Renato F. Dantas

Assessment of iron chelates efficiency for photo-Fenton at neutral pH

In this study, homogeneous photo-Fenton like at neutral pH was applied to remove sulfamethoxazole from water. The process was performed using different chelating agents in order to solubilize iron in a neutral water solution. The chelating agents tested were: ethylenediaminetetraacetic acid (EDTA); nitrilotriacetic acid (NTA); oxalic acid (OA) and tartaric acid (TA). The iron leaching was monitored over reaction time to evaluate the chelates stability and their resistance to HO· and UV-A radiation. Chelates of EDTA and NTA presented more stability than OA and TA, which also confirmed their higher efficiency. Total Organic Carbon (TOC) analyses were also performed to evaluate the contribution in terms of solution contamination related to the use of chelating agents. The better properties of biodegradability in respect of EDTA combined with better efficiency in terms of microcontaminant removal and the smallest TOC contribution indicate that NTA could represent a useful option to perform photo-Fenton processes at neutral pH.

Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants

This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All target OPFRs were detected in the WWTPs influents, and the total concentration ranged from 3.67 µg L(-1) to 150 µg L(-1). During activated sludge treatment, most OPFRs were accumulated in the sludge at concentrations from 35.3 to 9980 ng g(-1) dw. Chlorinated compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2,3-dichloropropyl) phosphate (TDCPP) were not removed by the conventional activated sludge treatment and they were released by the effluents at approximately the same inlet concentration. On the contrary, aryl compounds tris(methylphenyl) phosphate (TMPP) and 2-ethylhexyl diphenyl phosphate (EHDP) together with alkyl tris(2-ethylhexyl) phosphate (TEHP) were not detected in any of the effluents. Advanced oxidation processes (UV/H2O2 and O3) were applied to investigate the degradability of recalcitrant OPFRs in WWTP effluents. Those detected in the effluent sample (TCEP, TCIPP, TDCPP, tributyl phosphate (TNBP), tri-iso-butyl phosphate (TIBP) and tris(2-butoxyethyl) phosphate (TBOEP)) had very low direct UV-C photolysis rates. TBOEP, TNBP and TIBP were degraded by UV/H2O2 and O3. Chlorinated compounds TCEP, TDCPP and TCIPP were the most recalcitrant OPFR to the advanced oxidation processes applied. The study provides information on the partitioning and degradability pathways of OPFR within conventional activated sludge WWTPs.

Evaluation of copper slag to catalyze advanced oxidation processes for the removal of phenol in water

The aim of this work was to evaluate the use of copper slag to catalyze phenol degradation in water by advanced oxidation processes (AOPs). Copper slag was tested in combination with H(2)O(2) (slag/H(2)O(2)) and H(2)O(2)/UV (slag/H(2)O(2)/UV). The studied methods promoted the complete photocatalytic degradation of phenol. Besides, they were able to reduce about 50% the TOC content in the samples. Slag/H(2)O(2)/UV and slag/H(2)O(2) treatments have favored biodegradability increment along the reaction time. Nevertheless, the irradiated method achieved higher values of the biodegradability indicator (BOD(5)/TOC). The toxicity assessment indicated the formation of more toxic compounds in both treatments. However, the control of the reaction time would minimize the environmental impact of the effluents.

Ozonation of Propranolol: Transformation, Biodegradability, and Toxicity Assessment

This work studies the ozonation of the pharmaceutical propranolol (PRO) in aqueous solution. Experimental results demonstrated that ozonation was an efficient method to remove PRO, achieving its complete abatement after 8xa0min of treatment (ozone dose of 0.47u2009u2009mmolu2009L-1), starting from a PRO initial concentration of 0.38u2009u2009mmolu2009L-1. The total organic carbon (TOC) analysis indicated that 1xa0h of ozonation (ozone dose of 3.54u2009u2009mmolu2009L-1) was able to achieve only about 5% of the total organic carbon removal. The ozonation of PRO aqueous solutions has not promoted a prompt increase of the ratio of biological oxygen demand to chemical oxygen demand, thus indicating the need for higher ozone doses to initiate the biodegradability enhancement. The acute toxicity increased in the first minutes of reaction with a posterior reduction to values slightly higher than the toxicity of the PRO raw solution. Some early intermediate structures were proposed, and finally, kinetic constants for the direct attack of ozone on PRO s...

Synthesis and characterization of TiO2 and TiO2/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol–gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0xa0% silver exhibited superior photocatalytic activity for MV degradation.

Application of Different Advanced Oxidation Processes for the Degradation of Organic Pollutants

Water is not only an economic, but also an increasingly important social commodity. Potable water is an essential resource for sustaining economic and social development in all sectors. A safe water supply and appropriate sanitation are the most essential components for a healthy and prosperous life. However, increases in human activities have led to exposure of the aqueous environment to chemical, microbial and biological pollutants as well as to micropollutants. Thus, liquid effluents containing toxic substances are generated by a variety of chemistry-related industrial processes, as well as by a number of common household or agricultural applications.

