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1.
The influence of natural organic matter (NOM) rigidity on the sorption, desorption, and competitive displacement rates of 1,2-Dichlorobenzene (1,2-DCB) was evaluated using batch reactor experiments with two surface soils (Yolo and Forbes) and a shale (Ohio). Previous characterization suggests that the shale NOM is the most reduced and condensed, the Yolo soil is the most oxidized and amorphous, and Forbes soil has an intermediate NOM structure. The rate study for each sorbent was conducted under the same reactor parameters, and 1,2-DCB mass-transfer rates were determined using the distributed first-order mass-transfer rate model based on the gamma probability density function. To measure competitive displacement rates, 1,2,4-trichlorobenzene (1,2,4-TCB) was delivered as a competitor after 34 days pre-equilibration. Higher fractions of contaminant subject to instantaneous mass transfer and much faster rates of approach to apparent sorption equilibrium are found in Yolo soil when compared with Forbes soil and the shale. The size of the instantaneously desorbing fraction thus appears inversely related to the hard carbon fraction. In the NOM compartment where mass transfer is rate-limited, rate coefficient distributions are shifted toward lower rates for desorption and competitive displacement of 1,2-DCB in Ohio shale, followed by Forbes soil. Sorption and desorption rate distributions are almost the same for the shale, while desorption rates are a few times greater than sorption rates in Yolo and Forbes soils. Mass-transfer coefficients for competitive displacement are considerably slower than those for desorption in Forbes soil and the shale. However, the mass-transfer rates for the two processes seem to be similar in Yolo soil, which has a NOM matrix comprising a relatively larger soft organic carbon fraction. The concept of "solute induced softening" is discussed as a mechanistic rationale for the experimental observations.  相似文献   

2.
Roles of acetone-conditioning and lipid in sorption of organic contaminants   总被引:1,自引:0,他引:1  
Sorption of phenanthrene and 1-naphthol by a peat soil (PS) and its humic acid fractions (HAs) and humin (HM) was examined. Both phenanthrene and 1-naphthol consistently had decreased isotherm nonlinearity in the order PS > HA1 (first fraction) > HA7 (seventh fraction), due to decreased heterogeneity of soil organic matter (SOM). High isotherm nonlinearity of HM was attributed to the condensed structure of SOM in it. Acetone-conditioning increased sorption affinity and isotherm nonlinearity of HAs and HM for phenanthrene, and the conditioning effect was more pronounced at low solute concentrations. However, sorption of 1-naphthol by PS, HAs, and HM was insignificantly affected by acetone-conditioning, suggesting that 1-naphthol could have disparate distribution of sorbed sites from phenanthrene due to their structure and hydrophobicity difference. Lipid removal further increased sorption of phenanthrene and 1-naphthol by acetone-conditioned PS, HAs, and HM, due to increased accessibility of high-energy sites in SOM. Nonlinearity of phenanthrene and 1-naphthol also increased after lipid removal from the acetone-conditioned sorbents. In 1-naphthol- and phenanthrene-lipid competitive sorption systems, lipid had strong competition with phenanthrene, whereas 1-naphthol exhibited cooperative sorption with lipid on lipid-free PS, HAs, and HM, again showing the different sorption characteristics between phenanthrene and 1-naphthol.  相似文献   

3.
Knowledge of toxic chemical sorption by carbon nanotubes (CNTs) is critical for environmental application of CNTs as superior sorbents and for environmental risk assessment of both CNTs and toxic chemicals. Single-solute sorption results were reported in the literature, however, they cannot be used for predicting pollutant sorption by CNTs in wastewater and natural water systems where multiple organic contaminants are present. In this study, competitive sorption of pyrene, phenanthrene, and naphthalene on a multiwalled CNT material was investigated. All isotherms in single-, bi-, and tri-solute systems were fitted well by the Dubinin-Ashtakhov (DA) model. The isotherm of a given primary solute changed from being significantly nonlinear to nearly linear when competitors were added. The observed competitive sorption depended on the relative equilibrium concentrations of both primary and cosolutes. Significant competition was observed at relatively low concentrations of primary solute and high concentrations of competitors, while competition was much weaker in the case of relatively high concentrations of primary solute and low competitor concentrations. When the relative concentration of primary solute (Ce/Cs) approached 1, competition by other solutes seemed to disappear. Sorption and competition of three polycyclic aromatic hydrocarbons (PAHs) on CNTs could not be explained with either pore-filling or partition-adsorption mechanisms. A Polanyi-based surface adsorption mechanism was proposed to interpret the observed sorption and competition.  相似文献   

