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1.
Degradation of antibiotics in water by non-thermal plasma treatment   总被引:1,自引:0,他引:1  
The decomposition of three β-lactam antibiotics (amoxicillin, oxacillin and ampicillin) in aqueous solution was investigated using a dielectric barrier discharge (DBD) in coaxial configuration. Solutions of concentration 100 mg/L were made to flow as a film over the surface of the inner electrode of the plasma reactor, so the discharge was generated at the gas-liquid interface. The electrical discharge was operated in pulsed regime, at room temperature and atmospheric pressure, in oxygen. Amoxicillin was degraded after 10 min plasma treatment, while the other two antibiotics required about 30 min for decomposition. The evolution of the degradation process was continuously followed using liquid chromatography-mass spectrometry (LC-MS), total organic carbon (TOC) and chemical oxygen demand (COD) analyses.  相似文献   

2.
Ultrasonic treatment of water contaminated with ibuprofen   总被引:6,自引:0,他引:6  
The application of ultrasound (US) waves for remediation of wastewater is an area of increasing interest and promising results. The aim of this paper is to evaluate the influence of several parameters of the US process on the degradation of ibuprofen (IBP), a widely used non-steroidal anti-inflammatory recalcitrant drug found in water. Applied US power, dissolved gas, pH and initial concentration of IBP were the parameters investigated under sonication (300 kHz).Ultrasound increased the degradation of IBP from 30 to 98% in 30 min. Initial rate of IBP degradation was evaluated in the range of 1.35 and 6.1 μmol L−1 min−1 for initial concentrations of 2 to 21 mg L−1 or 9.7 μmol L−1 to 101 μmol L−1, respectively. Under air and oxygen the degradation rate of IBP was 4 μmol L−1 min−1 being higher than that when argon was used. The most favorable degradation pH was acidic media. Complete removal of IBP was achieved but some dissolved organic carbon (DOC) remained in solution showing that long-lived intermediates were recalcitrant to the US irradiation. However, chemical and biological oxygen demands (COD and BOD5) indicated that the process oxidize the ibuprofen compound to biodegradable substances removable in a subsequent biological step.  相似文献   

3.
Conventional and modified membrane bioreactors (MBRs) are increasingly used in small-scale wastewater treatment. However, their widespread applications are hindered by their relatively high cost and operational complexity. In this study, we investigate a new concept of wastewater treatment using a nonwoven fabric filter bag (NFFB) as the membrane bioreactor. Activated sludge is charged in the nonwoven fabric filter bag and membrane filtration via the fabric is achieved under gravity flow without a suction pump. This study found that the biofilm layer formed inside the NFFB achieved 10 mg/L of suspended solids in the permeate within 20 min of initial operation. The dynamic biofilter layer showed good filterability and the specific membrane resistance consisted of 0.3-1.9 × 1012 m/kg. Due to the low F/M ratio (0.04-0.10 kg BOD5/m3/d) and the resultant low sludge yield, the reactor was operated without forming excess sludge. Although the reactor provided aerobic conditions, denitrification occurred in the biofilm layer to recover the alkalinity, thereby eliminating the need to supplement the alkalinity. This study indicates that the NFFB system provides a high potential of effective wastewater treatment with simple operation at reduced cost, and hence offer an attractive solution for widespread use in rural and sparsely populated areas.  相似文献   

4.
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   

5.
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   

6.
A 20-40 nm anatase-titania film on a titanium electrode was fabricated using chemical vapor deposition (CVD). The film was characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The CVD deposition time and number of deposition coatings were evaluated to establish the appropriate film fabrication parameters. Results indicate that two coatings at a deposition time of 6 h each produced the best nano-TiO2 electrode films (NTEFs) with an even distribution of ca. 20 nm diameter nanoparticles in the anatase lattice. The NTEF was tested as an electrocatalytic anode to investigate the degradation efficiency in treating methyl orange dye wastewater. A high removal efficiency of methyl orange dye and total organic carbon (TOC) of 97 and 56%, respectively; was achieved using a current density of 20 mA cm− 2 for 160 min. Cyclic voltammetry showed that the electrochemical degradation reaction rate at the NTEF surface was predominately driven by molecular diffusion. The electrocatalytic decomposition rate of organic pollutants at the NTEF is controlled by mass transport, which was associated with the nanostructure of the electrocatalytic electrode.  相似文献   

