Photonic efficiency of the photodegradation of paracetamol in water by the photo-Fenton process.

An experimental study of the homogeneous Fenton and photo-Fenton degradation of 4-amidophenol (paracetamol, PCT) is presented. For all the operation conditions evaluated, PCT degradation is efficiently attained by both Fenton and photo-Fenton processes. Also, photonic efficiencies of PCT degradation and mineralization are determined under different experimental conditions, characterizing the influence of hydrogen peroxide (H2O2) and Fe(II) on both contaminant degradation and sample mineralization. The maximum photonic degradation efficiencies for 5 and 10 mg L(-1) Fe(II) were 3.9 (H2O2 = 189 mg L(-1)) and 5 (H2O2 = 378 mg L(-1)), respectively. For higher concentrations of oxidant, H2O2 acts as a "scavenger" radical, competing in pollutant degradation and reducing the reaction rate. Moreover, in order to quantify the consumption of the oxidizing agent, the specific consumption of the hydrogen peroxide was also evaluated. For all operating conditions of both hydrogen peroxide and Fe(II) concentration, the consumption values obtained for Fenton process were always higher than the corresponding values observed for photo-Fenton. This implies a less efficient use of the oxidizing agent for dark conditions.

New insights in the dihydroxybenzenes-driven Fenton reaction: electrochemical study of interaction between dihydroxybenzenes and Fe(III).

It has been reported that the dihydroxybenzene (DHB) driven Fenton reaction is more efficient to degrade recalcitrant substrates than the simple Fenton reaction. The enhanced reactivity of the DHB driven Fenton reaction is not clear, but it could be explained by the formation of oxidant species different from the ones formed by classical Fenton reaction or by the shift of the redox potential of the complex formed by DHB and Fe(III). The redox reaction between Fe(III) and the DHBs 1,2-dihydroxybenzene (catechol, CAT), 2,3-dihydroxybenzoic acid (2,3-DHBA), 3,4-dihydroxybenzoic acid (3,4-DHBA), and 1,2-dihydroxy-3,5-benzenedisulfonate (TIRON) was studied by cyclic voltammetry to better understand the enhanced reactivity of the DHB driven Fenton reaction. It was determined that the amount of Fe(II) produced by the redox reaction between Fe(III) and DHBs was insufficient to explain the enhanced reactivity. Cyclic voltammograms (CV) of the DHBs/Fe(III) systems show a quasi-reversible or irreversible behavior and also shifting and splitting the anodic peaks. This effect can be related to DHBs oxidation by Fe(III), but not to a real interaction.

Effect of temperature on Imidacloprid oxidation by homogeneous photo-Fenton processes.

This paper presents experimental results on the effect of temperature on the rate of Imidacloprid removal from waste water using homogeneous photo-Fenton processes. Experiments were conducted in a 2 L photo reactor set at 15-42 degrees C, initial concentrations in the range of 10 to 40 mg L(-1) Fe(II) and 100-450 mg L(-1) H(2)O(2); 30 150 min processing times. Initial H(2)O(2) concentration determined the extent of the oxidation process, whereas iron concentration played a key role in the process kinetics. Homogeneous photo-Fenton showed a fast initial reaction leading to 50% Imidacloprid degradation after less than 1 min of treatment, followed by a slower process until full removal was achieved. Rapid Fe(II) oxidation to Fe(III) seems responsible for the initial Imidacloprid removal. Imidacloprid removal fitted well a pseudo-first order kinetic scheme, with apparent activation energy of approximately 31.6 kJ/mole. Untreated Imidacloprid samples showed significant acute toxicity to Daphnia magna and genotoxic effects on Bacillus subtilis. Acute toxicity and genotoxicity remained detectable even after complete pesticide removal, showing that toxic by-products were present. The design and operation of photo Fenton processes should focus on toxicity removal rather than on specific target pollutants.

Oxolinic acid photo-oxidation using immobilized TiO(2).

