Carla Sirtori

Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation.

In this work, the photocatalytic degradation of the antibiotic sulfamethoxazole (SMX) by solar photo-Fenton at pilot plant scale was evaluated in distilled water (DW) and in seawater (SW). Degradation and mineralization of SMX were strongly hindered in SW compared to DW. The influence of H(2)O(2) and iron concentration on the efficiency of the photocatalytic process was evaluated. An increase in iron concentration from 2.6 to 10.4 mg L(-1) showed only a slight improvement in SMX degradation and mineralization. However, an increase in H(2)O(2) concentration up to 120 mg L(-1) during photo-Fenton in DW decreased SMX solution toxicity from 85% to 20%, according to results of Daphnia magna bioassays. The same behaviour was not observed after photo-Fenton treatment in SW. Despite 45% mineralization in SW, toxicity increased from 16% to 86% as shown by Vibrio fischeri bioassays, which suggests that the intermediates generated in SW are different from those in DW. A SMX degradation pathway during the photo-Fenton treatment in DW is proposed.

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.

Photodegradation of sulfamethoxazole in various aqueous media: Persistence, toxicity and photoproducts assessment

The photochemical transformation of sulfamethoxazole (SMX) was investigated in different water matrices: distilled water (DW), distilled water+nitrate (10 and 20 mg L(-1)) and seawater (SW) to evaluate its persistence, toxicity and degradation pathway. A solar simulator Suntest CPS+ was used for the irradiation experiments. Identification of transformation products was performed in DW by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Acute toxicity of irradiated solutions was monitored by Vibrio fischeri and Daphnia magna bioassays in DW. Differences in the degradation rates were observed between DW and SW, being slower in SW. Presence of nitrate (indirect photolysis) in distilled water did not affect SMX degradation rate. No dissolved organic carbon (DOC) removal was observed in any case, thus indicating the formation of abundant transformation products (TPs). Analysis by LC-TOF-MS allowed the identification of up to nine transformation products during photolysis in DW. Only three of them had been previously reported in the literature, detected with other techniques. The cleavage of the sulfonamide bond and the photoisomerization by rearrangement of the isoxazole ring represent the main pathways, at the time that generate the most abundant and persistent intermediates. The acute toxicity of SMX solution varied according to test organisms. Daphnia magna was the most sensitive showing an increase from 60% to 100% immobilization after 30 h of irradiation when depletion of SMX was achieved, thus indicating the higher toxicity of the phototransformation products generated.

Effect of water-matrix composition on Trimethoprim solar photodegradation kinetics and pathways.

Direct photolysis and solar TiO(2) photocatalysis of Trimethoprim (TMP) in different water matrices (demineralised and simulated seawater) have been studied. Direct photolysis yielded a similar, slow TMP degradation rate in both water matrices, and the formation of very stable photo-transformation products. Dissolved organic carbon decreased slightly after prolonged irradiation. The main intermediate identified was a ketone derivative (trimethoxybenzoylpyrimidine), which was proved to be a photosensitizer of TMP degradation. During TiO(2) photocatalysis, TMP was completely eliminated in both water matrices at a similar rate, however, the mineralization rate was appreciably reduced in seawater, which can be explained by the presence of inorganic species acting as hydroxyl radical scavengers, and directly affecting photocatalytic efficiency. Identification of intermediates showed differences between the two processes but hydroxylation, demethylation and cleavage of the original drug molecule were observed in both.

Photodegradation study of three dipyrone metabolites in various water systems : Identification and toxicity of their photodegradation products

The photochemical behaviour of three relevant metabolites of the analgesic and antipyretic drug dipyrone, 4-methylaminoantipyrine (4-MAA), 4-formylaminoantipyrine (4-FAA) and 4-acetylaminoantipyrine (4-AAA), was evaluated under simulated solar irradiation (Suntest system). For 4-MAA, different aqueous solutions (synthetic seawater, freshwater and Milli-Q water) as well as different operational conditions were compared. According to the experimental results, 4-MAA resulted as being an easily degraded molecule by direct photolysis, with half-life times (t1/2) ranging from 0.12 to 0.58 h, depending on the irradiation conditions. Faster degradation was observed in synthetic waters, suggesting that the photolysis was influenced by the salt composition of the waters. However, no effect on the degradation rate was observed by the presence of natural photosensitizers (dissolved organic matter, nitrate ions). 4-FAA and 4-AAA showed slower photodegradation kinetics, with t1/2 of 24 and 28 h, respectively. A study of photoproduct identification was carried out by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-time-of-flight mass spectrometry (LC-TOF-MS) (ESI positive mode), which allowed us to propose a tentative photodegradation pathway for 4-MAA and the identification of persistent by-products in all the cases. Finally, the application of an acute toxicity test (Daphnia magna) showed an increase in toxicity during the photolytic process, a consequence of the formation of toxic photoproducts.

Solar photo-Fenton degradation of nalidixic acid in waters and wastewaters of different composition. Analytical assessment by LC–TOF-MS

This work assessed the solar photo-Fenton degradation of nalidixic acid (NXA), a quinolone antibacterial agent, in several different aqueous solutions. It has been proven that the composition of the water clearly affects the efficiency of the photo-Fenton process. The presence of chlorine ions induces the concurrence of different mechanisms involving Cl() and Cl(2)(-) radicals, which slow down the process. Up to 35 transformation products (TPs) were identified and their structures characterized by accurate LC-TOF-MS mass measurements during treatment of the different model waters. Photocatalytic degradation was thus observed to proceed mainly through the attack of the hydroxyl radicals on the double bond C((2))C((3)) which induce further ring opening. All the TPs identified persisted after total degradation of NXA. NXA in real pharmaceutical effluent was treated by photo-Fenton as a first stage before biological treatment. As NXA has been demonstrated to be recalcitrant to biological treatment, photo-Fenton treatment of the effluent was continued until its total degradation. Although NXA was efficiently degraded, LC-MS analyses demonstrated that some of the TPs identified after the photo-Fenton treatment were also recalcitrant to biological treatment, persisting after the combined treatment. These results show that analytical assessment of photocatalytic water treatments is essential to assure they are functioning as intended.

