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1.
W S Kuo 《Chemosphere》1999,39(11):1853-1860
Synergistic effects including TOC elimination, ozone consumption and microtoxicity reduction for combination of photolysis and ozonation compared to those of direct photolysis and ozonation alone on destruction of chlorophenols including 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol were studied. It was found that the synergistic effects of combination of photolysis and ozonation increased obviously with increasing initial pH of solution to basic pH levels. Results showed that the synergistic effects of photolytic ozonation under the conditions imposed was notable with mineralization rate enlarging more than 100%, oxidation index (OI) decreasing 50%, and microtoxicity being reduced by 30%, indicating that the potentialities of photolytic ozonation compared to direct photolysis and ozonation alone was remarkable for treatment of industrial wastewater containing chlorophenols.  相似文献   

2.
The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is one of the most widely used pesticides in the Canadian prairies and is frequently detected as a ground and surface water contaminant. The objective of this paper was to determine the magnitude and extent of variation of 2,4-D mineralization in a cultivated undulating prairie landscape. Microcosm incubation experiments, using a 4 x 3 x 2 factorial experimental design (soil moisture, 4 levels: 60, 85, 110, 135% of field capacity; slope position, 3 levels: upper-, mid- and lower-slopes; soil depth, 2 levels: 0-5 and 5-15 cm), were used to assess 2,4-D mineralization. The first-order mineralization rate constant (k(1)) varied from 0.03 to 0.22 day(- 1), while total 2,4-D mineralization varied from 31 to 52%. At near-saturated conditions (110 and 135% of field capacity), the onset of 2,4-D degradation was delayed in soil obtained from the upper- and mid-slopes but not in soils obtained from the lower-slope position. The k(1) and total 2,4-D mineralization was significantly influenced by all three factors and their interactions. The Freundlich sorption coefficient of 2,4-D ranged from 0.83 to 2.46 microg (1-1/n)g(- 1) mL(1/n) and was significantly influenced by variations in soil organic carbon content across slope positions. The infield variability of 2,4-D sorption and mineralization observed across slope positions in this undulating field was comparable in magnitude and extent to the regional variability of 2,4-D sorption and mineralization observed in surface soils across Manitoba. The large variability of 2,4-D mineralization and sorption at different slope positions in this cultivated undulating field suggests that landform segmentation models, which are used to delineate slope positions, are important considerations in pesticide fate studies.  相似文献   

3.
This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2.4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 microg(1 - 1/n) g(-1) mL(1/n). First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.  相似文献   

4.
Chaudhary AJ  Grimes SM 《Chemosphere》2008,72(11):1636-1642
The effects of the presence of copper on the photooxidation of phenol and 4-chlorophenol and of the presence of the phenols on the recovery of copper by electrodeposition are studied in three systems: a photolytic cell in the presence and absence of TiO2 as a catalyst or H2O2 as an oxidant; an electrolytic cell and a combined photolytic-electrolytic system. The optimum system for the simultaneous removal of copper and destruction of the phenols which overcomes the effects of copper-phenol reactions is a combined system with concentrator electrode technology incorporated into the electrolytic cell. This combined system achieves >99% removal of copper and destruction of phenol or 4-chlorophenol in an 8 h period.  相似文献   

5.
In this study, the effects of size of adsorbent, temperature, pH of solution, ionic strength, presence of inorganic substances such as calcium ion, magnesium ions, chloride ions, fertilizers and presence of organic substances such as dissolved organic matter, surfactant, other herbicides on sorption of 2,4-D and atrazine onto rubber granules were investigated. The removal efficiency was more for fine adsorbent particles. Temperature played an important role in sorption process. Temperature effect was endothermic for 2,4-D and exothermic for atrazine, respectively. The removals were maximum at pH 4 for 2,4-D and at pH 6 for atrazine. The presence of other herbicide (butachlor) reduced sorption capacity of rubber granules by approximately 10% for both 2,4-D and atrazine. All other factors had insignificant effect on sorption capacity. The mathematical expressions were developed for predicting the overall percentage removal of 2,4-D and atrazine on the basis of major four controlling factors viz. adsorbent size, temperature, pH and presence of other herbicide.  相似文献   

