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1.
An enrichment culture was used to study atrazine degradation in mineral salt medium (MSM) (T1), MSM+soil extract (1:1, v/v) (T2) and soil extract (T3). Results suggested that enrichment culture required soil extract to degrade atrazine, as after second sequential transfer only partial atrazine degradation was observed in T1 treatment while atrazine was completely degraded in T2 and T3 treatments even after fourth transfer. Culture independent polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) technique confirmed selective enrichment of genus Bacillus along with Pseudomonas and Burkholderia. Degradation of atrazine/metabolites in the industrial wastewater was studied at different initial concentrations of the contaminants [wastewater-water (v/v) ratio: T1, 1:9; T2, 2:8; T3, 3:7; T4, 5:5 and T5, undiluted effluent]. The initial concentrations of atrazine, cyanuric acid and biuret ranged between 5.32 and 53.92 µg mL?1, 265.6 and 1805.2 µg mL?1 and 1.85 and 16.12 µg mL?1, respectively. The enrichment culture was able to completely degrade atrazine, cyanuric acid and biuret up to T4 treatment, while no appreciable degradation of contaminants was observed in the undiluted effluent (T5). Inability of enrichment culture to degrade atrazine/metabolites might be due to high concentrations of cyanuric acid. Therefore, a separate study on cyanuric acid degradation suggested: (i) no appreciable cyanuric acid degradation with accumulation of an unidentified metabolite in the medium where cyanuric acid was supplemented as the sole source of carbon and nitrogen; (ii) partial cyanuric acid degradation with accumulation of unidentified metabolite in the medium containing additional nitrogen source; and (iii) complete cyanuric acid degradation in the medium supplemented with an additional carbon source. This unidentified metabolite observed during cyanuric acid degradation and also detected in the enrichment culture inoculated wastewater samples, however, was degraded up to T4 treatments and was persistent in the T5 treatment. Probably, accumulation of this metabolite inhibited atrazine/cyanuric acid degradation by the enrichment culture in undiluted wastewater.  相似文献   

2.
Horikoshi S  Hidaka H 《Chemosphere》2003,51(2):139-142
Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times ().In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and chlorine atoms concerning the chemical structures of atrazine or cyanuric acid (only nitrogen).  相似文献   

3.
In this study, the rates of degradation of organic compounds by several AOPs (H2O2/UV, Fe(III)/UV, Fe(III)/H2O2/UV, Fe(II)/H2O2 and Fe(III)/H2O2) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H2O2/UV. Photo-Fenton process (Fe(III)/H2O2/UV) was found to be more efficient than H2O2/UV and Fe(II)/H2O2 for the mineralization of acetone ([Acetone]o = 1 mM).  相似文献   

4.
This research examines the degradation of atrazine by photocatalytic oxidation (PCO) under different experimental conditions. Deisopropylatrazine, deethylatrazine and deethyldeisopropylatrazine were formed as major intermediates based on gas chromatography-mass spectrometry. The reaction mixture was found to be toxic towards two bioassays, i.e. the Microtox and amphipods survival tests even when atrazine was completely degraded by PCO within 2 h under optimized conditions. The results indicate that adding H2O2 could significantly enhance the degradation of atrazine by PCO. Ammeline, ammelide and cyanuric acid (CA) became the major intermediates/products as detected by high performance liquid chromatography from 6th to the 40th h of PCO treatment. After 72 h PCO treatment, only CA was detectable in the reaction mixture. Further degradation of CA was carried out by a newly isolated CA-degrading bacterium, Sphingomonas capsulata. The photochemical pretreatment integrated with microbial degradation lead to the complete degradation and detoxification of atrazine.  相似文献   