Solar photocatalytic treatment of quinolones: intermediates and toxicity evaluation

In this study, degradation of Flumequine (FLU) and nalidixic acid (NXA) in distilled water by two solar photocatalytic processes, TiO(2) and photo-Fenton, was evaluated. Intermediates and acute toxicity of the photoproducts generated were also studied. Degradation efficiency by heterogeneous photocatalysis with TiO(2) was similar for NXA and FLU, which were completely degraded after 25 min of illumination. Less NXA mineralisation was reached after 80 min of illumination. Photo-Fenton degradation of both substances was very quick (<25 min of illumination time), and the same mineralisation was reached in both cases. The kinetic parameters of the two substances were calculated for comparison of their photocatalytic degradation. In all cases, photocatalytic processes were associated with a reduction in toxicity, as evaluated by Vibrio fischeri bioassay. Furthermore, a sharp decrease in inhibition was observed from the beginning of the treatment, even when FLU and NXA were still present in the reaction solution (first samples). These results demonstrate that in both photocatalytic processes studied, toxicity decreases significantly, producing a phototreated sample within safe toxicity limits. The intermediates formed during photocatalytic degradation were studied by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS).

Formation of chlorinated by-products during photo-Fenton degradation of pyrimethanil under saline conditions. Influence on toxicity and biodegradability

This study evaluated the formation of chlorinated transformation products during photo-Fenton treatment of pyrimethanil (PYR-20 mg L(-1)) in two water matrices, demineralised water (DW) and water containing 5 g L(-1) of NaCl (DW(NaCl)). All experiments were carried out in compound parabolic collectors (CPC) at an initial Fe(2+) concentration of 5 mg L(-1) and H(2)O(2) concentration of 150-350 mg L(-1). Dissolved Organic Carbon (DOC), High-Performance Liquid Chromatography with Diode-Array Detection (HPLC-DAD), Liquid Chromatography-Time-Of-Flight Mass Spectrometry (LC-TOF-MS), toxicity and biodegradability tests were conducted to control the photocatalytic treatment. In DW, PYR was completely eliminated after 11.8 min of illumination and initial DOC was reduced 50% after 79 min of illumination with 33 mM of H(2)O(2) consumed. On the other hand, in DW(NaCl) water matrix, the same reduction in DOC took 110 min of illumination and H(2)O(2) consumption of 39 mM, and total degradation of PYR was observed at 12 min of illumination. PYR transformation products (TPs) were identified by LC-TOF-MS. It was demonstrated that photo-Fenton in a DW(NaCl) produces some chlorinated TPs in addition to the non-chlorinated TPs identified during degradation in the DW. All TPs formed were eliminated during photo-Fenton. Additionally, the presence of chlorinated TPs does not increase the toxicity of the water, and TPs formed are more biodegradable than PYR.

Photolysis of flumequine: Identification of the major phototransformation products and toxicity measures

Direct photolysis of flumequine (FLU, 20 mg L(-1)) in different types of water (demineralised water (DW) and synthetic seawater (SW)), was conducted in a Suntest CPS+solar simulator to evaluate its persistence and toxicity, and to identify the major phototransformation products (PTPs) generated during photolysis in DW. It was observed that FLU is susceptible to transformation when subjected to direct solar radiation. The composition of the water affects the FLU degradation kinetics, which is slower in SW. Photolytic transformation products generated during direct photolysis were identified by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Fourteen PTPs generated in DW were identified. The transformation of FLU begins with the opening of the heterocyclic ring by oxidation of the double bond. Loss of the fluorine atom and the hydroxylation of the aromatic ring also appear as the majority, especially in the early stages. Comparative acute toxicity evaluation by Vibrio fischeri and Daphnia magna bioassays was performed for the first and last irradiated solutions in both matrices studied. These bioassays demonstrated that in the SW matrix, the most persistent PTPs are highly toxic to D. magna but less so to V. fischeri.

Characterization of intermediate products of solar photocatalytic degradation of ranitidine at pilot-scale

In the present study the mechanisms of solar photodegradation of H(2)-receptor antagonist ranitidine (RNTD) were studied in a well-defined system of a pilot plant scale Compound Parabolic Collector (CPC) reactor. Two types of heterogeneous photocatalytic experiments were performed: catalysed by titanium-dioxide (TiO(2)) semiconductor and by Fenton reagent (Fe(2+)/H(2)O(2)), each one with distilled water and synthetic wastewater effluent matrix. Complete disappearance of the parent compounds and discreet mineralization were attained in all experiments. Furthermore, kinetic parameters, main intermediate products, release of heteroatoms and formation of carboxylic acids are discussed. The main intermediate products of photocatalytic degradation of RNTD have been structurally elucidated by tandem mass spectrometry (MS(2)) experiments performed at quadrupole-time of flight (QqToF) mass analyzer coupled to ultra-performance liquid chromatograph (UPLC). RNTD displayed high reactivity towards OH radicals, although a product of conduction band electrons reduction was also present in the experiment with TiO(2). In the absence of standards, quantification of intermediates was not possible and only qualitative profiles of their evolution could be determined. The proposed TiO(2) and photo-Fenton degradation routes of RNTD are reported for the first time.