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1.
The influence of iron species on amoxicillin (AMX) degradation, intermediate products generated and toxicity during the photo-Fenton process using a solar simulator were evaluated in this work. The AMX degradation was favored in the presence of the potassium ferrioxalate complex (FeOx) when compared to FeSO4. Total oxidation of AMX in the presence of FeOx was obtained after 5 min, while 15 min were necessary using FeSO4. The results obtained with Daphnia magna biossays showed that the toxicity decreased from 65 to 5% after 90 min of irradiation in the presence of FeSO4. However, it increased again to a maximum of 100% after 150 min, what indicates the generation of more toxic intermediates than AMX, reaching 45% after 240 min. However, using FeOx, the inhibition of mobility varied between 100 and 70% during treatment, probably due to the presence of oxalate, which is toxic to the neonates. After 240 min, between 73 and 81% TOC removal was observed. Different pathways of AMX degradation were suggested including the opening of the four-membered β-lactamic ring and further oxidations of the methyl group to aldehyde and/or hydroxylation of the benzoic ring, generating other intermediates after bound cleavage between different atoms and further oxidation to carboxylates such acetate, oxalate and propionate, besides the generation of nitrate and ammonium.  相似文献   

2.
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 H2O2 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 H2O2 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.  相似文献   

3.
The complexation of iron ions with the herbicide tebuthiuron (TBH), during a solar photo-Fenton process, was investigated using cyclic voltammetry with a glassy carbon electrode. An oxidation peak was observed at +0.64 V after addition of Fe(NO3)3 to TBH solution, indicating the formation of a Fe-TBH complex, which was not observed in the presence of ferrioxalate or citrate complexes. This complexation hinders photoreduction of Fe(III), and consequently TBH degradation. The main degradation route, in the presence or absence of citric acid (in the latter case with Fe(NO3)3 only), is initiated by the hydroxylation of a terminal methyl group of the urea, indicating an identical degradation mechanism. Hydroxylation of the central methyl of urea, and of the tert-butyl group, was also observed after extended irradiation periods in the presence of citric acid, but was not observed in the presence of Fe(NO3)3, due to a slower degradation rate in the absence of the citrate complex. No intermediate, generated from opening of the thiadiazole ring, was identified under the various different conditions.  相似文献   

4.
This work investigated the application of a solar driven advanced oxidation process (solar photo-Fenton), for the degradation of antibiotics at low concentration level (μg L−1) in secondary treated domestic effluents at a pilot-scale. The examined antibiotics were ofloxacin (OFX) and trimethoprim (TMP). A compound parabolic collector (CPC) pilot plant was used for the photocatalytic experiments. The process was mainly evaluated by a fast and reliable analytical method based on a UPLC-MS/MS system. Solar photo-Fenton process using low iron and hydrogen peroxide doses ([Fe2+]0 = 5 mg L−1; [H2O2]0 = 75 mg L−1) was proved to be an efficient method for the elimination of these compounds with relatively high degradation rates. The photocatalytic degradation of OFX and TMP with the solar photo-Fenton process followed apparent first-order kinetics. A modification of the first-order kinetic expression was proposed and has been successfully used to explain the degradation kinetics of the compounds during the solar photo-Fenton treatment. The results demonstrated the capacity of the applied advanced process to reduce the initial wastewater toxicity against the examined plant species (Sorghum saccharatum, Lepidium sativum, Sinapis alba) and the water flea Daphnia magna. The phytotoxicity of the treated samples, expressed as root growth inhibition, was higher compared to that observed on the inhibition of seed germination. Enterococci, including those resistant to OFX and TMP, were completely eliminated at the end of the treatment. The total cost of the full scale unit for the treatment of 150 m3 day−1 of secondary wastewater effluent was found to be 0.85 € m−3.  相似文献   

5.
The present study provides results describing the degradation performance of the Sulfamethazine (SMT) antibiotic via photo-Fenton treatment. Experiments were carried out using 1 L solution samples of SMT (50 mg L−1) under different conditions. HPLC results reveal that both Fenton and photo-Fenton reactions were able to completely remove SMT antibiotic from the studied samples in less than 2 min treatment. Half-life times and kinetic parameters (assuming a pseudo-first-order kinetics at reaction initial stage, far from the equilibrium) for SMT degradation were determined and discussed. Hence, appropriate Fenton reagent loads are given to attain different targets proposed. TOC and HPLC data also revealed the presence of reaction intermediates; thus toxicity assays were performed regarding bacterial growth rate. The toxicity of an SMT solution was shown to increase during its degradation by means of photo-Fenton reactions.  相似文献   

