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1.
Sorption equilibrium of phenol and aniline onto the granular activated carbon and hyperreticulated un-functionalized polymeric resin (MN200) was investigated in single and binary component aqueous systems. Higher loading was obtained for aniline than phenol onto both sorbents, which is probably due to hydrophobic difference between both solutes and the greater electronic density of the aromatic ring of the aniline. Granular activated carbon reported larger uptake than resin MN200 for both solutes, which may be attributed to the better physical properties of the granular activated carbon, for instance, larger surface area. The experimental sorption could be properly described by the Langmuir and Freundlich isotherms. Five models for predicting the binary equilibrium sorption isotherm were compared in order to determine the best fit model to correlate binary experimental data: the extended Langmuir isotherm with and without a constant interaction factor, a simplified model based on the single equilibrium factors, the empirical extended Freundlich isotherm and the modified extended Langmuir equation, which considers the synergistic interactions between sorbate–sorbate and not only the competition between them defined by the extended Langmuir model. The modified extended Langmuir model provides the best agreement between predicted and experimental data indicating that the synergistic interactions between solutes play an important role in the binary phenol/aniline sorption system.  相似文献   

2.
This work was conducted to evaluate the sorption performance of hyper-cross-linked Macronet resin (MN200) compared to the granular activated carbon in order to remove phenol and aniline from aqueous solution in both single and binary solutions. Fixed-bed column experiments were used to obtain the breakthrough curves. The experimental data were fitted to the Thomas, Bed Depth Service Time and Yoon?CNelson models, well-established fixed-bed sorption models. The theoretical sorption capacities obtained by the Thomas model were in good agreement to the breakthrough capacities determined from the sorption data. The sorption capacity decreased in binary sorption for resin MN200, while activated carbon reported similar (aniline) or higher (phenol) sorption performance indicating a synergistic effect between both solutes on the activated carbon surface. A good prediction of the breakthrough curves in binary solution was obtained by using an approach that considers a simple model to describe a breakthrough curve (Thomas) and modified isotherm equilibrium. The resin MN200 fixed-bed columns were easily regenerated by using a methanol solution, reporting more above of 90% of recovery for both solutes, while about 50% was the recovery of activated carbon after single experiments. The regeneration after the binary sorption experiments reported a decrease in the solute recovery, effect that was especially evident for activated carbon.  相似文献   

3.
研究有机改良土壤对污染物的动力学吸附特征,有助于深入了解其对污染物的吸附机制。以十六烷基三甲基溴化铵单一改良(CB)和十六烷基三甲基溴化铵+十二烷基磺酸钠混合改良(CS)塿土耕层土样,采用批处理法通过不同的速度参数研究了改良土壤对苯胺的吸附动力学特征,并与苯酚对比探讨改良土样对有机污染物吸附的动力学机制。结果表明,塿土耕层土样的有机改良能够显著加快对苯胺的吸附速度,苯胺的吸附反应呈现快速反应和慢速反应两个阶段,且以快速吸附反应为主。总体上耕层土样Vt、V0.5、Vf的大小顺序均为100CB>120CS>(≈)50CB>CK。随温度升高和苯胺添加浓度增大,苯胺吸附速度增大,苯胺、苯酚的吸附动力学特征在改良土样上具有良好的相似性,从而证实有机污染物以分子状态存在导致的单一疏水吸附是改良土样吸附的决定机制。  相似文献   

