I. Oller

Combination of Advanced Oxidation Processes and biological treatments for wastewater decontamination—A review

Nowadays there is a continuously increasing worldwide concern for development of alternative water reuse technologies, mainly focused on agriculture and industry. In this context, Advanced Oxidation Processes (AOPs) are considered a highly competitive water treatment technology for the removal of those organic pollutants not treatable by conventional techniques due to their high chemical stability and/or low biodegradability. Although chemical oxidation for complete mineralization is usually expensive, its combination with a biological treatment is widely reported to reduce operating costs. This paper reviews recent research combining AOPs (as a pre-treatment or post-treatment stage) and bioremediation technologies for the decontamination of a wide range of synthetic and real industrial wastewater. Special emphasis is also placed on recent studies and large-scale combination schemes developed in Mediterranean countries for non-biodegradable wastewater treatment and reuse. The main conclusions arrived at from the overall assessment of the literature are that more work needs to be done on degradation kinetics and reactor modeling of the combined process, and also dynamics of the initial attack on primary contaminants and intermediate species generation. Furthermore, better economic models must be developed to estimate how the cost of this combined process varies with specific industrial wastewater characteristics, the overall decontamination efficiency and the relative cost of the AOP versus biological treatment.

Decontamination industrial pharmaceutical wastewater by combining solar photo-Fenton and biological treatment

Characterization and treatment of a real pharmaceutical wastewater containing 775 mg dissolved organic carbon per liter by a solar photo-Fenton/biotreatment were studied. There were also many inorganic compounds present in the matrix. The most important chemical in this wastewater was nalidixic acid (45 mg/L), an antibiotic pertaining to the quinolone group. A Zahn-Wellens test demonstrated that the real bulk organic content of the wastewater was biodegradable, but only after long biomass adaptation; however, the nalidixic acid concentration remained constant, showing that it cannot be biodegraded. An alternative is chemical oxidation (photo-Fenton process) first to enhance biodegradability, followed by a biological treatment (Immobilized Biomass Reactor--IBR). In this case, two studies of photo-Fenton treatment of the real wastewater were performed, one with an excess of H2O2 (kinetic study) and another with controlled H2O2 dosing (biodegradability and toxicity studies). In the kinetic study, nalidixic acid completely disappeared after 190 min. In the other experiment with controlled H2O2, nalidixic acid degradation was complete at 66 mM of H2O2 consumed. Biodegradability and toxicity bioassays showed that photo-Fenton should be performed until total degradation of nalidixic acid before coupling a biological treatment. Analysis of the average oxidation state (AOS) demonstrated the formation of more oxidized intermediates. With this information, the photo-Fenton treatment time (190 min) and H2O2 dose (66 mM) necessary for adequate biodegradability of the wastewater could be determined. An IBR operated in batch mode was able to reduce the remaining DOC to less than 35 mg/L. Ammonium consumption and NO3- generation demonstrated that nitrification was also attained in the IBR. Overall DOC degradation efficiency of the combined photo-Fenton and biological treatment was over 95%, of which 33% correspond to the solar photochemical process and 62% to the biological treatment.

Application of solar AOPs and ozonation for elimination of micropollutants in municipal wastewater treatment plant effluents.

Conventional municipal wastewater treatment plants are not able to entirely degrade some organic pollutants that end up in the environment. Within this group of contaminants, Emerging Contaminants are mostly unregulated compounds that may be candidates for future regulation. In this work, different advanced technologies: solar heterogeneous photocatalysis with TiO(2), solar photo-Fenton and ozonation, are studied as tertiary treatments for the remediation of micropollutants present in real municipal wastewater treatment plants effluents at pilot plant scale. Contaminants elimination was followed by Liquid Chromatography/Quadrupole ion trap Mass Spectrometry analysis after a pre-concentration 100:1 by automatic solid phase extraction. 66 target micropollutants were identified and quantified. 16 of those contaminants at initial concentrations over 1000 ng L(-1), made up over 88% of the initial total effluent pollutant load. The order of micropollutants elimination efficiency under the experimental conditions evaluated was solar photo-Fenton > ozonation > solar heterogeneous photocatalysis with TiO(2). Toxicity analyses by Vibrio fischeri and respirometric tests showed no significant changes in the effluent toxicity after the three tertiary treatments application. Solar photo-Fenton and ozonation treatments were also compared from an economical point of view.

