Humic-Like Substances as Auxiliaries to Enhance Advanced Oxidation Processes.

The application of humic-like substances (HLSs) in advanced oxidation processes for wastewater treatment is summarized in this work. HLSs share important characteristics with humic substances, and they can be isolated from different wastes using procedures that are related with their pH-dependent solubility. They are able to generate, upon irradiation, reactive species such as hydroxyl radicals and singlet oxygen or triplet excited states. Although photochemical removal of pollutants can be reached by HLSs, in general, irradiation times are very long. HLSs are good metal-complexing agents, and the Fe-HLS complex is able to participate in (photo)-Fenton-like processes at mild pH, preventing iron deactivation. Finally, novel hybrid materials with environmental applications have been synthesized using HLSs; in some cases, they also contain iron oxides, which allow a better separation but also the ability to drive heterogeneous (photo)-Fenton processes.

Valorization of UWWTP effluents for ammonium recovery and MC elimination by advanced AOPs.

The main objective of this study was to generate ready-to-use revalorized irrigation water for fertilization from urban wastewater treatment plant (UWWTP) effluents. The focus was on controlled retention of NH4+ and microcontaminants (MC), using nanofiltration. Retentates generated were treated by solar photo-Fenton at circumneutral pH using Ethylenediamine-N, N'-disuccinic acid (EDDS) iron complexing agent. Solar photo-Fenton degradation efficacy was compared with electrooxidation processes as anodic oxidation, solar-assisted anodic oxidation, electro-Fenton and solar photoelectro Fenton. Finally, phytotoxicity and acute toxicity tests were performed to demonstrate the potentially safe reuse of treated wastewater for crop irrigation. Nanofiltration was able to produce a ready-to-use permeate stream containing recovered NH4+. (valuable nutrient). Solar photo-Fenton treatment at circumneutral pH would only be of interest for rapid degradation of contaminants at less than 1 mg/L in nanofiltration retentates. Other alternative tertiary treatments, such as electrooxidation processes, are a promising alternative when a high concentration of MC requires longer process times. Anodic oxidation was demonstrated to be able to eliminate >80% of microcontaminants and solar-assisted anodic oxidation significantly reduced the electricity consumption. Electro-Fenton processes were the least efficient of the processes tested. Phytotoxicity results showed that irrigation with the permeates reduced germination, root development was mainly promoted and shoot development was positive only at low retention rate (concentration factor = 2). Acute and chronic Daphnia magna toxicity studies demonstrated that the permeate volumes should be diluted at least 50% before direct reuse for crop irrigation.

Effect of salinity on preconcentration of contaminants of emerging concern by nanofiltration: Application of solar photo-Fenton as a tertiary treatment.

This study focused on the effect of salinity on the performance of a pilot-scale nanofiltration (NF) for preconcentration of microcontaminants (MCs) in combination with solar photo-Fenton or photo-Fenton-like treatment for their elimination from NF permeate and concentrate streams. Photo-Fenton was carried out in a solar simulator at pH of 3 and at natural pH using Ethylenediamine-N, N'-disuccinic acid (EDDS) as an iron complexing agent. Degradation efficacy was tested with MCs commonly found in urban wastewater treatment plant effluents (caffeine, imidacloprid, thiacloprid, carbamazepine and diclofenac). Hydrogen peroxide and persulfate were compared in solar processes. Increase in salinity and pressure had a negligible influence on MC permeability order and NF selectivity. Solar photo-Fenton was able to degrade MCs present in the concentrated stream, and rapidly eliminate any residual MCs that might finally be present in permeate streams. Persulfate used instead of hydrogen peroxide was shown to be inefficient for the selected MCs. Fe(III):EDDS at circumneutral pH was able to remove MCs as quickly as classical photo-Fenton at acid pH, or even faster. This effect supports use of Fe(III):EDDS at natural pH for treating NF concentrates or polishing NF permeates when NF membranes are operated under extreme conditions of salinity.

Unveiling the Dependence between Hydroxyl Radical Generation and Performance of Fenton Systems with Complexed Iron.