6.
Degradation of the emerging contaminant ibuprofen in water by photo-Fenton   总被引:3,自引:0,他引:3  
In this study the degradation of the worldwide Non-Steroidal Anti-Inflammatory Drug (NSAID) ibuprofen (IBP) by photo-Fenton reaction by use of solar artificial irradiation was carried out. Non-photocatalytic experiments (complex formation, photolysis and UV/Vis-H2O2 oxidation) were executed to evaluate the isolated effects and additional differentiated degradation pathways of IBP. The solar photolysis cleavage of H2O2 generates hydroxylated-IBP byproducts without mineralization. Fenton reaction, however promotes hydroxylation with a 10% contamination in form of a mineralization. In contrast photo-Fenton in addition promotes the decarboxylation of IBP and its total depletion is observed. In absence of H2O2 a decrease of IBP was observed in the Fe(II)/UV-Vis process due to the complex formation between iron and the IBP-carboxylic moiety. The degradation pathway can be described as an interconnected and successive principal decarboxylation and hydroxylation steps. TOC depletion of 40% was observed in photo-Fenton degradation. The iron-IBP binding was the key-point of the decarboxylation pathway. Both decarboxylation and hydroxylation mechanisms, as individual or parallel process are responsible for IBP removal in Fenton and photo-Fenton systems. An increase in the biodegradability of the final effluent after photo-Fenton treatment was observed. Final BOD5 of 25 mg L−1 was reached in contrast to the initial BOD5 shown by the untreated IBP solution (BOD5 < 1 mg L−1). The increase in the biodegradability of the photo-Fenton degradation byproducts opens the possibility for a complete remediation with a final post-biological treatment.  相似文献   

7.
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.  相似文献   

8.
9.
The influence of dissolved humic materials (DHM) on the acute toxicity of diazinon, tetrabromobisphenol-A (TBP), 4-chloroanilin (4-CA) and pentachlorophenol (PCP) was evaluated using the zebrafish (Brachydanio rerio Hamilton-Buchanan) and waterflea (Daphnia magna Straus). The 96-h LC50 (zebrafish) and 48-h EC50 values for four chemicals were determined in the presence of 0, 0.5, 5.0 and 50 TOC mg/l. The effects of DHM on the toxicity of four test chemicals to B. rerio were not observed in all of the DHM treatments. In the daphnid toxicity test, DHM significantly reduced the toxicity of diazinon and 4-CA, while no reduction of the toxicity of TBP and PCP was observed. These results indicate that the interaction between DHM and chemicals can alter the toxicity of some chemicals to D. magna.  相似文献   

10.
Iron amendment and Fenton oxidation of MTBE-spent granular activated carbon   总被引:1,自引:0,他引:1  
Fenton-driven regeneration of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves an Fe amendment step to increase the Fe content and to enhance the extent of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate) were amended separately to GAC. Following Fe amendment, MTBE was adsorbed to the GAC followed by multiple applications of H2O2. Fe retention in GAC was high (83.8-99.9%) and decreased in the following order, FeSO4·7H2O > Fe2(SO4)3·9H2O > Fe(NO3)3·9H2O > FeCl3. A correlation was established between the post-sorption aqueous MTBE concentrations and Fe on the GAC for all forms of Fe investigated indicating that Fe amendment interfered with MTBE adsorption. However, the mass of MTBE adsorbed to the GAC was minimally affected by Fe loading. Relative to ferric iron amendments to GAC, ferrous iron amendment resulted in lower residual iron in solution, greater Fe immobilization in the GAC, and less interference with MTBE adsorption. MTBE oxidation was Fe limited and no clear trend was established between the counter-ion (SO42−, Cl, NO3) of the ferric Fe amended to GAC and H2O2 reaction, MTBE adsorption, or MTBE oxidation, suggesting these processes are anion independent.  相似文献   