4.
Sorption isotherms for five aromatic hydrocarbons were obtained with a natural wood char (NC1) and its residue after solvent extraction (ENC1). Substantial isotherm nonlinearity was observed in all cases. ENC1 showed higher BET surface area, higher nitrogen-accessible micropore volume, and lower mass of extractable organic chemicals, including quantifiable polycyclic aromatic hydrocarbons (PAHs),while the two chars showed identical surface oxygen/ carbon (O/C) ratio. For two chlorinated benzenes that normally condense as liquids at the temperatures used, sorption isotherms with NC1 and ENC1 were found to be statistically identical. For the solid-phase compounds (1,4-dichlorobenzene (1,4-DCB) and two PAHs), sorption was statistically higher with ENC1, thus demonstrating sorption effects due to both (1) authigenic organic content in the sorbentand (2)the sorbate's condensed state. Polanyi-based isotherm modeling, pore size measurements, and comparisons with activated carbon showthe relative importance of adsorptive pore filling and help explain results. With both chars, maximum sorption increased in the order of decreasing molecular diameter: phenanthrene < naphthalene < 1,2-dichlorobenzene/1,2,4-trichlorobenzene < 1,4-DCB. Comparison of 1,4- and 1,2-DCB shows that the critical molecular diameter was apparently more important than the condensed state, suggesting that 1,4-DCB sorbed in the liquid state for ENC1.  相似文献   

5.
Natural organic matter (NOM) hydration is found to change activity-based sorption of test organic compounds by as much as 2-3 orders of magnitude, depending on the compound and the specific NOM sorbent. This is demonstrated for sorption on humin, humic acid, and the NOM source material. Hydration assistance in organic compound sorption correlates with the ability of the sorbate to interact strongly with hydrated sorbents, demonstrating the important role of noncovalent polar links in organizing the sorbent structure. Differences in hydration effect between the sorbents are caused mainly by differences in compound-sorbent interactions in the dry state. For a given compound, hydration of the sorbent tends to equalize the sorption capability of the three sorbents. No correlation was found between the strength of sorbate-sorbent interactions or the type of sorbate functional groups and the extent of sorption nonlinearity. Sorption nonlinearity compared over the same sorbed concentration range is greater on the original NOM than on either of the two extracted fractions. In elucidating sorption mechanisms on hydrated NOM, it is important to explicitly consider the participation of water molecules in organic compound interactions in the NOM phase.  相似文献   

6.
Sorption hysteresis in environmental sorbents has important implications for pollutant transport and bioavailability. We examined the reversibility of sorption of benzene, toluene, and nitrobenzene, both singly and in pairs, by wood charcoal. A previous study showed that these compounds compete for the same set of adsorption sites on the char. Single-solute sorption was weakly hysteretic at high concentrations. The finding of comparable irreversibility for these compounds was taken as evidence that hysteresis is true and caused by pore elasticity. Hysteresis in the presence of a competitor was weak at low cosolute concentration but became stronger as the cosolute concentration increased. We attribute the growing hysteresis with cosolute concentration to a thermodynamic "competitor dilution effect"--a heretofore-unrecognized cause of hysteresis in multi-solute systems when the competing solute is simultaneously diluted with the target solute in the desorption step. It arises because the target solute re-equilibrates from a sorption point where competition is relatively high, to a desorption point where competition is relatively low. Simulations based on Ideal Adsorbed Solution Theory, a thermodynamic competition model, support the hypothesis. The cosolute also causes an increase in the linearity of the target solute isotherm, also attributable to competition thermodynamics. The competitive dilution effect can play a role in pollutant behavior in real systems if competing substances, natural or anthropogenic, are diluted or degraded making the target less accessible with time.  相似文献   