Humiclike substances (HLS) have been demonstrated to be useful auxiliaries to drive the (photo)-Fenton process at mild pH, by avoiding iron inactivation via formation of active complexes. However, the actual performance of the process is affected by a manifold of opposite processes. In this work, the generation of hydroxyl radical-like reactive species in the Fentonlike process has been investigated using electron paramagnetic resonance, employing 5,5-dimethyl-1-pyrroline-N-oxide as a probe molecule. The signal obtained with the Fe(II)-HLS-H2O2 system at pH = 5 was very intense but decreased with time, in line with the difficult reduction of the formed Fe(III) to Fe(II). On the contrary, the signal of the Fe(III)-HLS-H2O2 system was weak but stable. The most intense signal was observed at HLS concentration of ca. 30 mg/L. Interestingly, the performance of the Fenton system at pH = 5 to degrade caffeine followed the same trends, although caffeine removal was very low after 1 h of irradiation. The results were more evident in a solar simulated photo-Fenton process, where an increase in the abatement of caffeine was observed until an HLS concentration of 30 mg/L, where 98% removal was reached after 1 h.

New Route for Valorization of Oil Mill Wastes: Isolation of Humic-Like Substances to be Employed in Solar-Driven Processes for Pollutants Removal.

The valorization of olive oil mill solid wastes (OMW) has been addressed by considering it as a possible source of humic-like substances (HLSs), to be used as auxiliary substances for photo-Fenton, employing caffeine as a target pollutant to test the efficiency of this approach. The OMW-HLS isolation encompassed the OMW basic hydrolysis, followed by ultrafiltration and drying. OMW-HLS structural features have been investigated by means of laser light scattering, fluorescence, size exclusion chromatography, and thermogravimetric analysis; moreover, the capability of OMW-HLS to generate reactive species under irradiation has been investigated using spin-trap electronic paramagnetic resonance. The caffeine degradation by means of photo-Fenton process driven at pH = 5 was significantly increased by the addition of 10 mg/L of OMW-HLS. Under the mechanistic point of view, it could be hypothesized that singlet oxygen is not playing a relevant role, whereas other oxidants (mainly OH• radicals) can be considered as the key species in promoting caffeine degradation.

Hydroxyl radical as an unlikely key intermediate in the photodegradation of emerging pollutants.

In this work, a kinetic model, in combination with time-resolved experiments, is applied to assess the involvement of ·OH in the photodegradation of emerging pollutants (EPs) by means of advanced oxidation processes. In contrast with the general assumption, quenching of the short-lived ·OH in the real waters by the (highly diluted) EPs must be very inefficient, so removal of EPs cannot purely rely on the generation and reaction of ·OH. This suggests that more complex pathways have to be considered to explain the photodegradation of EPs actually achieved under the employed oxidative conditions, possibly involving other reactive species with longer lifetimes or chain degradation processes.

Some ozone advanced oxidation processes to improve the biological removal of selected pharmaceutical contaminants from urban wastewater.

Removal of nine pharmaceutical compounds--acetaminophen (AAF), antipyrine (ANT), caffeine (CAF), carbamazepine (CRB), diclofenac (DCF), hydrochlorothiazide (HCT), ketorolac (KET), metoprolol (MET) and sulfamethoxazole (SMX)-spiked in a primary sedimentation effluent of a municipal wastewater has been studied with sequential aerobic biological and ozone advanced oxidation systems. Combinations of ozone, UVA black light and Fe(III) or Fe3O4 constituted the chemical systems. During the biological treatment (hydraulic residence time, HRT = 24 h), only AAF and CAF were completely eliminated, MET, SMX and HCT reached partial removal rates and the rest of compounds were completely refractory. With any ozone advanced oxidation process applied, the remaining pharmaceuticals disappear in less than 10 min. Fe3O4 or Fe(III) photocatalytic ozonation leads to 35% mineralization compared to 13% reached during ozonation alone after about 30-min reaction. Also, biodegradability of the treated wastewater increased 50% in the biological process plus another 150% after the ozonation processes. Both untreated and treated wastewater was non-toxic for Daphnia magna (D. magna) except when Fe(III) was used in photocatalytic ozonation. In this case, toxicity was likely due to the ferryoxalate formed in the process. Kinetic information on ozone processes reveals that pharmaceuticals at concentrations they have in urban wastewater are mainly removed through free radical oxidation.