This work studied the photocatalysed oxidation of the antibiotic oxolinic acid (OA) in an annular reactor operated with immobilized TiO(2) on sintered glass cylinders (SGC). Experiments were carried out in 1l solution of OA (18 mg l(-1)) at pH 9 with oxygen bubbling. Irradiation was performed with black light (36 W). The reaction was monitored by COD, TOC and average oxidation state (AOS) calculations. The antibacterial activity of intermediates was followed using the inhibition halo technique on Escherichia coli cultures. The initial antibiotic concentration decreases in one order of magnitude after 60 min irradiation, and was completely eliminated at 100 min reaction. The TOC was reduced in 54% and the AOS reach values around +3 indicating the formation of low molecular weight carboxylic acids. The oxidation reaction fit well with the Langmuir-Hinshelwood kinetic model indicating the dependence of reaction rate with initial adsorption step. The antibacterial activity of the solution decreases with antibiotic removal, demonstrating that intermediates do not present antibiotic activity.

Photocatalyzed degradation of flumequine by doped TiO2 and simulated solar light.

Titanium dioxide was obtained in its pure form (TiO2) and in the presence of urea (u-TiO2) and thiourea (t-TiO2) using the sol-gel technique. The obtained powders were characterized by BET surface area analysis, Infrared Spectroscopy, Diffuse Reflectance Spectroscopy and the Rietveld refinement of XRD measurements. All the prepared catalysts show high anatase content (>99%). The a and b-cell parameters of anatase increase in the order TiO2u-TiO2>TiO2. The photocatalytic activities of the samples were determined on flumequine under solar-simulated irradiation. The most active catalysts were u-TiO2 and t-TiO2, reaching values over 90% of flumequine degradation after 15 min irradiation, compared with values of 55% for the pure TiO2 catalyst. Changing simultaneously the catalyst amount (t-TiO2) and pH, multivariate analysis using the response surface methodology was used to determine the roughly optimal conditions for flumequine degradation. The optimized conditions found were pH below 7 and a catalyst amount of 1.6 g L(-1).

Coupling of photocatalytic and biological reactors to remove EDTA-Fe from aqueous solution.

Degradation of 2.5 mM EDTA-Fe solution was performed in a coupled photocatalytic-biological reactor. The system consists of a photochemical annular reactor filled with TiO2 immobilized on glass Raschig rings coupled with an activated sludge continuous reactor. Around 50% of EDTA degradation was reached after 150 min irradiation. Simultaneously a four-fold increase in biodegradability, measured as BOD5/COD ratio, was observed. The activated sludge is not capable to degrade the complex EDTA-Fe but it removed partially the COD and efficiently the BOD5 of the photochemically treated solution.

Evidence for the hydration effect at the semiconductor phospholipid-bilayer interface by TiO2 photocatalysis.

The interactions of TiO2 with phospholipid bilayers found in cell membrane walls were observed to perturb the bilayer structure under UVA light irradiation. The structure changes in the phospholipid bilayers upon contact with TiO2 under light and in the dark were followed by X-ray diffraction. Hydration effects at the semiconductor-phospholipid interface played an important role in the degradation of dimyristoylphosphatidylcholine (DMPC) and dimyristoylphosphatidylethanolamine (DMPE) bilayers taken as cell wall lipid bilayer models. Evidence is provided that the fluidity of the phospholipid bilayers plays a significant role when interacting in the dark with the TiO2 or in processes mediated by TiO2 under light irradiation.

Combined oxidative and biological treatment of separated streams of tannery wastewater.

Leather tanning effluents are a source of severe environmental impacts. In particular, the unhairing stage, belonging to the beamhouse processes, generates an alkaline wastewater with high concentrations of organic matter, sulphides, suspended solids, and salts, which shows significant toxicity. The objective of this work was to evaluate the biodegradation of this industrial wastewater by combined oxidative and biological treatments. An advanced oxidation process (AOP) with Fenton's reagent was used as batch pretreatment. The relationships of H2O2/Fe2+ and H2O2/COD were 9 and 4, respectively, reaching an organic matter removal of about 90%. Subsequently, the oxidised beamhouse effluent was fed to an activated sludge system, at increasing organic load rates (OLR), in the range of 0.4 to 1.6 g COD/L x day. The biological organic matter removal of the pre-treated wastewater ranged between 35% and 60% for COD, and from 60% to 70% for BOD. Therefore, sequential AOP pretreatment and biological aerobic treatment increased the overall COD removal up to 96%, compared to 60% without pretreatment. Bioassays with D. magna and D. pulex showed that this kind of treatment achieves only a partial toxicity removal of the tannery effluent.