7.
Soil and sediment materials having organic matter matrixes of different geochemical character were examined with respect to their sorption and desorption of phenanthrene in the presence of order-of-magnitude larger concentrations of trichloroethylene (TCE) and dichlorobenzene (DCB). These co-contaminants depressed phenanthrene sorption in the lowest residual solution phase concentration ranges of that target solute investigated, whereas in its highest residual concentration regions phenanthrene sorption was either not affected or was actually enhanced. In both concentration ranges, the effects observed varied with the hydrophobicity and relative concentration of the co-contaminant and with the geological maturity and associated degree of condensation and aromatization of the soil/sediment organic matter (SOM). Desorption isotherms for phenanthrene indicate the occurrence of increased hysteresis in the presence of high concentrations of DCB and TCE, the effect increasing with increased degree of associated organic condensation. Tests in which high concentrations of DCB and TCE were added after completion of the phenanthrene desorption experiments show clear evidence of partial displacement of sorbed phenanthrene to the solution phase. The results of the work support the concept of SOM glass-transition concentrations, above which matrix deformation occurs and so-called "conditioning effects" are observed.  相似文献   

8.
Interactions of a wide set of organic compounds with model natural organic matter (NOM, Pahokee peat) were examined using a new approach that converts aqueous sorption to compound transfer from n-hexadecane to the hydrated NOM. This conversion accounts for solute-water interactions and applies the same inert reference medium for all compounds of interest, making it possible to classify sorbates according to the strength of sorbate-NOM interactions. Differences in strength of organic compound interactions in the sorbed phase as great as 4-5 orders of magnitude are demonstrated. The strongest interactions were observed for compounds with well-established H-bonding potentials. Considering hydrocarbons and Cl-substituted hydrocarbons, aliphatic compounds gain more upon distribution from the n-hexadecane medium to NOM than do aromatic compounds. Sorption nonlinearity was tested by comparing the change in n-hexadecane-hydrated NOM distribution coefficient (K(d,i)) versus sorbed concentration for the different compounds. Only those compounds that interact most strongly with NOM demonstrated significant sorption nonlinearity, expressed by a strong reduction in K(d,i) as a function of sorbed concentration. The relationship between compound ability to interact with NOM and reduction in K(d,i) as a function of sorbed concentration can be used to characterize compound distribution among different sorption domains.  相似文献   

9.
The sorption behavior of organic compounds (phenanthrene, lindane, and atrazine) to sequentially extracted humic acids and humin from a peat soil was examined. The elemental composition, XPS and (13)C NMR data of sorbents combined with sorption isotherm data of the tested compounds show that nonspecific interactions govern sorption of phenanthrene and lindane by humic substances. Their sorption is dependent on surface and bulk alkyl carbon contents of the sorbents, rather than aromatic carbon. Sorption of atrazine by these sorbents, however, is regulated by polar interactions (e.g., hydrogen bonding). Carboxylic and phenolic moieties are key components for H-bonding formation. Thermal analysis reveals that sorption of apolar (i.e., phenanthrene and lindane) and polar (i.e., atrazine) compounds by humic substances exhibit dissimilar relationships with condensation and thermal stability of sorption domains, emphasizing the major influence of domain spatial arrangement on sorption of organic compounds with distinct polarity. Results of pH-dependent sorption indicate that reduction in sorption of atrazine by the tested sorbents is more evident than phenanthrene with increasing pH, supporting the dependence of organic compound sorption on its polarity and structure. This study highlights the different interaction mechanisms of apolar and polar organic compounds with humic substances.  相似文献   

10.
Long-term sorption behaviors of phenanthrene (Phen) on the Borden sand from 1 min to 365 days and of Phen and 1,2-dichlorobenzene (DCB) on the isolated kerogen from 1 to 120 days were characterized by examining the time dependence of solute phase distribution relationships (PDRs) and compared with the prior reported sorption of tetrachlorobenzene (TeCB) and tetrachloroethene (PCE) on the pulverized and/or acid-treated bulk sand and size fractions. The sorption kinetics for Phen on the bulk sand and its kerogen isolate can well be described by the fractional power kinetics equation (q(e) = kt(b)). The similar rate parameter b for q(e)(t) vs t at 5-7 levels of initial concentrations of Phen on the two sorbents, respectively, ranging from 0.077 to 0.099 and from 0.072 to 0.086, indicates the similar sorption kinetics rate. The modified-Freundlich parameters of TeCB on the pulverized or acid-treated 0.3-mm size fraction match those of Phen on the isolated kerogen, suggesting the same natural organic matter (NOM) property of the two sorbents. As the prior investigation underestimated the Koc value for the TeCB sorption on the acid-treated 0.3-mm size fraction by a factor of 1.76, the estimated time to reach 95% of sorption equilibrium is much longer than the prior estimation (over 10 years vs about 2.5 years). The estimated times to reach 95% of sorption equilibrium at three levels of relative solubility for Phen on the bulk sand and its isolated kerogen are, respectively, longer than one decade, demonstrating the similar diffusion length for Phen on the two sorbents. The observed slow sorption kinetics is related to nanometer-pore diffusion within kerogen matrix. The investigation supplies new clues for explaining the often observed much longer persistence of organic contaminants in soils and sediments than the prediction based on the short-term laboratory experiment.  相似文献   