11.
Innovative disinfection technologies are being studied for seawater, seeking a viable alternative to chlorination. This study proposes the use of H2O2/UV254 and photo-Fenton as disinfection treatment in seawater. The irradiations were carried out using a sunlight simulator (Suntest) and a cylindrical UV reactor. The efficiency of the treatment was compared for Milli-Q water, Leman Lake water and artificial seawater. The presence of bicarbonates and organic matter was investigated in order to evaluate possible effects on the photo-Fenton disinfection treatment. The photo-Fenton treatment, employing 1 mg L−1 Fe2+ and 10 mg L−1 of H2O2, led to the fastest bacterial inactivation kinetics. Using H2O2/UV254 high disinfection rates were obtained similar to those obtained with photo-Fenton under UV254 light. In Milli-Q water, the rate of inactivation for Escherichia coli was higher than in Leman Lake water and seawater due to the lack of inorganic ions affecting negatively bacteria inactivation. The presence of bicarbonate showed scavenging of the OH radicals generated in the treatment of photo-Fenton and H2O2/UV254. Despite the negative effect of inorganic ions, especially HCO3-, the disinfection treatments with AOPs in lake water and seawater improved significantly the disinfection compared to light alone (simulated sunlight and UV254). In the treatment of photo-Fenton with simulated sunlight, dissolved organic matter had a beneficial effect by increasing the rate of inactivation. This is associated with the formation of Fe3+-organo photosensitive complexes leading to the formation of ROS able to inactivate bacteria. This effect was not observed in the photo-Fenton with UV254. Growth of E. coli surviving in seawater was observed 24 and 48 h after treatment with UV light. However, growth of surviving bacteria was not detected after photo-Fenton with UV254 and H2O2/UV254 treatments.  相似文献   

12.
A new approach to assess biocompatibility of an effluent, based on combination of different bioassays and chemical analyses, has been tested using a mixture of four commercial pesticides treated by a solar photo-Fenton as target effluent. A very fast elimination of the pesticides occurred (all of them were below detection limit at t30W = 36 min), but mineralisation was a more time-consuming process, due to the formation of organic intermediates and to the presence of solvents, as shown by GC-MS analysis. Measurements based on activated sludge indicated that detoxification was coincident with the removal of the active ingredients, while more sensitive Vibrio fischeri bacterium showed significant toxicity until the end of the experiment, although the effluent might be compatible with biological processes. Biodegradability of the solutions was enhanced by the photochemical process, to reach BOD5/COD ratios above 0.8. Longer time bioassays, such as the Zahn-Wellens' test, support the applicability of coupling photochemical with activated sludge-based biological processes to deal with these effluents.  相似文献   

13.
In the present study the degradation kinetics and mineralization of diclofenac (DCF) by the TiO2 photocatalysis were investigated in terms of UV absorbance and COD measurements for a wide range of initial DCF concentrations (5-80 mg L−1) and photocatalyst loadings (0.2-1.6 g TiO2 L−1) in a batch reactor system. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Artemia salina) was performed to evaluate the potential detoxification of DCF. A pseudo-first-order kinetic model was found to fit well most of the experimental data, while at high initial DCF concentrations (40 and 80 mg L−1) and at 1.6 g TiO2 L−1 photocatalyst loading a second-order kinetic model was found to fit the data better. The toxicity of the treated DCF samples on D. magna and P. subcapitata varied during the oxidation, probably due to the formation of some intermediate products more toxic than DCF. Unicellular freshwater algae was found to be very sensitive to the treated samples as well as the results from D. magna test were consistent to those of algae tests. A. salina was not found to be sensitive under the investigated conditions. Finally, UV absorbance analysis were found to be an useful tool for a fast and easy to perform measurement to get preliminary information on the organic intermediates that are formed during oxidation and also on their disappearance rate.  相似文献   