7.
The degradation of seven acidic drugs and two metabolites during chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). A triple-quadrupole (QqQ) system was used to follow the time course of the pharmaceuticals and by-products, while a quadrupole time-of-flight (Q-TOF) system was also used for the identification of the by-products. Under strong chlorination conditions (10 mg/L Cl2, 24 h), only four of the target compounds were significantly degraded: salicylic acid, naproxen, diclofenac and indomethacine. The degradation kinetics of these four compounds were investigated at different concentrations of chlorine, bromide and pH by means of a Box-Behnken experimental design. Depending on these factors, measured pseudo-first order half-lives were in the ranges: 23-573 h for salicylic acid, 13-446 min for naproxen, 5-328 min for diclofenac and 0.4-13.4 min for indomethacine. Also, it was observed that chlorine concentration was the overall most significant factor, followed by the bromide concentration (except for indomethacine), resulting in increased degradation kinetics as they are increased. The degradation path of salicylic acid, naproxen and diclofenac consisted of aromatic substitution of one or two hydrogens by chlorine and/or bromide. Moreover, for diclofenac, two other by-products corresponding to a decarboxylation/hydroxylation pathway from the monohalogenated products were also identified. On the other hand, indomethacine degradation did not lead to halogenation products but to oxidation ones. The investigation of these by-products in real samples by LC-MS/MS (QqQ) showed that the halogenated derivates of salicylic acid occurred in all the drinking water and wastewater samples analysed.  相似文献   

8.
Heather E. Byrne 《Water research》2009,43(17):4278-1831
Photochemical transformations of mercury were studied to determine its potential as a treatment mechanism to reduce mercury laden waters to trace concentrations. In this study, aqueous solutions of mercury nitrate in deionized water were exposed to UV irradiation and a gas purge. The impacts of purge gas (including rate and bubble size), UV irradiation wavelength, initial mercury concentration and time on mercury removal have been studied. Nitrogen purge with 254 nm UV irradiation resulted in the greatest net production of elemental mercury for all initial concentrations. These conditions followed pseudo first order kinetics and achieved the highest rate constant of 0.18 s−1. As oxygen was introduced into the solution, the quantity of elemental mercury volatilized decreased but still resulted in significant mercury losses through volatilization up to 90% in 60 min. Overriding, the loss of elemental mercury from the solution is dependent upon the gas purge rate and bubble size.  相似文献   

9.
Previous work demonstrates that widely used fluoroquinolone antibacterial agents, including ciprofloxacin, are degraded by means of aqueous ultraviolet photolytic and titanium dioxide (TiO2) photocatalytic (using both ultraviolet-A (UVA) and visible light (Vis) irradiation) treatment processes. In this study, we investigate the effects of photolytic and photocatalytic treatment processes on the antibacterial activity of ciprofloxacin solutions under controlled laboratory conditions. In agreement with earlier work, rates of ciprofloxacin degradation under comparable solution conditions (100 μM ciprofloxacin, 0 or 0.5 g/L TiO2, pH 6, 25 °C) follow the trend UVA-TiO2 > Vis-TiO2 > UVA. Release of ammonia and fluoride ions is observed and a range of organic products have been identified with liquid chromatography-tandem mass spectrometry. However, the identified organic products all appear to retain the core quinolone structure, raising concerns about residual antibacterial potency of the treated solutions. Quantitative microbiological assays with a reference Escherichia coli strain indicate that the antimicrobial potency of ciprofloxacin solutions track closely with the undegraded ciprofloxacin concentration during photolytic or photocatalytic reactions. Quantitative analysis shows that for each mole of ciprofloxacin degraded, the antibacterial potency of irradiated solutions decreases by approximately one “mole” of activity relative to that of the untreated ciprofloxacin solution. This in turn indicates that the ciprofloxacin photo(cata)lytic transformation products retain negligible antibacterial activity relative to the parent compound. The energy demands for achieving one order of magnitude reduction in antibacterial activity within the experimental system are estimated to be 175 J/cm2 (UVA-only), 29 J/cm2 (Vis-TiO2), and 20 J/cm2 (UVA-TiO2), which indicates that the UVA-TiO2 photocatalysis is the most energy efficient process for achieving ciprofloxacin inactivation under laboratory conditions.  相似文献   