4.
Treated and untreated rice straw extensively exists in the soil. In order to elucidate its possible effect on the fate of organic pollutants, sorption of pyrene by rice straw and its main constituents (lignin, cellulose, and hemi-cellulose) were studied, as single solute and in the presence of other co-existing organic pollutants, phenanthrene (Phen), benzo[a]pyrene (BaP), phenol, and pentachlorophenol (PCP). Pyrene showed the greatest sorption on lignin with greater aromaticity and smaller polarity, and the sorption coefficient was almost two orders of magnitude greater than those on cellulose and hemi-cellulose. Bi-solute sorption results showed that Phen, BaP and PCP exhibited apparent competitive sorption with pyrene on the four sorbents; while the existence of phenol promoted the sorption of pyrene on rice straw and lignin but inhibited the sorption on cellulose and hemi-cellulose. For the two polycyclic aromatic hydrocarbon (PAH) co-solutes and PCP, hydrophobicity and molecular size played important roles in competition, suggesting the direct competition for hydrophobic sorption sites and pore blockage mechanisms. In contrast, the polar co-solute, phenol showed different effects on pyrene sorption onto the four sorbents, suggesting that multiple interactions between polar organic compounds and sorbents are involved in the sorption.  相似文献   

5.
Prediction of the sorption behavior of environmental pollutants is of utmost importance within the framework of risk assessments. In this work two approaches are presented with the aim to describe sorption of aromatic substances to geosorbents. First, analytical solutions of kinetic models were fitted to experimental data of batch sorption experiments with aniline and 1-naphthylamine onto animal manure-treated soil and the soil mineral montmorillonite. The models, accounting for equilibrium and nonequilibrium sorption coupled to transformation and/or irreversible sorption processes, could well reproduce the concentration course of the sorbates. Results suggest that the amounts transformed/degraded and irreversibly bound were higher for the soil than for the clay mineral. In the second part, quantum chemical calculations were performed on aniline and 1-naphthylamine interacting with acetic acid, acetamide, imidazole, and phenol as models of functional groups present in humic substances. Molecular modeling showed that formation of hydrogen bonds is the dominating binding mechanism in all modeled complexes, which are energetically very similar between aniline and 1-naphthylamine.  相似文献   

6.
重金属和有机污染物在修饰土中的吸附   总被引:13,自引:0,他引:13  
Sorption characteristics of both an organic pollutant (phenol) and a heavy metal (cadmium ion) on the clay layer of a Lou soil (Eum-orthic Anthrosol in Chinese Soil Taxonomy) along with the sorption mechanism were investigated using three soil treatments: modification with a cationic surfactant cetyltrimethylammonium bromide added at an amount equivalent to 50% and 100% of the soil CEC (50? and 100?), modification with an amphoteric surface-modifying agent dodecyldimethylbetaine (commercially known as BS-12) added at an amount equivalent to 50% and 100% of the soil CEC (50% BS and 100%BS), and an unmodified control (CK). Results showed that the BS soil treatments increased sorption of both the heavy metal Cd^2+ and the organic pollutant phenol. The equilibrium sorption amount of Cd^2+ decreased in the order: 50%BS 〉 100%BS 〉 CK 〉 50? 〉 100?, with the BS soil treatments being about 1.3 to 1.8 times higher and the CB soil treatments about 23% to 41% lower than CK. Both the single-site and two-site Langmuir models could be applied to describe the sorption of Cd^2+ in each soil treatment. The equilibrium sorption amount of phenol on the soil samples decreased in the order: 100? 〉 50? 〉 100%BS 〉 50%BS 〉 CK, with the CB soil treatments being 41.0 to 79.6 times higher and the BS soil treatments 4.0 to 8.3 times higher than CK. The Freundlich equation could also be used to describe the sorption characteristics of phenol. In the BS soil treatments, both an organophobic long carbon chain and hydrophilic charged groups resulted in a relatively strong sorption ability for both heavy metals and organic pollutants. In addition, the sorption ratio K, the ratio of phenol sorption amount of the modified soil to that of CK, increased initially and decreased later with the amount of phenol added, and the critical sorption ratio Kc, the peak value of the sorption ratio curve plotted against the added phenol concentration, was a good index for evaluating the sorption ability of phenol in the soil.  相似文献   