6.
This study explored the biodegradation potential of two agricultural pesticides (2,4-D and isoproturon) as well as their effect on the performance of the anaerobic digestion process. Three 3.5 L batch reactors were used, having the same initial isoproturon concentration (25 mg/L) and different 2,4-D concentrations (i.e. 0, 100, or 300 mg/L, respectively). All systems were fed with equal amounts of primary sludge and digested sludge and operated at the low mesophilic range (32 +/- 2 degrees C). Following an acclimation period of approximately 30 days, complete 2,4-D removal was achieved, whereas isoproturon biodegradation was practically negligible. The presence of 2,4-D did not have a direct effect on acidogenesis since soluble organic carbon [expressed either as volatile fatty acids (VFAs) or as total organic carbon (TOC)] peaked within the first 10 days of operation in all bioreactors. Utilization of VFAs however appeared to follow two distinct patterns: one pattern was represented by acetate and butyrate (i.e. no acid accumulation) while the other was followed by propionate, isobuturate, valerate and isovalerate (i.e. acid accumulation, duration of which was related to the initial 2,4-D concentration). On the whole, all reactors exhibited a successful digestion performance demonstrated by complete VFAs utilization, considerable gas production (containing 45 to 65% methane by volume), substantial volatile suspended solids (VSS) reduction (42 to 50%), as well as pH and alkalinity recovery.  相似文献   

7.
This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg(-1), the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day(-1) and the total amount of 2,4-D mineralized at 130 days (M(130)) ranged from 24 to 39%. Both k and M(130) were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M(130) were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.  相似文献   

8.
Abstract

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2,4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 µg1?1/n  g?1 mL1/ n . First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.  相似文献   

9.
The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is one of the most widely used pesticides in the Canadian prairies and is frequently detected as a ground and surface water contaminant. The objective of this paper was to determine the magnitude and extent of variation of 2,4-D mineralization in a cultivated undulating prairie landscape. Microcosm incubation experiments, using a 4 × 3 × 2 factorial experimental design (soil moisture, 4 levels: 60, 85, 110, 135% of field capacity; slope position, 3 levels: upper-, mid- and lower-slopes; soil depth, 2 levels: 0–5 and 5–15 cm), were used to assess 2,4-D mineralization. The first-order mineralization rate constant (k1) varied from 0.03 to 0.22 day? 1, while total 2,4-D mineralization varied from 31 to 52%. At near-saturated conditions (110 and 135% of field capacity), the onset of 2,4-D degradation was delayed in soil obtained from the upper- and mid-slopes but not in soils obtained from the lower-slope position. The k1 and total 2,4-D mineralizationwas significantly influenced by all three factors and their interactions. The Freundlich sorption coefficient of 2,4-D ranged from 0.83 to 2.46 ug 1–1/ng? 1 mL1/n and was significantly influenced by variations in soil organic carbon content across slope positions. The infield variability of 2,4-D sorption and mineralization observed across slope positions in this undulating field was comparable in magnitude and extent to the regional variability of 2,4-D sorption and mineralization observed in surface soils across Manitoba. The large variability of 2,4-D mineralization and sorption at different slope positions in this cultivated undulating field suggests that landform segmentation models, which are used to delineate slope positions, are important considerations in pesticide fate studies.  相似文献   

10.
Using a laboratory-scale mixed reactor, the performance of alumina in degrading 2,4-Dichlorophenoxyacetic acid with ozone in the presence of tert-butyl alcohol radical scavenger was studied. The operating variables investigated were the dose of alumina catalyst and solution pH. Results showed that using ozone and alumina leads to a significant increase in 2,4-D removal in comparison to non-catalytic ozonation and adsorption processes. The observed reaction rate constants (k(obs)) for 2,4-D during ozonation were found to increase linearly with increasing catalyst dose. At pH 5, the k(obs) value increased from 19.3 to 26 M(-1) s(-1) and 67 M(-1) s(-1) when varying the alumina dose from 1 to 2 and 4 g L(-1), respectively. As pH was increased, higher reaction rates were observed for both non-catalytic ozonation and catalytic ozonation processes. Thus, at pH 3 and using a catalyst dose of 8 g L(-1), the k(obs) values for non-catalytic ozonation and catalytic ozonation processes were 3.4 and 58.9 M(-1) s(-1), respectively, whereas at pH 5 reaction rate constants of 6.5 and 128.5 M(-1) s(-1) were observed, respectively. Analysis of total organic carbon suggested that catalytic ozonation with alumina achieved a considerable level of mineralization of 2,4-D. Adsorption of 2,4-D on alumina was found to play an important role in the catalytic ozonation process.  相似文献   

11.
Concentration of 2,4-dichlorophenoxyacetic acid (2,4-D) may affect its degradation kinetics in advanced oxidation systems, and combinations of two or more systems can be more effective for its mineralization at low concentration levels. Degradations and mineralizations of 0.045mM 2,4-D using O(3), O(3)/UV, UV/TiO(2) and O(3)/UV/TiO(2) systems were compared, and influence of reaction temperature on the mineralization in O(3)/UV/TiO(2) system was investigated. 2,4-D degradations by O(3), O(3)/UV and UV/TiO(2) systems were similar to the results of earlier investigations with higher 2,4-D concentrations. The degradations and total organic carbon (TOC) removals in the four systems were well described by the first-order reaction kinetics. The degradation and removal were greatly enhanced in O(3)/UV/TiO(2) system, and further enhancements were observed with larger O(3) supplies. The enhancements were attributed to hydroxyl radical (()OH) generation from more than one reaction pathway. The degradation and removal in O(3)/UV/TiO(2) system were very efficient with reaction temperature fixed at 20 degrees C. It was suspected that reaction temperature might have influenced ()OH generation in the system, which needs further attention.  相似文献   

12.