Removal of EDTA by UV-C/hydrogen peroxide.

Mineralization of a 5 mM EDTA solution at pH 3 was evaluated via TOC removal under UV-C irradiation in the presence of H2O2 at various conditions. The highest TOC removal (78%) was obtained using a 40:1 H2O2/EDTA molar ratio, after 540 min irradiation. However, a 20:1 ratio gave slightly lower results, being economically more attractive. Best results of TOC removal were obtained under pH controlled conditions. Addition of TiO2 (1 g l(-1)) was detrimental, even in the presence of H2O2, indicating that at this concentration, TiO2 inhibits the mineralization, probably by scattering or by screening of the light.

A degradation and toxicity study of three textile reactive dyes by ozone.

Textile reactive dyes are very recalcitrant to biodegradation, causing aesthetic, acute and chronic toxicity problems in receiving waters. In this study, we present the degradation of three different reactive dyes (Reactive Black 5, Reactive Blue 19 and Reactive Blue 21) by ozone, at two different pH conditions. The ozonation process achieved a very fast decoloration rate for the studied dyes. The influence of pH in the ozonation of these dyes was only significant for Reactive Black 5. The toxicity of dyes, after pre-treatment, was evaluated using Vibrio fisheri (microtox). There was little change in toxicity for Reactive Black 5, but there was a reduction for Reactive Blue 19. A significant increase in toxicity for Reactive Blue 21 was verified, caused by the increase in the bioavailability of th e cooper ion that was in the complexed form before the treatment with ozone.

Photocatalyzed mineralization of kraft black liquor on ZnO/Fe2O3 coupled semiconductor.

Photocatalysis using ZnO-Fe2O3 coupled catalyst removed partially the organic matter dissolved in kraft black liquor obtained from pinus wood cooking. The photo-assisted oxidation using different ZnO/Fe2O3 ratios was studied following the CO, evolution during the course of the reaction. A synergy of the composite improves the mineralization observed. The optimal ZnO to Fe2O3 ratio varied from 0.5 to 0.7 which allowed the highest mineralization rates.

Ozonation of 1,2-dihydroxybenzene in the presence of activated carbon.

This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the presence of activated carbon, with a view to assessing possible changes in its surface chemical structure and adsorption capacity. Experiments were conducted in a 0.5 L reactor, loaded with 2 g Filtrasorb 400 granular activated carbon, and 1-5 mM DHB aqueous solution at pH 2-8. Ozone gas was generated with an Ozocav generator, and fed into the reactor for a given exposure time, in the range 0.5-240 min, at 25 degrees C and 1 atm. After each run, liquid and activated carbon samples were taken for chemical assays. Soluble organic groups present on the active carbon surface were desorbed and analysed by GC-MS and HPLC. Activated carbon chemical surface properties were analysed using TPD, FT-IR, and XPS techniques. Reactions between ozone and adsorbed DHB were shown to be fast, leading to formation of C-6, C-4 and C-2 by-products. Oxygenated surface groups, particularly, COOH and C = O, increased as a result of ozonation.

Reactive dyes decolouration by TiO2 photo-assisted catalysis.

The photocatalytic degradation of three reactive azo dyes (yellow-2, orange-16 and red-2) and one anthraquinone reactive dye (blue-19) was studied. The reactions were carried out in a reactor with recirculation using TiO2 immobilised on glass Raschig rings (system A) and compared with a batch system using the catalyst in aqueous suspension (system B). Both reaction systems were irradiated with a 125 W, lambda > 254 nm lamp. The suspended TiO2 system was also studied using a 125 W 360 nm lamp (system C). Kinetic studies indicated a rapid colour removal, following the order B > A > C. The same trend was observed in COD and TOC removal profiles. The energy consumption per order of magnitude of catalytic degradation of the dyes was lower in the batch reactor (system B) than in the reactor with recirculation and immobilised TiO2 (system A).

Kinetics and toxicity of direct reaction between ozone and 1,2-dihydrobenzene in dilute aqueous solution.