7.
Chemical extraction, multi‐element stable isotopic dilution (ID) and multi‐surface modelling were used to investigate the lability of cadmium (Cd) and copper (Cu) in nine types of soil with different properties and contaminated or not with Cd and Cu. The chemical extraction and ID analyses both showed that Cd was more labile than Cu in all the soil types studied. From the ID results, 32.8–93.3% of total Cd and 14.7–71.8% of total Cu were isotopically exchangeable after 3 days of equilibration. A single extraction in 0.43 m HNO3 gave similar results to the 3‐day ID assay for Cu in most of the soils and for Cd in the non‐calcareous soils. However, an eight‐step selective sequential extraction (SSE) procedure gave different results from the ID assay for both metals. Predictions of the multi‐surface model for the amounts of Cd and Cu adsorbed, based on measured metal ion activities in the soil solution and the concentrations of reactive surfaces in the soil, agreed with the ID results. The model predicted that soil organic matter was the predominant sorbent for Cd and Cu in the soils and that manganese oxide was the least important sorbent. The contributions of iron oxides to sorption were predicted to be small except in soil with a high pH and little organic matter. The predicted sorption on different soil components did not match SSE measurements.  相似文献   

8.

Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal concentration, kaolinite concentration and time. The organic acids used were p-hydroxybenzoic acid, o-toluic acid, and 2,4-dinitrophenol. Titrations were used to derive previously unavailable aqueous conditional stability constants for the organometallic complexes. Batch results showed that aqueous lead-organic complexation reduced sorption of Pb by kaolinite. Cadmium behavior was similar, except for 2,4-dinitrophenol, where Cd sorption was increased. Metal sorption increased with increasing pH and decreasing ionic strength. Distribution ratios (K d 's) decreased with increasing solid/solution ratio. The subsurface transport of lead and cadmium may be enhanced via complex interactions with organic wastes or their degradation products and sorbent mineral surfaces.

  相似文献   

9.
秸秆生物质炭吸附溶液中Cu2+ 的影响因素研究   总被引:2,自引:0,他引:2  
贾明云  王芳  卞永荣  杨兴伦  谷成刚  宋洋  蒋新 《土壤》2014,46(3):489-497
生物质炭在吸附土壤中重金属和有机污染物方面发挥着重要作用,然而关于生物质炭吸附重金属的影响因素研究较少。以小麦和玉米秸秆为原料制备生物质炭,分析了生物质炭和溶液性质对水溶液中Cu2+吸附的影响。结果表明生物质炭可有效吸附Cu2+,且不易解吸。Cu2+吸附量随pH和Cu2+初始浓度的升高而增加;高温炭对Cu2+的吸附随离子强度增强而增大;柠檬酸抑制低温炭对Cu2+的吸附,而腐植酸促进Cu2+吸附;生物质炭灰分对Cu2+吸附无显著影响。  相似文献   

10.
采用批量平衡实验,研究了黄河兰州段沉积物对p,p′-DDT的吸附/解吸特性,并考察了环境因素温度、pH值、沉积物粒度等对吸附的影响。结果表明,p,p′-DDT在黄河兰州段沉积物上的吸附在24h内可以充分达到平衡。吸附过程是非线性的,Freundlich模型可以较好地描述吸附行为,分配作用和表面吸附作用同时存在;解吸过程存在明显滞后性,即解吸要比吸附困难。正交结果表明吸附质浓度和吸附剂浓度对p,p′-DDT在沉积物上的吸附量有显著影响,而温度、pH值、有机质含量、沉积物粒度影响不显著。  相似文献   

11.
A carbonaceous sorbent produced from rice husk via sulphuric acid treatment was used to remove Cr(VI) from aqueous solutions varying contact time, pH, Cr(VI) concentration and sorbent status (wet and dry). Cr(VI) was removed from the aqueous solution via reduction to Cr(III) and sorption. Reduction and sorption processes were investigated in terms of kinetics and equilibrium. The rate of reduction removal of Cr(VI) at pH 2 followed a pseudo first-order model while the rate of sorption of total chromium followed pseudo second-order model. Chromium sorption was highly dependent on the initial pH value with reduction taking place in solution with pH up to 7 showing sorption maxima in the pH range 1.8–2.8 for concentration range 100–500 mg/l with an increase in the equilibrium pH. Carbon dioxide evolved from the sorption media was determined. Reduction–sorption mechanism was investigated via physicochemical tests including cation exchange capacity, base neutralization and sorbent acidity in addition to FTIR studies for sorbent samples before and after sorption reaction.  相似文献   

12.

