Are iron chelates suitable to perform photo-Fenton at neutral pH for secondary effluent treatment?

There have been concerns about which iron chelate is most suitable for application in the photo-Fenton process as well as the fate of these chelates after application. In this study, five chelating agents, i.e. citric acid (CA), oxalic acid (OA), ethylenediamine disuccinic acid (EDDS), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), representing the most used iron chelates were assessed for suitability of application in homogeneous photo-Fenton-like process at pH of 7. The efficiency of the iron chelates were assessed in the disinfection of secondary effluent. The results for the disinfection and bacteria regrowth followed the order EDTA>OA>NTA>CA>OA. All the iron chelates were observed to have increased the COD of the effluent with EDDS having the highest COD contribution. The ability of the chelates to remove aromaticity was measured by the UV254 measurement. The efficiency of the chelates to remove aromaticity decreased in the order CA>EDDS>NTA>CA>OA. To determine the fate of the chelates, toxicity tests were conducted on the chelates before and after irradiation and the results revealed a decrease in toxicity after photoirradiation, implying the chelates were degraded and the products/intermediates produced were of less toxicity as compared to the parent compounds.

Integration of ozone, UV/H2O2 and GAC in a multi-barrier treatment for secondary effluent polishing: Reuse parameters and micropollutants removal.

Current studies tend to combine different advanced treatment technologies to reduce costs and increase efficiency. The objective of this work was to assess the combination of ozonation and UV/H2O2 with activated carbon adsorption for the removal of effluent quality parameters and micropollutants from secondary effluent samples. The experiments were carried out using the following configurations: O3 + GAC + O3 (1); O3 + GAC + UV/H2O2 (2); UV/H2O2 + GAC + O3 (3); UV/H2O2 + GAC + UV/H2O2 (4). Configurations 1, 3 and 4 were the most efficient for organic matter removal, while configuration 1 had the lowest cost on laboratory scale. An additional ultra-filtration membrane unit (UF) was tested at the end of configuration 1, which was optimized in terms of ozone doses for the removal of three organophosphate micropollutants in ultrapure water (TNBP, TCIPP and TPHP at 10 µgL-1). The best cost-effective configuration of this treatment train was the one using 1 mg L-1 of ozone before and after GAC, which achieved around 100% of micropollutants abatement. The role of each treatment to the final micropollutant removal was also discussed, being the first ozone treatment responsible for about 15% removal of the mixture of contaminants, while GAC was responsible for an additional 80% removal. The complete treatment train reached almost 100% of contaminants removal (under detection limit of the method), as well as added security to the system. The achieved results were also compared to international reuse legislations, proving that the combination of O3 and GAC was an interesting option to achieve enough quality for some reuse purposes.

A review on the use of chelating agents as an alternative to promote photo-Fenton at neutral pH: Current trends, knowledge gap and future studies.

In this review, we have critically examined the alternatives to conventional photo-Fenton process such as the strategies to perform it in circumneutral pH in the so-called photo-Fenton like process. They include iron chelation, iron replacement with another metal and use of iron immobilized on surfaces of solid materials, use of iron oxides, among others. The use of such strategies can be employed to overcome the challenges identified in conventional photo-Fenton, moreover, advantages and drawback of each technique must be clarified and the recent achievements should be shared with the scientific community. The use of a chelating agent to make iron soluble at circumneutral pH presents many advantages when compared to other current techniques. However, the correct understanding of the chelating process, complex activity and the complex resistance along with the mechanism of radical production should be taken into account to prepare an effective photo-Fenton with complexed iron. The review also identifies the current trends in chelate assisted photo-Fenton process and the unexplored areas in this field of study. A discussion about the environmental and safety issues in the application of these methods, with emphasis to the Fe chelation strategy, was also considered with detailed review over the past ten years.

Optimization of UV/H2O2 and ozone wastewater treatment by the experimental design methodology.

The objective of this study was to optimize UV/H2O2 and ozonation systems by means of an experimental design using as a response the efficiency of the operational conditions to remove the methylene blue (MB) dye. Two classes of experimental planning were used: the Doehlert matrix (DM) and the central composite design (CCD). The most important variables for each process were hydrogen peroxide concentration, the ratio of illuminated volume/total volume of the reactor and recirculation flow rate for UV/H2O2, and ozone flow rate, consumed ozone and MB concentration for the ozonation. The DM was more efficient in optimizing the systems, since it used a smaller number of experiments and achieved similar results when compared to the CCD. After optimization, the disinfection efficiency of the systems was tested with secondary effluent evaluating the inactivation of microbiological indicators, Escherichia coli and total coliforms, using the optimized and the worst condition previously obtained with MB removal as response. The inactivation efficiencies in the optimum conditions were about 99%, allowing an efficient disinfection as well as the production of an effluent with quality to be reused according to specific legislations, while at the worse conditions, the inactivation did not reach standards for reuse.