5.
Atrazine degrading enrichment culture was prepared by its repeated addition to an alluvial soil and its ability to degrade atrazine in mineral salts medium and soil was studied. Enrichment culture utilized atrazine as a sole source of carbon and nitrogen in mineral salts medium and degradation slowed down when sucrose and/or ammonium hydrogen phosphate were supplemented as additional source of carbon and nitrogen, respectively. Biuret was detected as the only metabolite of atrazine while deethylatrazine, deisopropyatrazine, hydroxyatrazine and cyanuric acid were never detected at any stage of degradation. Enrichment culture degraded atrazine in an alkaline alluvial soil while no degradation was observed in the acidic laterite soil. Enrichment culture was able to withstand high concentrations of atrazine (110 μg/g) in the alluvial soil as atrazine was completely degraded. Developed mixed culture has the ability to degrade atrazine and has potential application in decontamination of contaminated water and soil.  相似文献   

6.
The Ti02-mediated photomineralization of 8–1000 ppm of methanoic acid, of 6–100 ppm of ethanoic acid, of 6–180 ppm of propanoic acid, and of 6–90 ppm of n-decanoic acid in aqueous solutions was studied at 296± 2 K or 308 ± 2 K, with low and high pressure mercury arc lamps (radiant power in the absorption range 8 and 145 W respectively), using PHOTOPERM® CPP/313 membranes containing immobilized 30±3 wt.% Ti02, and, in parallel runs, 7 wt.% of a synergic mixture of tri(t-butyl)- and tri-(i-propyl) vanadate(V) as photocatalytic promoter. Stoichiometric H202 was used or, in some of the runs, 03, at saturation, as oxygen suppliers. Disappearance of total organic carbon (TOC) was followed as a function of time. To fit kinetic curves up to complete photomineralization, a kinetic model was employed, already used successfully in previous studies, which considers appearance and disappearance of all intermediates, as if they were represented by a hypothetical single molecule, mediating all of them. The photocatalytic activity of trialkyl vanadates was evaluated from quantum yields at “infinite” concentration, with respect to the maximum allowable efficiencies. When using O3, a dark catalysis effect clearly appeared towards intermediate species produced during the photocatalysed degradation.  相似文献   

7.
The plasma–chemical degradation of Forafac 1110, a perfluorinated non-ionic surfactant, in aqueous solutions was investigated using TiO2 catalysts. The considered plasma was the gliding arc in humid air, which results from an electric discharge at atmospheric pressure and quasi-ambient temperature. Two titanium dioxide powders were used and their synergistic effects on the Forafac degradation were compared. The results were discussed through the evolution of the pH, the conductivity, the fluoride ions concentration released in solutions, the surfactant concentration remaining after treatment and the chemical oxygen demand (COD) measurement.

The combination of the plasma–chemical treatment with heterogeneous catalysis through the use of TiO2 accelerated the Forafac degradation, since only 60 min was sufficient to remove 96% instead of 360 min needed in the absence of TiO2. The use of anatase and rutile under the trade-name of Rhodia TiO2 and Merck TiO2, respectively, led to different results, because Rhodia TiO2 has proven to be more efficient. It would seem that the crystalline phase as well as the crystallite size, explain the efficiency of anatase. The advantage of the plasma-catalysis is due to the fact that there is a significant production of the OH radicals not only generated by the gliding arc discharge but also by TiO2.  相似文献   


8.
Degradation of aquatic humic material by ultraviolet light   总被引:1,自引:0,他引:1  
Peter Backlund 《Chemosphere》1992,25(12):1869-1878
Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H2O2. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H2O2. The decreases were dependent on the time of irradiation (UV dose) as well as on the H2O2 dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H2O2-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H2O2 treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.  相似文献   


9.
Delphin JE  Chapot JY 《Chemosphere》2006,64(11):1862-1869
A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C0) was 1 × 10−3 and 0.2 × 10−3, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C0) of atrazine, metolachlor and diuron were 10 × 10−3, 1 × 10−3 and 0.3 × 10−3 at 150 cm, respectively; 1/(C/C0) was correlated with Koc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V0) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V0 of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V0 was correlated with Koc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high Koc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.  相似文献   