Purpose

Sorption of heavy metals on soil components plays an important role in reducing their mobility and bioavailability. Organic matter is an important sorbent of heavy metals in soil. Crop residues which are important sources of soil organic matter will undergo decomposition after addition to the soil. However, few studies reported the effect of organic matter decomposition on heavy metal sorption. This study aimed to investigate the effect of straw decomposition on the sorption of Cu.

Materials and methods

Rice straw was decomposed in aerobic conditions for 1, 3, 6, and 12 months, respectively. Solid organic matter in decomposed rice straw was collected and marked OM-1, OM-3, OM-6, and OM-12, respectively. Sorption isotherms and kinetics of Cu on solid organic matter were studied by batch experiments. The sorption of Cu was calculated by the difference between the amount of Cu added initially and that remained in the supernatant. Sorption thermodynamics of Cu were studied by isothermal titration calorimetry technique. Potential mechanisms of Cu sorption were analyzed by combining the information from sorption thermodynamics, desorption experiments, and Fourier transform infrared spectroscopy observations. All sorption experiments were carried out at pH 5.0.

Results and discussion

The maximum sorption of Cu was 165.8, 170.5, 186.6, and 226.9 mmol kg?1, and the rate constant of Cu sorption was 0.80, 0.58, 0.50, and 0.32 kg mmol?1 h?1 on OM-1, OM-3, OM-6, and OM-12, respectively, indicating that the maximum sorption of Cu increased while sorption rate of Cu decreased with increasing the duration of straw decomposition from 1 to 12 months. The negative values of Gibbs free energy change and positive values of enthalpy change and entropy change revealed that Cu sorption was spontaneous, endothermic in nature, and the randomness was increased during sorption. Carboxyl and hydroxyl in solid organic matter were involved in Cu sorption. The percentage of Cu desorbed by NH4Ac from OM-1, OM-3, OM-6, and OM-12 was 45.0, 43.5, 42.8, and 37.8 %, respectively.

Conclusions

In the current study, the decomposition of straw promoted the sorption capacity but reduced the sorption rate of Cu on solid organic matter. Copper sorption was an endothermic and spontaneous process. The formation of inner-sphere complexes was the main mechanism of Cu sorption, and its role in Cu sorption tended to increase with increasing the duration of straw decomposition. The information will facilitate the understanding of the contamination and remediation of heavy metal in cropland.
  相似文献   

13.
The amounts of inorganic P sorbed by a range of Fe- and Al- containing components varied appreciably and decreased in the order allophane > fresh Al gel > Fe gel pseudoboehmite > aged Al gel > dried Fe gel > Fe-coated kaolinite > haematite > goethite > akaganeite > gibbsite = ground kaolinite > dispersed kaolinite. Al gel sorbed 30 to 70 times more P than gibbsite, and Fe gel sorbed approximately 10 times more P than its crystalline analogues (haematite, goethite. and akaganeite). Despite large differences in the extent of P sorption, the form of the isotherm was essentially the same for each sorbent. The ability of freshly-prepared Al gel suspensions to sorb P decreased with ageing, a property not shown by Fe gel. Drying of Fe gel at 80°C, however, caused an approximately 4-fold decrease in P sorption. Precipitation of Fe gel (2% Fe) on the surface of kaolinite increased P sorption by a factor of 10. The occurrence of Fe gel as a coating apparently presents more sorption sites to solution per unit weight of Fe gel than Fe gel alone. A linear relationship (r= 0.98) was obtained between the amount OH? sorbed per unit increase in pH value (‘hydroxyl buffering’) and the overall P sorption maximum for each sorbent. Hydroxyl buffering provided a better index of P sorption potential than specific surface area. Except for the crystalline Fe sorbents, isotherms obtained by plotting fractional sorption saturation against final solution P concentration for the sorbents were essentially coincident with those for several contrasting soils. For crystalline Fe components a lower relative amount of weaker sorption, as opposed to chemisorption, of the overall sorption maximum was obtained. Differences in the extent of P sorption. however, appear to be primarily related to the number of functional M-OH groups presented at the solid-solution interface.  相似文献   