Mechanism considerations for photocatalytic oxidation, ozonation and photocatalytic ozonation of some pharmaceutical compounds in water.

Aqueous solutions of four pharmaceutical compounds, belonging to the group of emergent contaminants of water: atenolol (ATL), hydrochlorothiazide (HCT), ofloxacin (OFX) and trimethoprim (TMP), have been treated with different oxidation systems, mainly, photocatalytic oxidation, ozonation and photocatalytic ozonation. TiO2 has been used as semiconductor for photocatalytic reactions both in the presence of air, oxygen or ozone-oxygen gas mixtures. Black light lamps mainly emitting at 365 nm were the source of radiation. In all cases, the influence of some variables (concentrations of semiconductor, ozone gas and pharmaceuticals and pH) on the removal of pharmaceuticals, total polyphenol content (TPC) and total organic carbon (TOC) was investigated. A discussion on the possible routes of pharmaceutical and intermediates (as TPC and TOC) elimination has been developed. Thus, OFX TiO2/UVA degradation mechanism seems to develop through the participation of non-hydroxyl free radical species. Furthermore, the presence of OFX inhibits the formation of hydroxyl radicals in the photocatalytic process. The most effective processes were those involving ozone that lead to complete disappearance of parent compounds in less than 30 min for initial pharmaceutical concentrations lower than 2.5 mg L(-1). In the ozonation systems, regardless of the pH and the presence of TiO2, pharmaceuticals are degraded through their direct reaction with ozone. Photocatalytic ozonation was the most efficient process for TPC and TOC removals (≥ 80% and ≥60% elimination after 2 h of treatment, respectively) as well as in terms of the ozone consumption efficiency (1, 5.5 and 4 mol of ozone consumed per mol of TOC mineralized, at pH 4, 7 and 9, respectively). Weakly acid conditions (pH 4) resulted to be the most convenient ones for TPC and TOC removal by photocatalytic ozonation. This was likely due to formation of hydroxyl radicals through the ozonide generated at these conditions.

Photochemical fate of a mixture of emerging pollutants in the presence of humic substances.

The photodegradation of a mixture of the emerging pollutants (EPs) clofibric acid, amoxicillin, acetamiprid, acetaminophen, carbamazepine, and caffeine was studied under irradiation with a xenon lamp. The quantum efficiencies of the EPs were determined when irradiated individually. Experiments with the mixture of the EPs showed that indirect photoprocesses attributable to interaction between EPs can either enhance the photodegradation rate by photosensitization or decrease it by quenching processes. The addition of humic substances (HS) to the solutions resulted in an increase of indirect photoprocesses with higher effects on acetaminophen and carbamazepine; this was more remarkable when a filter was used to cut off radiation in the range 280-295 nm. Experiments carried out with chemical probes indicated that the triplet excited states of HS play a major role in the photosensitization process, although the contribution of other species cannot be completely ruled out. Additionally, V. fischeri toxicity tests showed a synergistic effect produced by the mixture of EPs before irradiation. Photodegradation resulted in an enhanced toxicity of the solution at the initial steps of the process, which was associated both with synergistic effects and with the formation of toxic photodegradation by-products of clofibric acid.

Reactivity of hydroxyl radicals with neonicotinoid insecticides: mechanism and changes in toxicity.