10.
Ca alginate polymer fibers were developed to effectively disperse and stabilize an efficient photocatalyst such as AEROXIDE® TiO2 P25 in their matrix. The biopolymer/TiO2 fibers were prepared and tested either in the hydrogel non-porous form or in the highly porous aerogel form prepared by sc-CO2 drying. Batch photocatalytic experiments showed that the porous, Ca alginate/TiO2 fibers, exhibited high efficiency for the removal of methyl orange (MO) from polluted water. In addition, their high porosity and surface area led to high MO degradation rate which was faster than that observed not only for their non-porous analogs but also of the bulk P25 TiO2 powder. Specifically, 90% removal for 20 μM MO was achieved within 220 min for the porous sc-CO2 dried fibers while for their non-porous analogs at 325 min. The corresponding value (at 60 μM MO) for the porous sc-CO2 dried fibers was 140 min over 240 min for the AEROXIDE® TiO2 P25 as documented in the literature. Furthermore the composite alginate/photocatalyst porous fibers were combined with TiO2 membranes in a continuous flow, hybrid photocatalytic/ultrafiltration water treatment process that led to a three fold enhancement of the MO removal efficiency at 400 ml of 20 μM MO total treated volume and to dilution rather than condensation in the membrane retentate as commonly observed in filtration processes. Furthermore the permeability of the photocatalytic membrane was enhanced in the presence of the fibers by almost 20%. This performance is achieved with 26 cm2 and 31 cm2 of membrane and stabilized photocatalyst surfaces respectively and in this context there is plenty of room for the up-scaling of both membranes and fibers and the achievement of much higher water yields since the methods applied for the development of the involved materials (CVD and dry-wet phase inversion in a spinning set-up) are easily up-scalable and are not expected to add significant cost to the proposed water treatment process.  相似文献   

11.
Research examined the anaerobic degradation of 17α-ethynylestradiol, acetaminophen, acetylsalicylic acid, ibuprofen, metoprolol tartrate, and progesterone by methanogenic bacteria. Using direct sample analysis and respirometric testing, anaerobic degradation was examined with (a) each compound as the sole organic carbon source and (b) each compound at a lower concentration (250 µg/L) and cellulose serving as the primary organic carbon source. The change in pharmaceutical concentration was determined following 7, 28, 56, and 112 days of anaerobic incubation at 37 °C. Only acetylsalicylic acid demonstrated significant degradation; the remaining compounds showed a mixture of degradation and abiotic removal mechanisms. Experimental results were compared with BIOWIN, an anaerobic degradation prediction model of the US Environmental Protection Agency. The BIOWIN model predicted anaerobic biodegradability of the compounds in the order: acetylsalicylic acid > metoprolol tartrate > ibuprofen > acetaminophen > 17α-ethinylestradiol > progesterone. This corresponded well with the experimental findings which found degradability in the order: acetylsalicylic acid > metoprolol tartrate > acetaminophen > ibuprofen.  相似文献   