14.
An experimental study was performed to determine the feasibility of usingorganobentonite modified with quarternary ammonium cations (QACs) as a reactive medium in immobilization and biodegradation barriers for mixed contaminants in the subsurface soil. Various factors, including interactions between heavy metals, organic contaminants, and soil microorganisms, were investigated when they coexisted with untreated bentonite and organobentonite. Batch sorption tests for cadmium and lead were conducted to quantify sorption selectivity of these metals on untreated bentonite and organobentonite. Metal concentrations of 50 × 10-6 M slightly reduced the growth of soil microbes and partially interfered with the biodegradation of phenol. Soil microorganisms tested with untreated bentonite grew after approximately 25 hr of lag period and degraded phenol completely within 350 hr. The results from this study demonstrate that organobentonite could be used as a reactive medium for immobilization and biodegradation of organic contaminants in the presence of heavy metals in the subsurface soil.  相似文献   

15.
Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.  相似文献   

16.
Soil sorption and dissipation of fluometuron (FLM) and three metabolites, desmethyl fluometuron (DMF), trifluoromethyl phenyl urea (TFMPU), and trifluoromethyl aniline (TFMA), were assessed in conservation tillage soils. In study I, surface Dundee silt loam soils from no-tillage (NT) and reduced-tillage (RT) areas were treated with 14C ring-labeled FLM or TFMA or unlabeled DMF, incubated for 34-42 days, extracted, and analyzed. Mineralization and volatilization of 14C-labeled FLM or TFMA were monitored. In study II, batch sorption assays (solute concentrations 2-50 micromol L-1; 2:1 solution:soil; 18 h) were conducted using various soils from reduced- (RT) and conventional-tillage (CT) areas to determine the relative affinity of FLM and metabolites for soils with differing characteristics. Mineralization of FLM (3%, day 42) or TFMA (4%, day 34) and FLM volatilization (approximately 2%) were low for both soils. FLM and DMF dissipated more rapidly in RT soil than in NT soil. In FLM-treated RT soil, DMF and TFMPU accumulated more rapidly than in NT as FLM degraded. TFMA dissipated rapidly, primarily as nonextractable residues (approximately 70%, day 42) and volatilization (approximately 16%). For all respective soils in study II, sorption of all four compounds was higher for organic C-enriched RT soils than for CT soils, indicating strong relationships between organic C and FLM and metabolite sorption. For either tillage treatment, the percentage sorption was greater for metabolites (e.g., at lowest initial dosing concentration, TFMPU range, 45-91%; DMF range, 45-90%; and TFMA range, 45-98%) than for FLM (RT soils range, 19-65%). Nonsubstituted amino groups likely facilitated sorption to organic C, with nonsubstituted aniline in TFMA having the greatest affinity. NMR spectra of humic acid extracts from NT and CT Dundee soils indicated similar patterns of humic acid functional groups, but the potential capacity for sorption was greater in NT than in CT. The greater capacity for FLM and metabolite sorption in NT soil helps explain their longer persistence.  相似文献   