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.

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.

Kinetic studies of the reaction between pesticides and hydroxyl radical generated by laser flash photolysis.

BACKGROUND: Due to contamination of the environment by pesticides and their mishandling, there is the need for treatment of contaminated sites and correct disposal of materials containing them. Thus, studies with advanced oxidation processes are expanding and can determine the rate constant of the hydroxyl radical with organic compounds of great importance in environmental contamination. In this context, the use of laser flash photolysis has been shown to be viable for the determination of these constants. RESULTS: The reaction rate constants of different pesticides with HO(•) in degassed acetonitrile have been determined. They were 1.6 × 10(9) M(-1) s(-1), 0.6 × 10(9) M(-1) s(-1), 1.2 × 10(9) M(-1) s(-1), 2.4 × 10(9) M(-1) s(-1) and 2.2 × 10(9) M(-1) s(-1) for the pesticides carbaryl, propoxur, fenoxycarb, ethoxysulfuron and chlorimuron-ethyl, respectively. These values are about an order of magnitude smaller than the diffusion controlled rate and correlate with the relative rates of disappearance of the pesticides in the photo-Fenton reaction in water. CONCLUSION: The correlation of the relative rate constants determined by laser flash photolysis with the relative rates of photo-Fenton degradation of the pesticides is compelling evidence for the participation of the hydroxyl radical in the degradation of these pesticides in the latter system.

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 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

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.

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.

Assessment of cationic surfactants mineralization by ozonation and photo-Fenton process.

Aqueous solutions of two important quaternary ammonium compounds--16-BAC (benzyl-dimethyl-hexadecylammonium-chloride) and 18-BAC (benzyl-dimethyl-stearylammonium-chloride)--were treated by the ozonation and photo-Fenton processes at different ozone doses and hydrogen peroxide concentrations, respectively. During the photo-Fenton experiments, two different types of lamps were used--a UV mercury vapor medium pressure lamp and a xenon lamp, which simulates solar radiation. The total organic carbon removal was monitored to follow the mineralization of the surfactants. According to the experimental results, after 90 minutes of treatment, the photo-Fenton process achieved up to 80% of mineralization when the UV lamp was used. The efficiency of the photo-Fenton with the xenon lamp was lower. The ozonation process reached, at most, 50% mineralization at the used conditions (ozone dose = 7.57 g/h).

Sulfamethoxazole abatement by means of ozonation.

Sulfamethoxazole (SMX) is a bacteriostatic antibiotic largely used for diverse types of illness. Its widely use in humans and even in animals releases unmetabolized and active metabolites that have a strong potential in terms of effect in organisms. In this work, 200 mg L(-1) solution of sulfamethoxazole was treated by ozonation at different pH. Results showed that ozonation was proved to be an efficient method to degrade sulfamethoxazole. After 15 min of ozonation (corresponding dose=0.4 g of ozone L(-1)), the complete antibiotic abatement was almost achieved with just 10% of mineralization. The biodegradability and toxicity of the ozonation intermediates were also studied. A biodegradability enhancement (increment of BOD(5)/COD ratio) from 0 to 0.28 was observed after 60 min of ozonation. The acute toxicity of the intermediates was followed by the Microtox test and the toxicity profile showed a slight acute toxicity increment in the first stage of ozonation. The pH variation had an important role in the TOC and COD removal, promoting their growth with the increment of alkalinity. The second order kinetic constants for the ozonation of the SMX in an order of magnitude of 10(5) L mol(-1)s(-1) were also determined for pH 5 and 7.

Bezafibrate removal by means of ozonation: primary intermediates, kinetics, and toxicity assessment.

Bezafibrate (BZF) is a lipid regulator largely used for the treatment of hyperlipidaemia. As a result of its wide use, unmetabolized BZF is released in the environment with potential toxic effects for aquatic living organisms. The results obtained in this work show that ozonation is an efficient method to degrade BZF: after 10 min of treatment (corresponding to a dose of 0.73 mmol L(-1) of ozone), the complete BZF abatement is achieved, starting from an initial concentration of 0.5 mmol L(-1). However, only a small part of the substrate is mineralized. Two different experimental approaches (absolute and competition method) are adopted to estimate the second-order kinetic constants for the ozone attack at pH=6.0, 7.0 and 8.0. A good agreement was observed between the two kinetic methods adopted. The identification of main intermediates, attempted by high-performance liquid chromatograph (HPLC)-MS technique, indicates that the oxidation of BZF develops through both the hydroxylation of the aromatic ring and the attack of ozone on the unchlorinated aromatic one. The assessment of by-products biodegradability and acute toxicity demonstrates that ozonation is a suitable technique to improve the biodegradability and reduce the toxicity of waters containing BZF.