The presence of toxic aromatic organic compounds in industrial wastewater affects the efficiency of conventional biological treatment. The oxidizing power of ozone represents an interesting pretreatment to reduce toxicity and increase biodegradability. At low pH, ozone is known to attack electron-rich structures by direct electrophilic reactions which open aromatic rings, and generate smaller oxidized compounds. This paper reports experimental results on kinetic and toxicity aspects of ozone direct reactions with 1,2-dihydrobenzene. This toxic compound is frequently found in cellulose bleaching effluents. Although the reaction pathway is rather complex, 4-carbon compounds, such as maleic acid, are readily formed during the first stage of ozonation. These 4-carbon compounds are further oxidized to form smaller molecules (mostly 2-carbon, such as oxalic acid). The apparent kinetics of 1,2-dihydrobenzene follows a second order law, with a rate constant around 0.36 (dm3 mmol-1s-1), at pH 2 and 20 degrees C. Results show that the BOD:COD ratio increase five-fold as ozonation progresses. Furthermore, the mutagenicity of 1,2-dihydrobenzene totally disappears as the aromatic compound is destroyed by ozonation.

Photocatalytic degradation of cellulose bleaching effluent by supported TiO2 and ZnO.

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.

Bacterial response to photocatalytic degradation of 6-chlorovanillin.

The oxidation of a 186 ppm 6-chlorovanillin solution was performed using impregnated TiO2 glass rings in a 1 l photochemical reactor. Fifty per cent degradation was obtained after 60 min with recirculation of the solution. Then, oxidised samples were submitted under aerobic conditions to bacterial degradation in the Pseudomonas paucimobilis (S37) and Burkholderia cepacia (PZK). Both selected aerobic bacteria degrade more efficiently the photocatalysed samples, being PZK strain better than S37. A first-order kinetic was observed in both systems photocatalytic and bacterial degradation.

Advanced oxidation of a pulp mill bleaching wastewater.

The degradation, by several advanced oxidation reactions, of a pulp mill ECF bleaching effluent, was studied. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD5/COD, was low (0.3). When the effluent was submitted to ozonation and to five different advanced oxidation systems (O3/UV, O3/UV/ZnO, O3/UV/TiO2, O2/UV/ZnO, O2/UV/TiO2), the biodegradability increase significantly. After five minutes of reaction, the O3/UV system appears as the most efficient in to transform the organic matter to more biodegradable forms. A similar effect was observed when the effluent was submitted to an activated sludge treatment. The COD, TOC and toxicity reduction correlated well with the biodegradability enhancement after AOPs treatments.

Somatostatin antisense oligodeoxynucleotide-mediated stimulation of lymphocyte proliferation in culture.

We have previously shown that somatostatin (SRIF) is synthesized in B and T lymphocytes of rat spleen and thymus and released into the medium of cultured lymphocytes. To determine the role of SRIF in the control of lymphocytes proliferation, the expression of SRIF in normal lymphocytes was inhibited using a 3'-terminal phosphorothioate-modified antisense oligonucleotide complementary to a sequence that includes the translation start site of the rat SRIF messenger RNA. Spleens were obtained from adult male rats, and their lymphocytes were cultured for 24 or 72 h to measure SRIF content and cell proliferation, respectively. For the proliferation studies, [3H]thymidine was incorporated during the final 18 h. The lymphocytes were incubated with 15-30 micrograms/ml SRIF antisense and control antisense. SRIF antisense (25 micrograms/ml) increased lymphocyte proliferation 15-fold (P < or = 0.001), reaching a plateau (25- to 30-fold increase) between 25-30 micrograms/ml SRIF antisense. SRIF was extracted from lymphocytes and measured by RIA. Levels of SRIF content were almost undetectable with 10 micrograms/ml antisense and were significantly lower (P < or = 0.01) with 25 micrograms/ml antisense. When RC 160 (10(-5) M), a SRIF agonist analog, was used in the incubation, the stimulation of cell proliferation exerted by the SRIF antisense was completely abolished. Control antisense had no effect on proliferation or SRIF content. These findings indicate that 1) lymphocytes in culture are able to incorporate SRIF antisense; and 2) SRIF antisense inhibits the expression of lymphocytic SRIF, which leads to lymphocyte proliferation. In conclusion, cell proliferation is dramatically increased by eliminating the expression of SRIF from the lymphocytes, which indicates that in vitro SRIF is acting in a paracrine and/or autocrine fashion to inhibit lymphocyte proliferation.