11.
According to a recent conceptual model for hydration-assisted sorption of organic compounds in natural organic matter (NOM), certain polar moieties of dry NOM are unavailable for compound sorption due to strong intra- and intermolecular NOM interactions. Water molecules solvate these moieties creating new sorption sites at solvated contacts. It is expected that the greater a compound's ability to undergo specific interactions with NOM, the greater will be the hydration-assisted sorption effect, because penetration of compounds into solvated contacts must involve competition with water at the solvated contact. To test this model, we compare the hydration effect on sorption kinetics and equilibrium for 4 compounds with differing abilities to undergo specific interactions with NOM. Sorption measured on Pahokee peat in aqueous systems was fast compared with n-hexadecane (dry) systems. No concentration effect on attainment of sorption equilibrium was observed. m-Nitrophenol exhibited the greatest hydration-assisted sorption effect, benzyl alcohol showed an intermediate effect and acetophenone and nitrobenzene showed no hydration-assisted sorption, on an activity scale. The extent of hydration-assisted sorption effect correlates with compound ability to undergo specific interactions. These results support the conceptual model and demonstrate the importance of polar NOM noncovalent links in organizing the NOM phase and in controlling the hydration effect on sorption of organic compounds.  相似文献   

12.
Sorption of pyrene and phenanthrene to model (illite and charcoal) and natural (Yangtze sediment) geosorbents were investigated by batch techniques using fluorescence spectroscopy. A higher adsorption of phenanthrene was observed with all sorbents, which is related to the better accessibility of smaller molecules to micropores in the molecular sieve sorbents. In addition, pyrene sorption in binary-solute systems with a constant initial concentration of phenanthrene (0.1 μmol L(-1) or 2 μmol L(-1)) was studied. A 0.1 μmol L(-1) concentration of phenanthrene causes no competitive effect on the pyrene sorption. A 2 μmol L(-1) concentration of phenanthrene significantly suppresses the sorption of pyrene, especially in the low concentration range; nonlinearity of the pyrene sorption isotherms thus decreases. The competitive effect of 2 μmol L(-1) phenanthrene on the pyrene sorption is overestimated by the ideal adsorbed solution theory (IAST) using the fitted single sorption results of both solutes. An adjustment of the IAST application by taking into account the molecular sieve effect is proposed, which notably improves the IAST prediction for the competitive effect.  相似文献   

13.
There is an increasing concern about the protection of groundwater from contamination by enteric viruses and the prevention of outbreaks of waterborne diseases. Knowledge of survivability and transport of viruses from their point of origin is necessary to determine their potential effects on the neighboring groundwater systems. The distribution of virus is, in turn, dependent on the physical and chemical compositions of the surrounding soil and subsurface systems. For the present study, we have determined the effects of different surfactants (cationic, anionic, nonionic, and biological) and natural organic matter (NOM) on bacteriophages. Results indicated that surfactants and NOM adversely affect phage survival in binary systems, with surfactants being the most harmful. Studies with ternary systems also showed that the presence of surfactants reduced sorption of phages on sorbents either by occupying available sorption sites on the sorbent material or by displacing the sorbed phages from the sorbent surface. Water contact angles of the selected phages and different sorbent surfaces have been measured. Experimental data demonstrated that the sorption of hydrophobic viruses was favored by hydrophobic sorbents, while the sorption of hydrophilic viruses was favored by hydrophilic sorbents.  相似文献   