Degradation of a four-pesticide mixture by combined photo-Fenton and biological oxidation.

Complete degradation of a pesticide mixture by a combination of a photo-Fenton pretreatment and an activated-sludge batch reactor is demonstrated. Four commercial pesticides, Laition, Metasystox, Sevnol and Ultracid were chosen for this experiment. The active ingredients are, respectively, dimethoate, oxydemeton-methyl, carbaryl and methidathion. The original pesticide concentration was 200 mg L(-1). Biotreatment began after 31% photocatalytic mineralization, which after 5 h in a 6-L stirred batch-mode tank reactor with non-acclimated activated sludge, leaves the photo-Fenton effluent completely degraded. This biotreatment time is shorter than commonly found in municipal wastewater treatment plants (approximately 8-10 h). Therefore, the combined process is effective for rapid pesticide degradation in wastewater with complete removal of parent compounds and the associated DOC concentration. Nonetheless, assessment of this technology should take into account higher pesticide concentrations and how this factor affects both the photocatalytic and the biological oxidation.

Mature landfill leachate treatment by coagulation/flocculation combined with Fenton and solar photo-Fenton processes

This work reports the treatment of a mature landfill leachate through the application of chemical-based treatment processes in order to achieve the discharge legal limits into natural water courses. Firstly, the effect of coagulation/flocculation with different chemicals was studied, evaluating the role of different initial pH and chemicals concentration. Afterwards, the efficiency of two different advanced oxidation processes for leachate remediation was assessed. Fenton and solar photo-Fenton processes were applied alone and in combination with a coagulation/flocculation pre-treatment. This physicochemical conditioning step, with 2 g L(-1) of FeCl3 · 6H2O at pH 5, allowed removing 63% of COD, 80% of turbidity and 74% of total polyphenols. Combining the coagulation/flocculation pre-treatment with Fenton reagent, it was possible to reach 89% of COD removal in 96 h. Moreover, coagulation/flocculation combined with solar photo-Fenton revealed higher DOC (75%) reductions than single solar photo-Fenton (54%). In the combined treatment (coagulation/flocculation and solar photo-Fenton), it was reached a DOC reduction of 50% after the chemical oxidation, with 110 kJ L(-1) of accumulated UV energy and a H2O2 consumption of 116 mM. Toxicity and biodegradability assays were performed to evaluate possible variations along the oxidation processes. After the combined treatment, the leachate under study presented non-toxicity but biodegradability increased.

A comparative study of different tests for biodegradability enhancement determination during AOP treatment of recalcitrant toxic aqueous solutions

Four biodegradability tests (Pseudomonas putida bioassay, Zahn-Wellens test, BOD5/COD ratio and respirometry assay) have been used to determine the biodegradability enhancement during the treatment of wastewater containing 200 mg L(-1) of dissolved organic carbon (DOC) of a five commercial pesticides mixture (Vydate, Metomur, Couraze, Ditumur and Scala) by an advanced oxidation process (AOP). A comparative study was carried out taking into account repeatability and precision of each biodegradability test. Solar photo-Fenton was the AOP selected for pesticide degradation up to three levels of mineralization: 20%, 40% and 60% of initial DOC. Intra- and interday precisions were evaluated conducting each biodegradability test by triplicate and they were applied three times on different dates over a period of three months. Fishers least significant difference method was applied to the means, P. putida and Zahn-Wellens tests giving higher repeatability and precision. The P. putida test requires a shorter time to obtain reliable results using a standardized inoculum and constitutes a worthwhile alternative to estimate biodegradability in contrast to other less accurate or more time consuming methods.

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.