17.
The retention of phenol, o-cresol, 2,4-dichlorophenol (DCP), and their peroxidase-catalyzed polymerization products was evaluated on two surface soils. The extractability of the parent solutes and their polymerization products was also investigated. (14)C-Labeled radioisotopes were used to quantify the contaminant retained on soil as water-extractable, methanol-extractable, humic/fulvic (HA/FA) acid-bound, and soil/humin bound. Between 2 and 20% of the solute retained on soil after a 7-day contact period remained bound to the HA/FA and soil/humin components in unamended soils; in the presence of peroxidase this amount was as high as 40-75%. The alkali-extractable HA/FA component contained the largest fraction of radioactivity in peroxidase-amended soils. Whereas the soil organic matter content was the predominant factor controlling the extent of sorption of the parent phenols, the clay content and particle surface area appeared to contribute to the retention of the polymerization products. High molecular weight oligomers produced during peroxidase-mediated polymerization of phenols associate strongly with soil components and are likely incorporated into the soil organic matter via oxidative coupling reactions.  相似文献   

18.
Wood is a complex structure of various macromolecules, mainly cellulose, hemicellulose, and lignin. Although the sorption process of some organic compounds by wood has been elucidated, the relative contribution of its different fractions in the sorption mechanism is not clearly determined. Certain works predict the amount of organic compounds sorbed on wood as a direct relationship to its lignin fraction. All wood macromolecules, however, seem to have the capacity to sorb organic compounds. Sorption of phenolic compounds on individual wood macromolecules has been studied and compared to that on wood. Wood-water partition coefficients ( K wood) for phenolic volatiles and their sorption rates in the presence of lignin display a linear relationship. Results show that cellulose and hemicellulose sorb all phenolic compounds without apparent distinction, whereas lignin is a selective sorbent of these compounds. Sorbant availability and sorbate chemical structure seem to be the key factors governing the sorption mechanism. Sorption kinetics study gives apparent diffusion coefficient values of aroma compounds, bringing new kinetic data for understanding the ternary system of wood, hydroalcoholic solution, and phenolic compounds.  相似文献   

19.
This study presents the application of soybean seed hulls for the decontamination and/or detoxification of phenol and chlorophenol polluted soils. The effect of soil was examined on both catalytic activity of soybean seed hull peroxidase (SBP) and enzymatic transformation of phenol, 2-chlorophenol, and 2,4-dichlorophenol through the polymerization reaction. The sorption of the enzyme to soil organic matter was found to account for the loss of partial catalytic activity of soybean seed hulls in a soil slurry environment. The organic matter present in loamy soils, rather than other soluble soil constituents and soil micro-organisms, is a factor in SBP inhibition by soil and the corresponding decline in treatment efficiency of phenol and chlorophenols. Under improved conditions, however, soybean seed hulls demonstrated a satisfactory ability to catalyze the polymerization reaction. Over 96% of total phenols were removed using soybean seed hulls in a soil slurry bioreactor, which demonstrates a great potential in use of soybean seed hulls, a readily available and inexpensive source of SBP, for bioremediation of soils contaminated with phenolic compounds.  相似文献   

20.
The herbicide diuron is widely used in agricultural areas in Brazil, whereas it has high potential for subsurface water contamination due to its physicochemical characteristics. Recent studies have demonstrated the potential of biochar as a sorbent and possible pesticide leaching mitigation. The objective of this study was to investigate the long-term effect of biochar application on the kinetics of sorption and desorption of diuron in a Cerrado Haplic Plinthosol. Samples were collected in an experiment conducted in the field in a randomized block design consisting of the combination of two levels of fertilizer application (0 and 300 kg ha-1 of 5-25-15 formula of NPK fertilizers) and three doses of biochar (0, 16, and 32 Mg ha-1). The Freundlich isotherm accurately described the sorption of diuron in all treatments. Biochar application increased the sorption and reduced the desorption of diuron. This effect was attributed to the contribution of biochar to total organic carbon (C) and C in the humin fraction and to the increase in the reactivity of the humic acid and humin fractions, which was significantly highly correlated with the sorption coefficient (Kf). A positive correlation between the partition coefficient of organic C and Kf confirmed the importance of the soil organic compartment for the sorption of diuron. The higher diuron sorption and lower diuron desorption capacities of sandy soils after biochar application could reduce the potential risk of diuron leaching and contamination of subsurface water.  相似文献   

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