The reactivity of hydroxyl radicals (HO ) towards three neonicotonoid insecticides, namely imidacloprid, thiacloprid and acetamiprid was investigated. These radicals were generated by photolysis of H(2)O(2) solutions. Flash photolysis experiments were used to determine the rate constants of 5.5 x 10(10) M(-1)s(-1), 6 x 10(10) M(-1)s(-1), and 7.5 x 10(10) M(-1)s(-1), for the reactions of HO with acetamiprid, imidacloprid, and thiacloprid, respectively. Continuous irradiation experiments in the absence and presence of H(2)O(2) allowed the identification and toxicity evaluation of the primary photo- and oxidation products of the insecticides. In all cases, the less toxic 6-chloronicotinic acid was found to be the major product at higher degrees of oxidation. The results reported here indicate that the half life of the insecticides due to their reaction with HO radicals in natural aquatic reservoirs may vary between 5 h and 19 days, and therefore the hydroxyl radical-mediated oxidation may be a significant abiotic elimination route. However, elimination of the insecticide under such conditions might not improve the quality of the contaminated water, as the primary products of degradation still show considerable toxicity to Vibrio fischeri assays.

Involvement of triplet excited states in the electron transfer photodegradation of cinnamic acids using pyrylium and thiapyrylium salts as photocatalysts.

The mechanistic pathway for degradation of cinnamic acids using 2,4,6-triphenylpyrylium as well as 2,4,6-triphenyl(thia)pyrylium salts (,) as solar photocatalysts has been unambiguously established. Results obtained in steady-state experiments have been correlated with time-resolved photophysical studies. High percentages of photodegradation (60-70%) were achieved when aqueous solutions of caffeic and ferulic acids (,) as model pollutants were submitted to irradiation in the presence of ,. Electron-transfer quenching of both the singlet and triplet excited states of , by , has been proved, and the quenching rate constants (close to diffusion control) have been determined. However, the percentages of singlet quenching by ,, even at relatively high concentrations of the model pollutants, is lower than 5%. In addition to this, growth of the signal corresponding to the pyranyl radical occurs in the microsecond timescale, incompatible with the singlet state as precursor. Thus, photodegradation of , mainly involves the triplet state of the photocatalysts.

Oxidative degradation of 2,4-xylidine by photosensitization with 2,4,6-triphenylpyrylium: homogeneous and heterogeneous catalysis.

The possibility of using zeolites containing the 2,4,6-triphenylpyrylium cation as photocatalysts for the degradation of pollutants has been tested on aqueous xylidine (2,4-dimethylaniline) solutions as models for contaminated wastewaters. The influence of the photocatalyst and substrate concentrations on xylidine oxidation has been investigated in homogeneous solution, by performing a series of experiments chosen according to the experimental design methodology (Doehlert uniform array). The empirical models and the corresponding response surfaces obtained from data analysis have been used for simulating and predicting degradation efficiency. The results have shown that conversion increases with increasing amounts of photocatalyst and decreasing concentration of the model pollutant. The fluorescence of 2,4,6-triphenylpyrylium was quenched by xylidine with a rate constant k(q) of 3.1x10(9)M(-1)s(-1). This result suggests a direct electron transfer between the excited pyrylium salt and xylidine. Because of the limited stability of the photocatalyst in homogeneous media, a pyrylium containing Y-zeolite has been tested for the photocatalytic oxidation of xylidine under heterogeneous conditions. The results suggest that the supported catalyst has a much improved stability and that xylidine oxidation rates remain nearly constant during the whole reaction time. An additional advantage of the pyrylium containing zeolite photocatalyst is that it can be recycled and used for further experiments.

Ozonisation coupled with biological degradation for treatment of phenolic pollutants: a mechanistically based study.

Phenolic acids constitute an important group of pollutants which are reluctant to biological treatment. Solutions containing a mixture of cinnamic acid, p-coumaric acid, caffeic acid and ferulic acid were submitted to ozonisation. Then, the changes in biodegradability along the process were studied by means of respirometry. There is an optimum ozone dosage in the interval 3-5 min of treatment which allows to achieve the maximum increase in biodegradability (more than 10 times) and a high efficiency of the ozonisation process (COD decreases to a half of its initial value). Further ozonisation does not help to increase biodegradability and is clearly disadvantageous. Similar results are obtained with actual samples of olive oil wastewaters. This behaviour is explained based on the formation of highly biodegradable benzaldehydes as key ozonisation intermediates, in the early reaction stages.