10.
Tong SP  Liu WP  Leng WH  Zhang QQ 《Chemosphere》2003,50(10):1359-1364
The characteristics of different types of MnO2 catalytic ozonation of sulfosalicylic acid (SSal) and propionic acid (PPA) have been investigated in this paper. The experimental results show the dependence of catalytic activity of MnO2 on organic compounds and the pH of solutions, but it is independent on the type of MnO2. For example, three types of MnO2 have not any catalytic activity when ozonation of PPA under the condition of this experiment. All MnO2 catalytic ozonation of SSal at pH=1.0 have a greater total organic carbon removal than ozonation alone has, however, at pH=6.8 and 8.5, catalytic efficiency is not observed. Furthermore, the batch experimental results indicate that there are no direct relationship between the activity of metal oxide catalytic decomposition of ozone and that of its catalytic degradation of organic compounds.  相似文献   

11.
Wet peroxide degradation of atrazine   总被引:4,自引:0,他引:4  
The high temperature (150-200 degrees C), high pressure (3.0-6.0 MPa) degradation of atrazine in aqueous solution has been studied. Under these extreme conditions atrazine steadily hydrolyses in the absence of oxidising agents. Additionally, oxygen partial pressure has been shown not to affect atrazine degradation rates. In no case mineralisation of the parent compound was observed. The addition of the free radical generator hydrogen peroxide to the reaction media significantly enhanced the depletion rate of atrazine. Moreover, partial mineralisation of the organics was observed when hydrogen peroxide was used. Again, oxygen presence did not influence the efficiency of the promoted reaction. Consecutive injections of hydrogen peroxide throughout the reaction period brought the total carbon content conversion to a maximum of 65-70% after 40 min of treatment (suggesting the total conversion of atrazine to cyanuric acid). Toxicity of the effluent measured in a luminometer decreased from 93% up to 23% of inhibition percentage. The process has been simulated by means of a semi-empirical model.  相似文献   

12.
腐殖酸和铁对阿特拉津光降解影响的研究   总被引:2,自引:0,他引:2  
为考察除草剂在水体中的自净性能,对模拟太阳光(λ> 290 nm)下腐殖酸和铁元素对阿特拉津的光化学降解进行了研究。结果表明,单独辐照阿特拉津几乎不降解。在分别加入3、5和10 mg/L的腐殖酸时,阿特拉津的降解率分别为34.36 %、40.74%和15.66 %;在Fe(Ⅲ)投加量从0.01 mmol/L增加到0.2 mmol/L时,阿特拉津的降解率从24.36 %增加到34.97 %。而在当腐殖酸与铁共存时,阿特拉津降解率则进一步提高。紫外可见光谱和荧光光谱均表明,腐殖酸-铁络合物的形成及其光化学作用,促进了阿特拉津的降解。  相似文献   

13.
A loamy clay soil containing unextractable 14C-ring labeled atrazine residues was incubated in microcosms under abiotic and biotic conditions. The mineralization activity of the soil microflora was evaluated by the release of total CO2 and 14C02. After 63 days of sample incubation the total organic carbon mineralization was of 1.71%, that of 14C-residues was of 0.72% of the initial radioactivity. No direct relationship was established between the mineralization of atrazine residues and the global mineralization. The contribution of soil microorganisms in the release of 14C-residues was weak. The availability of non-extractable residues was mainly controlled by physico-chemical factors. The low value of the reextractability rate and the distribution of bound residues during the soil sample incubation shown the active role of organic matter in detoxification procedure. Ninety percent of the residues remained bound after 63 days of incubation and were thus, potentially available without biocide activity.