14.
Size is one of important factors determining titanium dioxide nanoparticle (TiO2 NP) toxicity since penetration is eased with decreasing particle size and bioavailability is increased. The effect of particle size on oxidative stress against titanium dioxide nanoparticle (TiO2 NP) exposure to Daphnia magna was investigated with both acute and chronic toxicity tests. Experiments on biochemical responses, repeatedly performed after size fractionation of the NPs using filtration, focused on the activities of four antioxidant enzymes: catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPX), and glutathione-S-transferase (GST). In the chronic bioassay, the mortality was significantly increased at TiO2 NP concentrations of 5 and 10 mg/L; however, no reduction of the reproduction ability was observed. Biochemical measurements showed that TiO2 NP exposure significantly increased the antioxidant enzyme activities in D. magna. CAT, GPX and GST, but not SOD, showed a concentration-dependent increase. In terms of size fraction, particles ranging from 400 to 800 nm exhibited an increase of antioxidant enzyme activities in GST and GPX. These biochemical level observations suggested that TiO2 NP toxicity was mediated by reactive oxygen species (ROS) generation via oxidative stress in D. magna. The increased mortality at the concentration of 5 mg/L in the chronic bioassay was attributed to accumulated TiO2 NPs in the intestine of D. magna, which might induce effects such as oxidative stress relating to the induction of antioxidant enzymes.  相似文献   

15.
The application of sonolysis (US) for remediation of wastewater is an area of increasing interest. The aim of this study was to evaluate the ultrasonic (US) process on the degradation of pharmaceuticals (diclofenac (DCF), amoxicillin (AMX), carbamazepine (CBZ)) in single solutions and also in three mixtures spiked in urban wastewater effluent. Several operating conditions, such as power density (25-100 W L−1), initial substrate concentrations (2.5-10 mg L−1), initial solution pH (3-11), and air sparging were varied for the evaluation and understanding of the process. The degradation (as assessed by measuring UV absorbance), the generation of hydroxyl radicals (as assessed measuring H2O2 concentration), the mineralization (in terms of TOC and COD removal), and the aerobic biodegradability (as assessed by the BOD5/COD ratio) were monitored during sonication. Ecotoxicity to Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum before and after treatment was also evaluated. It was found that the pharmaceuticals conversion is enhanced at increased applied power densities, acidic conditions and in the presence of dissolved air. The reaction rate increases with increasing initial concentration of single pharmaceuticals but it remains constant in the mixtures, indicating different kinetic regimes (i.e. first and zero order respectively). Mineralization is a slow process as reaction by-products are more stable than pharmaceuticals to total oxidation; nonetheless, they are also more readily biodegradable. The toxicity of the wastewater samples before and after contamination with pharmaceuticals both in mixtures and in single substance-containing solutions was observed more severely on P. subcapitata; a fact that raises concerns in regards to the discharge of such effluents. D. magna displayed less sensitivity compared to P. subcapitata because it belongs in a lower taxonomic species than D. magna. The germination index of L. sativum in the presence of the drugs' mixture was stimulated instead of inducing any toxicity effect and this might be attributed to the fact the sample, laden with very low drug concentrations was able to act as a provider of additional nutrient elements.  相似文献   

16.
This paper explores the degradation of a model pollutant, bisphenol A, by an advanced oxidation process that combines sonolysis, Fe2+, and TiO2 in a photoassisted process. Experiments were done under saturated oxygen conditions. The effect of different Fe2+ (0.56 and 5.6 mg/L) and TiO2 (10 and 50 mg/L) concentrations was investigated on both the elimination and mineralization of the pollutant. A pronounced synergistic effect that led to the complete and rapid elimination of dissolved organic carbon (DOC) was observed even at low catalyst loadings. In this system, almost a complete removal of DOC (93%) was observed after 4 h using 10 and 5.6 mg/L of TiO2 and Fe2+, respectively, whereas at the same time, only 5, 6, and 22% of DOC was removed by an individual process alone (TiO2 photocatalysis, ultrasound, and photo-Fenton, respectively). In this system, ultrasound has the principal role of eliminating the initial substrate and providing hydrogen peroxide for the photocatalytic systems, while photo-Fenton and TiO2 photocatalysis are mainly responsible for the transformation of the intermediates in CO2 and H2O. The role of H2O2 generated from the sonochemical process is also discussed.  相似文献   