Solar treatment of cork boiling and bleaching wastewaters in a pilot plant

This paper reports on cork boiling and bleaching wastewaters treatment by solar photocatalytic processes, TiO(2)/UV and Fe(2+)/H(2)O(2)/UV (TiO(2)-only for bleaching wastewater), in a pilot plant with compound parabolic collectors. The photo-Fenton reaction (k=0.12L/kJ(UV), r(0)=59.4 mg/kJ(UV)) is much more efficient that TiO(2) photocatalysis and TiO(2)+S(2)O(8)(2-) (k=0.0024 L/kJ(UV), r(0)=1.36 mg/kJ(UV)), leading to 94% mineralization of the bleaching wastewater after 31.5 kJ(UV)/L, consuming 77.1mM of H(2)O(2) (3.0 mmol/kJ(UV)) and using 20 mg/L of iron. For the cork boiling wastewater, after a slow initial reaction rate, the DOC degradation curve shows a first-order kinetics behaviour (k=0.015 L/kJ(UV), r(0)=20.8 mg/kJ(UV)) until 173 kJ(UV)/L ( approximately 300 mgC/L). According to the average oxidation state (AOS), toxicity profiles, respirometry and kinetic results obtained in two solar CPCs plants, the optimal energy dose estimated for phototreatment to reach a biodegradable effluent is 15 kJ(UV)/L and 114 kJ(UV)/L, consuming 33 mM and 151 mM of H(2)OT:/PGN/ELSEVIER/WR/web/00007490/(2), achieving almost 49% and 48% mineralization of the wastewaters, respectively for the cork bleaching and boiling wastewaters.

Combination of nanofiltration and ozonation for the remediation of real municipal wastewater effluents: Acute and chronic toxicity assessment.

The purpose of this work was to study the ozonation of nanofiltration (NF) retentates of real municipal wastewater treatment plant (MWTP) effluents for removal of microcontaminants (MCs) and toxicity. MCs present in these effluents were monitored using LC-MS/MS. Acute and chronic toxicity was addressed with Daphnia magna, Vibrio fischeri and Selenastrum capricornutum. Up to 40 MCs were found, most of them in concentrations over 100ng/L. 90% degradation of the sum of MCs was the critical point of comparison. When the NF membrane system was applied to MWTP effluents, treatment of NF rejection needed 2.75-4.5g O3/m3,4.5g O3/m3, which is less than 50% of the ozone needed for direct treatment of MWTP effluent. Treatment time (lower than 11min) was not influenced by MCs concentration, at least in the range tested (25-190μg/L). It has been demonstrated that consumption of ozone increased with organic load and inorganic content of different real effluents. MCs were eliminated by ozonation but acute toxicity (against V. fischeri and D. magna) increased. Chronic toxicity results were different and contrary in D. magna and S. capricornutum, due to the generation of new transformation products more toxic to D. magna than the parent contaminants. S. capricornutum inhibition percentage decreased in all cases after ozonation treatment. According to these results, before ozonation is implemented in MWTPs for the removal of MCs, the transformation products must first be examined and the treatment time or ozone doses should be extended to complete degradation if necessary.

Photolytic and photocatalytic transformation of methadone in aqueous solutions under solar irradiation: Kinetics, characterization of major intermediate products and toxicity evaluation

The present manuscript describes the transformation and mineralization of methadone (MET) in aqueous solutions (demineralized water (DW) and synthetic municipal wastewater effluent (SWeff)) by natural solar irradiation and two solar photocatalytic processes: heterogeneous photocatalysis with titanium dioxide (TiO2) and homogeneous photocatalysis by photo-Fenton. Direct solar irradiation resulted in almost complete transformation of MET in the investigated matrices after 20 h of normalized irradiation time. MET photocatalytic transformation required shorter illumination times in DW compared to SWeff. Only 16 and 36 min of solar illumination were required during photo-Fenton and photocatalysis with TiO2, respectively, to transform MET completely in SWeff. Mineralization of the dissolved organic carbon took place only during photocatalytic treatments. Kinetics parameters were calculated for processes comparison. Additionally, phototransformation intermediates generated during each treatment were investigated and characterized by means of ultra-performance liquid chromatography coupled to quadrupole-time of flight tandem mass spectrometry (UPLC-QqTOF-MS/MS). The main MET phototransformation pathways were observed to be hydroxylation, and fragmentation and cyclization. According to the Vibrio fischeri bioassay, the acute toxicity of the generated phototransformation products was not relevant, since the observed inhibition percentages of bacterial bioluminescence were always below 30% after 30 min of sample contact.