The fractionation of soil organic matter allowed to specify the distribution of bound residues within the organic compartments. After a long-stay of pesticides in soils, approximately 65% of bound residues were associated with humin.  相似文献   


14.
Andreozzi R  Raffaele M  Nicklas P 《Chemosphere》2003,50(10):1319-1330
The presence of pharmaceutical compounds in surface waters is an emerging environmental issue. Sewage treatment plants (STPs) are recognized as being the main point discharge sources of these substances to the environment. A monitoring campaign of STP effluents was carried out in four European countries (Italy, France, Greece and Sweden). More than 20 individual pharmaceuticals belonging to different therapeutic classes were found. For six selected pharmaceuticals (carbamazepine, diclofenac, clofibric acid, ofloxacin, sulfamethoxazole and propranolol) present in the STP effluents, the persistence towards abiotic photodegradation was evaluated submitting them to solar experiments at 40° N latitude during spring and summer. Based on experimentally measured quantum yields for the direct photolysis in bi-distilled water, half-life times (t1/2) at varying seasons and latitude were predicted for each substance. In salt- and organic-free (bi-distilled) water carbamazepine and clofibric acid are characterized by calculated half-life times of the order of 100 days at the highest latitudes (50° N) in winter, whereas under the same conditions sulphamethoxazole, diclofenac, ofloxacin and propranolol undergo fast degradation with t1/2 respectively of 2.4, 5.0, 10.6 and 16.8 days. For almost all studied compounds, except propranolol the presence of nitrate ions in aqueous solutions results in a reduction of t1/2. When present, humic acids act as inner filters towards carbamazepine and diclofenac, and as photosensitizers towards sulphamethoxazole, clofibric acid, oflaxocin and propranolol.  相似文献   

15.
Yuan BL  Li XZ  Graham N 《Chemosphere》2008,72(2):197-204
The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO2 suspension under UV illumination has been investigated using oxygen (O2) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O2 for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO2–UV–O2 system, while in contrast phthalic acid was found to be the main intermediate product in the TiO2–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO2–UV–O2 and TiO2–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO2–UV–O2 reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO2–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO2–UV–O2 and TiO2–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO2–UV–O2 reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO2–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.  相似文献   

16.
Tracer-based ground-water ages, along with the concentrations of pesticides, nitrogen species, and other redox-active constituents, were used to evaluate the trends and transformations of agricultural chemicals along flow paths in diverse hydrogeologic settings. A range of conditions affecting the transformation of nitrate and pesticides (e.g., thickness of unsaturated zone, redox conditions) was examined at study sites in Georgia, North Carolina, Wisconsin, and California. Deethylatrazine (DEA), a transformation product of atrazine, was typically present at concentrations higher than those of atrazine at study sites with thick unsaturated zones but not at sites with thin unsaturated zones. Furthermore, the fraction of atrazine plus DEA that was present as DEA did not increase as a function of ground-water age. These findings suggest that atrazine degradation occurs primarily in the unsaturated zone with little or no degradation in the saturated zone. Similar observations were also made for metolachlor and alachlor. The fraction of the initial nitrate concentration found as excess N2 (N2 derived from denitrification) increased with ground-water age only at the North Carolina site, where oxic conditions were generally limited to the top 5 m of saturated thickness. Historical trends in fluxes to ground water were evaluated by relating the times of recharge of ground-water samples, estimated using chlorofluorocarbon concentrations, with concentrations of the parent compound at the time of recharge, estimated by summing the molar concentrations of the parent compound and its transformation products in the age-dated sample. Using this approach, nitrate concentrations were estimated to have increased markedly from 1960 to the present at all study sites. Trends in concentrations of atrazine, metolachlor, alachlor, and their degradates were related to the timing of introduction and use of these compounds. Degradates, and to a lesser extent parent compounds, were detected in ground water dating back to the time these compounds were introduced.  相似文献   