12.
Glyphosate is the organophosphate herbicide most widely used in the world. Any form of spill or discharge, even if unintentional, can be transferred to the water due to its high solubility. The combination of hydrogen peroxide and UV radiation could be a suitable option to decrease glyphosate concentration to acceptable limits. In this work, the effects of initial pH, hydrogen peroxide initial concentration, and incident radiation in glyphosate degradation were studied. The experimental device was a cylinder irradiated with two tubular, germicidal lamps. Conversion of glyphosate increases significantly from pH = 3-7. From this value on, the increase becomes much less noticeable. The reaction rate depends on the initial herbicide concentration and has an optimum plateau of a hydrogen peroxide to glyphosate molar concentration ratio between 7 and 19. The expected non linear dependence on the irradiation rate was observed. The identification of critical reaction intermediaries, and the quantification of the main end products were possible and it led to propose a plausible degradation path. The achieved quantification of the mineralization extent is a positive indicator for the possible application of a rather simple technology for an in situ solution for some of the problems derived from the intensive use of glyphosate.  相似文献   

13.
Monodispersed carboxymethyl cellulose (CMC)-stabilized Fe-Cu bimetal nanoparticles with an average diameter of less than 20 nm were successfully synthesized by a modified water-based approach. The as-resulting particles exhibit a core-shell structure and are quite uniform in size and shape. Batch experiments demonstrated that these nanoparticles could effectively dechlorinate 1,2,4-trichlorobenzene (1,2,4-TCB). Near 90% of reduction efficiency was achieved by CMC-stabilized Fe-Cu for 24 h treatment. By monitoring the reaction products with time by GC-MS, it was found that 1,2,4-TCB transformation mainly followed the sequential hydrogenolysis to 1,2-dichlorobenzene (12DCB), then chlorobenzene (CB) and eventually benzene. The pseudo first order 1,2,4-TCB degradation rate were 0.09 h−1 and 0.06 h−1 as CMC-to-Fe molar ratios were 0.00248 and 0.00124, respectively. Dechlorination mechanism was also proposed in this study.  相似文献   

14.
This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD = 1662-1960 mg O2 L−1; DOC = 513-696 mg C L−1), with a high biodegradable organic carbon fraction (81%; BOD5 = 1350-1600 mg O2 L−1) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45 mg L−1 (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD5/COD ratio, was only 2.3 kJUV L−1 (45 min of photo-Fenton at a constant solar UV power of 30 W m−2), consuming 16 mM of H2O2, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150 mg O2 L−1, which is in agreement with Portuguese discharge limits regarding water bodies.  相似文献   

15.
Diclofenac (DCF), a common analgesic, anti-arthritic and anti-rheumatic drug, is one of the most frequently detected compounds in water. This study deals with the degradation of diclofenac in aqueous solution by ozonation. Biodegradability (BOD5/COD ratio and Zahn-Wellens test), acute ecotoxicity and inhibition of activated sludge activity were determined in ozonated and non-ozonated samples. Liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) was used to identify the intermediates formed in 1 h of ozonation. Eighteen intermediates were identified by these techniques and a tentative degradation pathway for DCF ozonation is proposed.Experimental results show that ozone is efficient at removing DCF: > 99% removal (starting from an initial concentration of 0.68 mmol L− 1) was achieved after 30 min of ozonation (corresponding to an absorbed ozone dose of 0.22 g L− 1, which is 4.58 mmol L− 1). However, only 24% of the substrate was mineralized after 1 h of ozonation. The biodegradability, respiration inhibition in activated sludge and acute toxicity tests demonstrate that ozonation promotes a more biocompatible effluent of waters containing DCF.  相似文献   

16.
Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating 12C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with 14C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.  相似文献   

17.
Peng Ye 《Water research》2009,43(5):1303-1312
The adsorption and degradation of 4,6-o-dinitrocresol (DNOC) and p-nitrophenol (PNP) in SWy-2 montmorillonite clay slurry were investigated. The pH and type of cation of the slurry were varied. Results showed that adsorption of DNOC and PNP increased at lower pH values, and when pH < pKa (4.4) of DNOC, DNOC was almost completely adsorbed on the clay under given experimental conditions. The specific cation also had a significant effect on adsorption, which was dramatically enhanced in the presence of K+ and NH4+, compared with the presence of Na+ or Ca2+. Anodic Fenton treatment (AFT) degradation of DNOC and PNP in the clay slurry was studied, and it was found that DNOC degradation rates were greatly affected by the initial pH and the types of electrolytes. Due to the higher adsorption, the degradation rate substantially decreased in the clay slurry system in the presence of K+ and low pH, with a large amount of DNOC residue remaining after 60 min treatment. AFT degradation of PNP was completed within 30 min treatment. Based on LC-MS data, a DNOC degradation pathway was proposed. Overall, the results showed the inhibition effect of adsorption on the degradation of nitroaromatic compounds in montmorillonite clay slurry by AFT, providing important implications for water and soil remediation.  相似文献   