14.
Arsenic mobility in natural environments is controlled primarily by sorption onto metal oxide surfaces, and the extent of this sorption may be influenced strongly by the presence of other dissolved substances that interact with surfaces or with arsenic itself. Natural organic matter (NOM), a prevalent constituent of natural waters, is highly reactive toward both metals and surfaces and is thus a clear candidate to influence arsenic mobility. The objectives of this study were therefore to reveal the influences of diverse NOM samples on the sorption of arsenic onto hematite, a model metal oxide, as well as to reveal influences of arsenic on the sorption of NOM, using conditions and concentrations relevant to natural freshwater environments. Of the six NOM samples tested, four formed aqueous complexes with arsenate and arsenite. The extent of complexation varied with the NOM origin and, in particular, increased with the cationic metal (primarily Fe) content of the NOM sample. In addition, every NOM sample showed active redox behavior toward arsenic species, indicating that NOM may greatly influence redox as well as complexation speciation of arsenic in freshwater environments. When NOM and As were incubated together with hematite, NOM dramatically delayed the attainment of sorption equilibrium and diminished the extent of sorption of both arsenate and arsenite. Consistent with this result, when NOM and As were introduced sequentially, all NOM samples displaced sorbed arsenate and arsenite from hematite surfaces, and arsenic species similarly displaced sorbed NOM from hematite in significant quantities. Competition between NOM and As for sorption thus appears to be a potentially important process in natural waters, suggesting that NOM may play a greater role in arsenic mobility than previously recognized. In addition, in all sorption experiments, arsenite was consistently desorbed or prevented from sorbing to a greater extent than arsenate, indicating that interactions with NOM may also partially explain the generally greater mobility of arsenite in natural environments.  相似文献   

15.
The effects of superheated water processing on enhancement of phenanthrene sorption by various source materials of natural organic matter (NOM) were systematically examined. Sorption capacities and subsequent phenanthrene retention characteristics of all organic materials tested were markedly increased by superheated water processing. Temperature effects on enhancement of the sorption behaviors of the test materials were greater than those of processing time, moisture content, and the presence of mineral catalysts. Greatest enhancement was observed for processing at 250 degrees C for 5 h with a moisture content of 50%. Strong correlations of sorption capacities and isotherm nonlinearities with processing temperature, and with the atomic ratios of oxygen to carbon (O/C), aromaticity, and hydrophobicity of the processed materials were observed. The sorption/desorption hysteresis indices of the processed materials also increased linearly with processing temperatures and O/C ratios. This is consistent with our observations of increased condensation and aromatization of NOM during superheated water processing presented in the first paper of this series. The relationships described provide direct experimental evidence that the sorption-desorption properties of NOM geosorbents are closely related to their degree of aromatization and condensation, and the work suggests strong potential for production of efficient and cost-effective engineered natural organic sorbents for environmental applications.  相似文献   

16.
The effect of cationic copper (Cu2+) on the sorption of anionic metsulfuron-methyl (Me) and cationic difenzoquat (DZ) to peat and soil was studied using a batch equilibration method. The results showed that Cu2+ increased the sorption of Me but diminished the sorption of DZ. The adsorption of Cu2+ on the surface of peat and soil neutralizes the negative charge, making the zeta potential (zeta) of peat and soil less negative, consequently decreasing the repulsion between the surface of peat or soil and Me and increasing the sorption of Me. Cu2+ may additionally form Cu-Me complexes in aqueous solution, which was preferentially sorbed to peat and soil over the anionic Me. In contrast, the decreased negative surface charge of soil and peat does not favor the sorption of cationic DZ. Fourier transform infrared showed that DZ may be sorbed through interaction with -OH or -COOH groups of peat and soil and that surface complexes of Cu2+ may form through these groups. A competitive sorption between Cu2t and DZ for the same sorption sites is indicated, leading to mutual sorption inhibition of both cations.  相似文献   