Solar photo-Fenton treatment of petroleum extraction wastewater

Abstract The purpose of this study is to investigate the treatment of petroleum-extraction wastewater by means of a photo-Fenton like process using sunlight as irradiation source. According to the experimental results, a reduction of the wastewater UV absorption spectral intensity indicates that polycyclic aromatic hydrocarbons and aromaticity removal of approximately 92.7 and 96.2%, respectively, were obtained after 7u2009h of sunlight exposure using 485.3u2009mmolu2009L−1 of hydrogen peroxide. For the investigated treatment condition, the H2O2 optimum concentration was 485.3u2009mmolu2009L−1 since an increment in H2O2 concentration did not promote a significant increment in treatment efficiency. H2O2 single oxidation was also important during the photo-Fenton treatment. A moderate level of mineralization was also observed. Finally, photo-Fenton process using sunlight was able to reduce sample acute phytotoxicity by about 50%.

Role of oxygen and DOM in sunlight induced photodegradation of organophosphorous flame retardants in river water

The wide use of organophosphorous flame retardants (OPFR) and plasticizers causes a continuous release of large quantities into natural waters. One of the main contributors to micropollutants depletion in surface water is sunlight induced phototransformations. This study aims to elucidate whether alkyl, chloroalkyl and aryl organophosphorus flame retardants undergo phototransformations in river water. To perform the experiments, nine OPFR were subjected to natural sunlight, Xe lamp (simulated sunlight) and UV-C irradiations in ultra-pure Milli-Q water, Milli-Q water with humic acid and river water. Experiments demonstrated that OPFR achieve an important degree of photodegradation noticeable at long irradiation time, although direct photolysis did not account as the main photodegration mechanism. Results indicated that sunlight absorbing OPFR exhibited photosensitizing activity. The presence of azide in ultra- pure water inhibited some OPFR photodegration by singlet oxygen (1O2) scavenging, and the absence of dissolved oxygen significantly depleted most of OPFR removal. In the conditions studied, humic acid inhibited OPFR phototransformations, while river water enhanced their removal. Results from this study point out the need to further investigate the role of some OPFR as photosensitizers, which are important for fate and ecological risk assessment of flame retardants and other micropollutants in water.

Tolfenamic acid degradation by direct photolysis and the UV-ABC/H2O2 process: factorial design, kinetics, identification of intermediates, and toxicity evaluation.

This study employed direct UV-ABC photolysis and the UV-ABC/H2O2 process to investigate the degradation of tolfenamic acid (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 23 factorial design with added center point was used to evaluate the effect of three independent variables-namely, H2O2 concentration ([H2O2]), TA concentration ([TA]), and experiment time (time)-on TA degradation and H2O2 photolysis during UV-ABC/H2O2 treatment using a high-pressure mercury vapor lamp (photon flux of 2.6307 × 104 J s-1) as the UV irradiation source. The responses yielded similar values, revealing a linear behavior, with correlation coefficients R = 0.9968 and Radj = 0.9921 for TA degradation and R = 0.9828 and Radj = 0.9570 for H2O2 photolysis. The most efficient combination of variables was [H2O2] = 255 mg L-1 and [TA] = 25 mg L-1, resulting in 100% TA degradation and 98.87% H2O2 photolysis by 90 min of treatment. Additionally, the second-order kinetic constant of the reaction between TA and HO● was determined using a competitive kinetic model, employing 2,4-dichlorophenoxyacetic acid (2,4D) as the reference compound. The kinetic constant was 1.9 × 1010 M-1 s-1 in alkaline medium. TA degradation by direct photolysis generated quinone imines as by-products, responsible for the formation of a dark red internal filter that increased the value of acute toxicity to Artemia salina. The UV-ABC/H2O2 process did not promote formation of quinone imines by 90 min of treatment and therefore did not increase acute toxicity values. Several by-products generated during TA degradation were identified and possible degradation pathways for the UV-ABC and UV-ABC/H2O2 processes were proposed.

Ozone/H2O2 Performance on the Degradation of Sulfamethoxazole

This work aims to analyze the contribution of H2O2 on ozonation of Sulfamethoxazole (SMX). A single ozonation was able to totally remove SMX. TOC and COD depletion rates after a transferred ozone dose of 60 mg/L was related to the formation and decomposition of H2O2. An increase on O3 gas inlet concentration from 10 g/m3 to 20 g/m3 improved COD abatement from 11% to 36%. When the presence of H2O2 at the beginning of ozonation was tested, it was verified that COD and TOC degradation were enhanced, attaining maximum values of 76% and 32%, respectively, when compared with 35% and 15% reached in a single ozonation.