Background and purposes

The pathways used by microorganisms for the metabolism of every xenobiotic substrate are specific. The catabolism of a xenobiotic goes through a series of intermediate steps and lower intermediates (metabolites) appear in sequence. The structure of the metabolites can be similar to the parents due to kinship. The purposes of this study were to examine if the degradation pathways that were developed for a parent xenobiotic are effective to degrade the parent??s lower metabolites, and if the reverse is true.

Materials and methods

The xenobiotic substrates, 2,4-dichlorophenoxyacetic acid (2,4-D, the parent xenobiotic) and its metabolite 2,4-dichlorophenol (2,4-DCP), were independently subjected to acclimation and degradation tests by the biomasses of mixed-culture activated sludge and a pure culture of Arthrobacter sp.

Results

Activated sludge and Arthrobacter sp. that were acclimated to 2,4-D effectively degraded 2,4-D and the lower metabolites of 2,4-D, typically 2,4-DCP. During the degradation of 2,4-D, accumulations of the lower metabolites of 2,4-D were not found. The degradation pathways acquired from acclimation to 2,4-D are effective for all the metabolites of 2,4-D. However, pathways acquired from acclimation to 2,4-DCP are not effective in the degradation of the parent 2,4-D.

Conclusions

Microorganisms acclimated to 2,4-D evolve their degradation pathways by a scheme that is different from the scheme the microorganisms employ when they are acclimated to the metabolites of 2,4-D.  相似文献   

13.
Paterlini WC  Nogueira RF 《Chemosphere》2005,58(8):1107-1116
The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20 min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated.  相似文献   

14.
This study explored the biodegradation potential of two agricultural pesticides (2,4-D and isoproturon) as well as their effect on the performance of the anaerobic digestion process. Three 3.5 L batch reactors were used, having the same initial isoproturon concentration (25 mg/L) and different 2,4-D concentrations (i.e. 0, 100, or 300 mg/L, respectively). All systems were fed with equal amounts of primary sludge and digested sludge and operated at the low mesophilic range (32 ± 2°C). Following an acclimation period of approximately 30 days, complete 2,4-D removal was achieved, whereas isoproturon biodegradation was practically negligible. The presence of 2,4-D did not have a direct effect on acidogenesis since soluble organic carbon [expressed either as volatile fatty acids (VFAs) or as total organic carbon (TOC)] peaked within the first 10 days of operation in all bioreactors. Utilization of VFAs however appeared to follow two distinct patterns: one pattern was represented by acetate and butyrate (i.e. no acid accumulation) while the other was followed by propionate, isobuturate, valerate and isovalerate (i.e. acid accumulation, duration of which was related to the initial 2,4-D concentration). On the whole, all reactors exhibited a successful digestion performance demonstrated by complete VFAs utilization, considerable gas production (containing 45 to 65% methane by volume), substantial volatile suspended solids (VSS) reduction (42 to 50%), as well as pH and alkalinity recovery.  相似文献   

15.
Kinetics and mechanism of TNT degradation in TiO2 photocatalysis   总被引:9,自引:0,他引:9  
Son HS  Lee SJ  Cho IH  Zoh KD 《Chemosphere》2004,57(4):309-317
The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.  相似文献   

16.
I G Dubus  E Barriuso  R Calvet 《Chemosphere》2001,45(6-7):767-774
The sorption behaviour of a new wheat hybridising agent (clofencet, 2-4-(chlorophenyl)-3-ethyl-2,5-dihydro-5-oxopyridazine-4-carboxylic acid) was investigated in batch equilibrium experiments and compared to that of two other organic acids (2,4-D and salicylic acid). Sorption coefficients Kd for the three compounds were determined in 18 Cambisols and Ferralsols. Kd values for clofencet were 0.3-9.4 l/kg for Cambisols and 2.1-68 l/kg for Ferralsols. Sorption of clofencet was strongly related statistically to that of salicylic acid. Sorption of clofencet and salicylic acid decreased exponentially with increasing solution pH in Cambisols whereas a bell-shaped curve was obtained for the sorption of salicylic acid in Ferralsols. Sorption of 2,4-D (2,4-dichlorophenoxyacetic acid) was not statistically related to the pH of the different soils. Positively charged oxide surfaces were shown to play a significant role in the sorption of clofencet and salicylic acid. The use of simple correlation and multiple linear regressions suggested that the main sorption mechanisms of clofencet in soils were likely to be ligand exchange on oxide surfaces and, to a lesser extent, cation bridging. Differences in the sorption behaviour of clofencet/salicylic acid and 2,4-D might be attributed to the possibility of the two former compounds forming bidentate complexes with metals.  相似文献   