17.
Degradation kinetics and mineralization of an urban wastewater treatment plant effluent contaminated with a mixture of pharmaceutical compounds composed of amoxicillin (10 mg L−1), carbamazepine (5 mg L−1) and diclofenac (2.5 mg L−1) by TiO2 photocatalysis were investigated. The photocatalytic effect was investigated using both spiked distilled water and actual wastewater solutions. The process efficiency was evaluated through UV absorbance and TOC measurements. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum) was performed to evaluate the potential toxicity of the oxidation intermediates. A pseudo-first order kinetic model was found to fit well the experimental data. The mineralization rate (TOC) of the wastewater contaminated with the pharmaceuticals was found to be really slow (t1/2 = 86.6 min) compared to that of the same pharmaceuticals spiked in distilled water (t1/2 = 46.5 min). The results from the toxicity tests of single pharmaceuticals, their mixture and the wastewater matrix spiked with the pharmaceuticals displayed a general accordance between the responses of the freshwater aquatic species (P. subscapitata > D. magna). In general the photocatalytic treatment did not completely reduce the toxicity under the investigated conditions (maximum catalyst loading and irradiation time 0.8 g TiO2 L−1 and 120 min respectively).  相似文献   

18.
The present study evaluated the effect of increasing oxygen concentrations in overlying surface water on the accumulation and toxicity of sediment-bound metals in the aquatic invertebrates Lumbriculus variegatus, Asellus aquaticus and Daphnia magna. A 54 days experiment using three experimental treatments (90% O2 in overlying surface water, 40% O2 and a non-polluted control) was conducted. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured in the superficial sediment layer (0-1 cm). At each time point, accumulated metal levels as well as the available energy stores were measured in L. variegatus and A. aquaticus and each time D. magna was exposed to surface water in a 24 h toxicity test. Additionally metallothionein-like protein (MTLP) induction was quantified in L. variegatus. Oxygen induced changes in sediment AVS resulted in faster accumulation of metals from contaminated sediments in A. aquaticus, while no differences in toxicity in this species were observed. Ag, Cr, As and Co accumulation as well as toxicity in water exposed D. magna were clearly enhanced after 54 days, caused by oxidation of metal-sulfide complexes. Due to their feeding and burrowing behaviour, metal accumulation and toxicity in L. variegatus was not influenced by geochemical characteristics. Nevertheless, a rapid induction of MTLP was observed in both the 90% O2 and the 40% O2 treatment. The present study showed that elevated oxygen concentrations in overlying surface water can directly enhance metal accumulation and toxicity in aquatic invertebrates, however this is highly dependent on the organisms ecology and most dominant metal exposure route (water vs. sediment).  相似文献   

19.
Degradation of the biorecalcitrant pharmaceutical micropollutant ibuprofen (IBP) was carried out by means of several advanced oxidation hybrid configurations. TiO2 photocatalysis, photo-Fenton and sonolysis - all of them under solar simulated illumination - were tested in the hybrid systems: sonophoto-Fenton (FS), sonophotocatalysis (TS) and TiO2/Fe2+/sonolysis (TFS). In the case of the sonophoto-Fenton process, the IBP degradation (95%) and mineralization (60%) were attained with photo-Fenton (FH). The presence of ultrasonic irradiation slightly improves the iron catalytic activity. On the other hand, total removal of IBP and elimination of more than 50% of dissolved organic carbon (DOC) were observed by photocatalysis with TiO2 in the presence of ultrasound irradiation (TS). In contrast only 26% of mineralization was observed by photocatalysis with H2O2 (TH) in the absence of ultrasound irradiation. Additional results showed that, in the TFS system, 92% of DOC removal and complete degradation of IBP were obtained within 240 min of treatment. The advanced oxidation hybrid systems seems to be a promising alternative for full elimination/mineralization for the recalcitrant micro-contaminant IBP.  相似文献   

20.
Experiments on bacterial leaching of heavy metals from aerobically stabilized surplus activated sludge at the Bortnichi aeration plant in Kiev have been conducted with addition of FeSO4 ? 7H2O as a stimulant of iron-oxidizing bacteria. The mechanism of heavy metal leaching involving the ferrous iron oxidation by bacteria with subsequent formation of Fe(OH)3 was confirmed. This process is accompanied by the reduction of pH level of wastewater sludge that results in leaching of heavy metals.  相似文献   

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