with zero-valent iron (ZVI). Toluene addition enhanced the percentage of degradation of DDX. DDNS was the main compound degraded (around 86%) under aerobic conditions, suggesting cometabolic degradation of DDX by toluene-degrading soil bacteria. Glycerol addition under anoxic conditions favored the abiotic degradation of DDX mediated by sulfate-reducing bacteria activity, where DDT was the main compound degraded (around 90%). The 16S rDNA metagenomic analyses revealed Rhodococcus ruber and Desulfosporosinus auripigmenti as the predominant bacterial species after 40 days of treatment with toluene and glycerol additions, respectively. This study provides evidence of biotic and abiotic DDX degradation by the addition of toluene and glycerol as cosubstrates in ZVI pretreated DDX-contaminated soil., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This work assesses the influence of the operating conditions H2O2 dose (20 or 100% of the stoichiometric amount), temperature (20 or 70°C), and the presence of chloride in the oxidation medium in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during Fenton treatment of aqueous samples of 2-chlorophenol, 2-CP, one of the strongest precursor of PCDD/Fs. After 4h of oxidation in the experiments carried out with 20% H2O2 chlorinated phenoxyphenols and biphenyls, which are intermediates in PCDD/Fs formation, as well as PCDD/Fs were observed, resulting in concentrations 11 times higher than in the untreated sample. Additionally, when NaCl was also present in the reaction medium, PCDD/Fs were formed at higher extent, with a total concentration 74.4 times higher than in the untreated 2-CP solution. Results depicted a preferential formation of PCDFs over PCDDs, with dominance of lower chlorinated PCDD/Fs (tetra and penta-PCDD/Fs). Besides, the formation of the most toxic PCDD/Fs congeners (2,3,7,8-PCDD/Fs) was not favored under the operating conditions used in this work., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This work reports the feasibility of applying emulsion pertraction technology (EPT) aiming at zinc recovery and waste minimization in the zinc electroplating processes that include Cr (III) passivation. The assessment consists of firstly the lifetime extension of the passivation baths by selective removal of the tramp ions zinc and iron, and secondly, the recovery of zinc for further reuse. Spent passivation baths from a local industry were tested, being the major metallic content: Cr(3+) 9000mg L(-1), Zn(2+) 12,000mg L(-1), Fe(3+) 100mg L(-1). Working in a Liqui-Cel hollow fiber membrane contactor and using the extractant bis(2,4,4-trimethylpentyl) phosphinic acid, reduction of zinc and iron concentrations below 60mg L(-1) and 2mg L(-1), respectively were obtained, while trivalent chromium, the active metal that generates the passivation layer, was retained in the baths. Zinc was selectively transferred to an acidic stripping phase that in the experimental time reached a concentration of 157,000mg L(-1). Zinc recovery by electrowinning from the acidic stripping phase without any pretreatment of the electrolyte solution provided a purity of 98.5%, matching the lower commercial zinc grade. As a result of the extension of the life time of the passivation bath, significant environmental advantages are derived such as minimization of the volume of hazardous wastes and savings in the consumption of raw materials., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Kinetic data regarding COD oxidation were measured in a laboratory scale cell and used to scale-up an electro-oxidation process for landfill leachate treatment by means of boron-doped diamond anodes. A pilot-scale reactor with a total BDD anode area of 1.05 m(2) was designed. Different electrode gaps in the laboratory and pilot plant cells resulted in dissimilar reactor hydrodynamics. Consequently, generalised dimensionless correlations concerning mass transfer were developed in order to define the mass transfer conditions in both electrochemical systems. These correlations were then used in the design equations to validate the scale-up procedure. A series of experiments with biologically pre-treated landfill leachate were done to accomplish this goal. The evolution of ammonia and COD concentration could be well predicted., (Copyright 2010 Elsevier B.V. All rights reserved.)

This paper reports the integration of advanced and conventional technologies to deal with the treatment of landfill leachates. The raw leachate, with average values of COD=4430 mg/L and N-NH(4)(+)=1225 mg/L, was first treated on site by an activated sludge large-scale process reducing the former parameters to 1750 mg/L (av.) of COD and 750 mg/L (av.) of N-NH(4)(+). Next, 50 L/h of the effluent were pumped to a pilot plant that included Fenton oxidation followed by an electrooxidation unit, provided with boron doped diamond anodes (anode area=1.05 m(2)); almost complete removal of the organic matter and ammonium nitrogen was achieved. Comparison of the results with those obtained in the laboratory (70 cm(2) of anode area) was performed observing a similar performance in the kinetics of COD removal, while differences were found in the ammonium removal rates. The specific energy consumption necessary to electro-oxidize the organic load below the disposal limit (COD<160 mg/L) at pilot plant scale was 35 kWh/m(3).

Treatment of landfill leachates by electrochemical oxidation led to the complete removal of chemical oxygen demand and ammonium nitrogen. However, as result of the ammonium oxidation, the partial formation of nitrate ions was observed. Ion exchange technology was investigated as a polishing step in the treatment of landfill leachates. Removal of nitrate from aqueous solutions was studied using two selective anion exchangers: Purolite A 520E and Purolite A 300, under a fixed bed configuration. The following aspects of the ion exchange system were experimentally analyzed: (i) the influence of the presence of other competitive anions in solution, sulfate and chloride, during the loading step, (ii) the breakthrough point and resin saturation as a function of chloride concentration in the feed stream and, (iii) the efficiency of the regeneration step working with NaCl solutions at several concentrations. After a comparison of the experimental results, it was concluded that the resin Purolite A 300 showed a better behavior. Experimental analysis of the equilibrium isotherms made it possible to determine the equilibrium constant (K=3.21) and the maximum capacity (q(max)=183mgg(-1)), important parameters in the design of the treatment process.

Advanced oxidation processes (AOPs), namely photo-Fenton, Fenton-like, Fenton and UV/H(2)O(2), have been investigated in the removal of organic matter and colour from landfill leachates. The leachate was characterised by high COD, low biodegradability and intense dark colour. Evaluation of COD removal as a function of the operation variables (H(2)O(2), Fe(2+), Cu(2+), UV) led to results that ranged between 30% and 77% and it was observed that the removal efficiencies decreased in the order: photo-Fenton>Fenton-like>Fenton>UV/H(2)O(2)>UV. Thus, a detailed experimental analysis was carried out to analyse the effect of the hydrogen peroxide and iron concentrations and the number of reagent additions in the photo-Fenton process, observing that: (i) the COD removal ranged from 49% to 78% depending on the H(2)O(2) dose, (ii) the total amount of organic matter removed was increased by adding the reagent in multiple steps (86%), (iii) iron concentration corresponding to a Fe(2+)/COD mass ratio=0.33 was found to be the most favourable and, (iv) after a neutralization step, the colour and residual concentrations of iron and H(2)O(2) were practically negligible in the final leachate solution.

The feasibility of removing ammonium from landfill leachates by electrochemical oxidation was studied. Raw leachates and biologically/physico-chemically pretreated leachates from a municipal landfill site were treated. Boron doped diamond was used as anode and stainless steel as cathode, both electrodes with an area of 70 cm(2). The effects of the applied current density (15-90 mA cm(-2)), the initial ammonium concentration (480-2000 mg L(-1)), and the initial chloride concentration were experimentally studied. Total ammonium removal was obtained after 360 min of processing and almost half of the initial ammonium nitrogen was oxidized to nitrate. On the other hand, the concentration of chloride enhanced the rate of ammonium oxidation. In addition, the amount of N-NH(4)(+) transformed into N-NO(3)(-) decreased when additional chloride was provided.