17.
采用低频超声与Fe-Ni-Mn/Al2O3催化剂协同降解偶氮染料酸性绿B模拟废水,考察染料初始浓度和pH值、催化剂、饱和气体及H2O2等因素对酸性绿B降解效果的影响,结果表明:催化剂Fe-Ni-Mn/Al2O3与低频超声存在协同效应,催化剂的最佳投加量为6g/L;酸性条件有利于染料的超声降解,当pH=3.8时,可取得最佳的降解效果;酸性绿B降解率随初始浓度的增大而降低,其优化初始浓度为100mg/L,此外,在反应体系中鼓入饱和气体也可促进酸性B的降解,且影响顺序为混合气体(air+Ar)〉氧气〉氩气;在反应过程中投加H2O2有利于染料降解率的提高。在优化实验条件下降解150min,酸性绿B色度去除率达到91.4%。  相似文献   

18.
Cui H  Hwang HM  Zeng K  Glover H  Yu H  Liu Y 《Chemosphere》2002,47(9):991-999
The effect of the photosensitizer riboflavin (0, 10, 50, 100 microM) on the fate of atrazine (10 mg/l) in a freshwater environment was studied. It was found that at 100 microM riboflavin significantly enhanced the degradation of atrazine and more than 80% of atrazine in a natural water environment was depleted in 72 h. The relative contribution of microbial assemblages and the freshwater matrix to the degradation of atrazine and the degradation kinetics of atrazine were compared under different experimental conditions. The products and pathways of atrazine transformation were studied with GC-MS and HPLC with a photodiode array detector. The results show that dealkylation and alkyl chain oxidation are involved in the degradation of atrazine.  相似文献   

19.
Fenton''s type reaction and chemical pretreatment of PCBs   总被引:3,自引:0,他引:3  
This study evaluates the effects of Fenton's reagent (FR) on the rate and extent of the oxidative degradation of individual mono, di-, tri- and tetrachlorobiphenyls in the commercial mixture DELOR 103, equivalent to AROCLOR 1248. The oxidation effect of FR strongly increased with increasing the molar ratio of Fe2+/H2O2. The most effective oxidation of DELOR 103 (10 μg.ml−1) was achieved in a solution containing 1M H2O2 and 1 mM Fe2+. The FR elimination rate constants of PCB congeners decrease with increasing number of chlorine substituents in the biphenyl molecule and show a good correlation with the values of molecular weights of the PCB congeners and their 1-octanol/water partition coefficients.  相似文献   

20.
Atrazine, a broad-leaf herbicide, has been used widely to control weeds in corn and other crops for several decades and its extensive used has led to widespread contamination of soils and water bodies. Phytoremediation with switchgrass and other native prairie grasses is one strategy that has been suggested to lessen the impact of atrazine in the environment. The goal of this study is to characterize: (1) the uptake of atrazine into above-ground switchgrass biomass; and (2) the degradation and transformation of atrazine over time. A fate study was performed using mature switchgrass columns treated with an artificially-created agricultural runoff containing 16 ppm atrazine. Soil samples and above-ground biomass samples were taken from each column and analyzed for the presence of atrazine and its chlorinated metabolites. Levels of atrazine in both soil and plant material were detectable through the first 2 weeks of the experiment but were below the limit of detection by Day 21. Levels of deethylatrazine (DEA) and didealkylatrazine (DDA) were detected in soil and plant tissue intermittently over the course of the study, deisopropylatrazine (DIA) was not detected at any time point. A radiolabel study using [14C]atrazine was undertaken to observe uptake and degradation of atrazine with more sensitivity. Switchgrass columns were treated with a 4 ppm atrazine solution, and above-ground biomass samples were collected and analyzed using HPLC and liquid scintillation counting. Atrazine, DEA, and DIA were detected as soon as 1 d following treatment. Two other metabolites, DDA and cyanuric acid, were detected at later time points, while hydroxyatrazine was not detected at all. The percentage of atrazine was observed to decrease over the course of the study while the percentages of the metabolites increased. Switchgrass plants appeared to exhibit a threshold in regard to the amount of atrazine taken up by the plants; levels of atrazine in leaf material peaked between Days 3 and 4 in both studies.  相似文献   

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