18.
Potential of perfluorooctanoic acid (PFOA) to degrade via indirect photolysis in aquatic solution under conditions representing surface water was studied. Globally distributed and bioaccumulative PFOA does not absorb solar radiation by itself, but may be potentially photochemically transformed by the natural sensitizers such as dissolved organic matter (DOM), nitrate or ferric iron. Reaction solutions containing purified water, fulvic acid (representing DOM), nitrate, ferric iron or sea water from the Baltic Sea were spiked with PFOA and irradiated with an artificial sun (290-800 nm). In comparison similar samples were also irradiated under UV radiation at 254 nm in order to study the direct photolysis. UV radiation at 254 nm decomposed PFOA to perfluoroheptanoic-, perfluorohexanoic- and perfluoropentanoic acids. The samples irradiated with an artificial sun contained no decomposition products and no decrease in PFOA concentration was observed. According to the detection limit of the products and typical solar radiation at the surface of ocean, the photochemical half-life for PFOA was estimated to be at least 256 years at the depth of 0 m, > 5000 years in the mixing layer of open ocean and > 25,000 years in coastal ocean. This is significantly more than the previously reported photochemical half-life of PFOA (> 0.96 years).  相似文献   

19.
In this work a batch-optimised mixture (w/w %: 6% leaves, 9% compost, 3% Fe(0), 30% silica sand, 30% perlite, 22% limestone) was investigated in a continuous fixed bed column reactor for the treatment of synthetic acid-mine drainage (AMD). A column reactor was inoculated with sulphate-reducing bacteria and fed with a solution containing sulphate and heavy metals (As(V), Cd, Cr(VI), Cu and Zn). At steady state, sulphate abatement was 50 ± 10%, while metals were totally removed. A degradation rate constant (k) of 0.015 ± 0.001 h−1 for sulphate removal was determined from column data by assuming a first order degradation rate. Reduction of AMD toxicity was assessed by using the nematode Caenorhabditis elegans as a test organism. A lethality assay was performed with the toxicants before and after the treatment, showing that only 5% of the animals were still alive after 48 h in presence of the contaminants, while the percentage increased to 73% when the nematodes were exposed to the solution eluted from the column.  相似文献   

20.
Hakami O  Zhang Y  Banks CJ 《Water research》2012,46(12):3913-3922
The preparation and testing of thiol-functionalised silica-coated magnetite nanoparticles (TF-SCMNPs) is described. The characteristics of these particles are assessed at different stages in the production process using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), and a magnetometer. The particles were found to be almost spherical with a uniform mesoporous structure with a pore size of ∼2.1 nm. The particles were strongly responsive to an external magnetic field making separation from solution possible in less than 1 min. The adsorption characteristics of the particles were quantified in a series of isotherm experiments using Hg(II) solution concentrations between 40 and 1000 μg l−1 at adsorbent concentrations of 4 and 8 mg l−1. The adsorption capacity was higher than for other commonly used adsorbents with 90% of Hg(II) removed during the first 5 min and equilibrium in less than 15 min. Both the Langmuir and Freundlich isotherm models were applied to the isotherm data and the maximum adsorption capacity was achieved when the ratio of adsorbent to adsorbate was low. Both temperature and pH had an effect on adsorption but when the TF-SCMNPs were used for removal of Hg(II) from tap water and bottled water, which contained other ions, there appeared to be no interference. Hg(II) could be successfully desorbed using thiourea in a 3 M HCl solution; this did not result in the destruction of the nanoparticles and they could subsequently be reused without loss of their activity in repetitive adsorption tests.  相似文献   

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