17.
Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe3O4 was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L?1 nanoscale Fe3O4, and the reaction rates increased with increasing dosage of nanoscale Fe3O4. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe3O4 was slower than that by nanoscale Fe3O4. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.  相似文献   

18.
The fate and transport of 2,4-dichlorophenoxyacetic acid (2,4-D) in the subsurface is affected by a complex, time-dependent interplay between sorption and mineralization processes. 2,4-D is biodegradable in soils, while adsorption/desorption is influenced by both soil organic matter content and soil pH. In order to assess the dynamic interactions between sorption and mineralization, 2,4-D mineralization experiments were carried using three different soils (clay, loam and sand) assuming different contact times. Mineralization appeared to be the main process limiting 2,4-D availability, with each soil containing its own 2,4-D decomposers. For the clay and the loamy soils, 45 and 48% of the applied dose were mineralized after 10 days. By comparison, mineralization in the sandy soil proceeded initially much slower because of longer lag times. While 2,4-D residues immediately after application were readily available (>93% was extractable), the herbicide was present in a mostly unavailable state (<2% extractable) in all three soils after incubation for 60 days. We found that the total amount of bound residue decreased between 30 and 60 incubation days. Bioaccumulation may have led to reversible immobilization, with some residues later becoming more readily available again to extraction and/or mineralization.  相似文献   

19.
The inhibitory effect of the herbicides 2-methyl-4-chlorophenoxyacetic acid (MCPA) and 2,4-dichlorophenoxyacetic acid (2,4-D) in Saccharomyces cerevisiae growth is strongly dependent on medium pH (range 2.5-6.5). Consistent with the concept that the toxic form is the liposoluble undissociated form, at values close to their pK(a) (3.07 and 2.73, respectively) the toxicity is high, decreasing with the increase of external pH. In addition, the toxicity of identical concentrations of the undissociated acid form is pH independent, as observed with 2,4-dichlorophenol (2,4-DCP), an intermediate of 2,4-D degradation. Consequently, at pH values above 3.5 (approximately one unit higher than 2,4-D pK(a)), 2,4-DCP becomes more toxic than the original herbicide. A dose-dependent inhibition of growth kinetics and increased duration of growth latency is observed following sudden exposure of an unadapted yeast cell population to the presence of the herbicides. This contrasts with the effect of 2,4-DCP, which essentially affects growth kinetics. Experimental evidences suggest that the acid herbicides toxicity is not exclusively dependent on the liposolubility of the toxic form, as may essentially be the case of 2,4-DCP. An unadapted yeast cell population at the early stationary-phase of growth under nutrient limitation is significantly more resistant to short-term herbicide induced death than an exponential-phase population. Consequently, the duration of growth latency is reduced, as observed with the increase of the size of the herbicide stressed population. However, these physiological parameters have no significant effect either on growth kinetics, following growth resumption under herbicide stress, or on the growth curve of yeast cells previously adapted to the herbicides, indicating that their role is exerted at the level of cell adaptation.  相似文献   

20.
Ninety strains of fungi from the collection of our mycology laboratory were tested in Galzy and Slonimski (GS) synthetic liquid medium for their ability to degrade the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its by-product, 2,4-dichlorophenol (2,4-DCP) at 100 mg l(-1), each. Evolution of the amounts of each chemical in the culture media was monitored by HPLC. After 5 days of cultivation, the best results were obtained with Aspergillus penicilloides and Mortierella isabellina for 2,4-D and with Chrysosporium pannorum and Mucor genevensis for 2,4-DCP. The data collected seemed to prove, on one hand, that the strains responses varied with the taxonomic groups and the chemicals tested, and, on the other hand, that 2,4-D was less accessible to fungal degradation than 2,4-DCP. In each case, kinetics studies with the two most efficient strains revealed that there was a lag phase of 1 day before the onset of 2,4-D degradation, whereas there was none during 2,4-DCP degradation. Moreover, 2,4-DCP was detected transiently during 2,4-D degradation. Finally, M. isabellina improved its degradation potential in Tartaric Acid (TA) medium relative to GS and Malt Extract (ME) media.  相似文献   

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