17.
Equilibrium sorption isotherms were measured for five different low-polarity organic compounds (benzene, trichloroethene, 1,2- and 1,4-dichlorobenzene, and phenanthrene) over a wide concentration range. The investigated sorbents can be grouped into the following three classes: (1) humic soil organic matter, which shows linear sorption isotherms (solely partitioning, as observed in the peat sample); (2) carbon materials, which were thermally altered (due to their natural history or industrial production) and thus contain a high specific surface area and exhibit nonlinear isotherms, and (3) pure engineered microporous materials (e.g., zeolites and activated carbon), where adsorption is solely due to a pore-filling process. Sorption of all compounds was fitted very well by the Polanyi-Dubinin-Manes (PDM) model, which for sorbents containing humic organic matter (e.g., peat) was combined with linear partitioning. Both the partitioning and the Polanyi-Dubinin-Manes model predict unique sorption isotherms of similar compounds if the solubility-normalized aqueous concentration is used. In addition, an inverse linear relationship between the distribution coefficient (Kd) and water solubility, which was very well confirmed by the data, is obtained. This also leads to unit-equivalent Freundlich sorption isotherms and explains the often observed apparent correlation between sorption capacity at a given concentration (e.g., Freundlich coefficient) and sorption nonlinearity (Freundlich exponent).  相似文献   

18.
Subcritical water treatment was used to effect rapid compositional and functional changes to peat organic matter that mimic those of the natural diagenesis process. Elemental, solid state 13C NMR, FTIR, and calorimetry analyses all indicated that the organic matter of the artificially aged peat was chemically similar to that of geologically mature coal kerogens. This paper extends the work of the previous paper in this series, which investigated the effects of subcritical water treatment of humic topsoil on subsequent phenanthrene sorption and desorption equilibria. As opposed to the previous study, however, changes in sorptive reactivity herein were unequivocally related to changes in organic matter rather than other soil constituents, and organic matter functional changes due to the simulated diagenesis were more accurately characterized. Phenanthrene sorption capacity and isotherm nonlinearity both increased with increasing degrees of artificial aging, supporting the viewpoint that hydrophobic organic contaminant sorption equilibrium properties can be directly related to the degree of diagenesis of geosorbent organic matter. In addition, this work investigated effects of subcritical water treatment of a geologically mature, kerogen-containing shale sample. In contrast to the peat, the functional characteristics of the shale were unchanged by this treatment, and subsequent phenanthrene sorption equilibria were altered far less.  相似文献   

19.
Sorption of nitrobenzene, phenol, and m-nitrophenol from water and n-hexadecane was measured on Na-montmorillonite and organoclays in which 41 and 90% of the exchange capacity of the Na-clay was occupied by hexadecyltrimethylammonium. The strength of sorbate-sorbent interactions in n-hexadecane for all three sorbents was in the following order: nitrobenzene < phenol < m-nitrophenol. The magnitude of the distribution coefficients suggests that the contribution to solute uptake of partitioning between n-hexadecane and the organic pseudophase of the dried organoclays is minor, whereas the major contribution is from adsorptive sorbate-sorbent interactions. Sorption isotherms obtained in different solvents were compared using a sorbate activity scale. In the organoclays, the stronger the tendency of a sorbate to interact with sorption sites, the less pronounced is the reduction in the activity-based sorption due to competition with water. The order of this reduction for the different sorbates is nitrobenzene > phenol > m-nitrophenol. The weakening of sorbate-sorbent interactions resulting from water-sorbate competition might be mitigated by interaction between the organic sorbate and sorbed water molecules. Since the more strongly interacting organic compounds are less susceptible to suppression of sorption in the presence of water, hydrating organoclays may result in an increased differentiation between "weakly" and "strongly" interacting ("nonpolar" and "polar") compounds in the organoclay phase.  相似文献   

20.
The influence of plant lipids on the equilibrium sorption of three aromatic solutes from water was studied. The plant-water sorption isotherms of benzene, 1,2-dichlorobenzene, and phenanthrene were measured over a large range of solute concentrations using sealed vessels containing water, dried plant material, and solute. The plant materials studied include the shoots of annual rye, tall fescue, red fescue, and spinach as well as the roots of annual rye. Seven out of eight sorption isotherms were linear with no evidence of competitive effects between the solutes. For a given plant type, the sorption coefficient increased with decreasing solute water solubility. For a given solute, sorption increased with increasing plant lipid content. The estimated lipid-water partition coefficients of individual solutes were found to be significantly greater than the corresponding octanol-water partition coefficients. This indicates that plant lipids are a more effective partition solvent than octanol for the studied aromatic compounds. As expected, the solute lipid-water partition coefficients were log-linearly related to the respective water solubilities. For the compounds studied, partitioning into the lipids is believed to be the primary sorption mechanism.  相似文献   

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