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1.
A model Suwannee fulvic acid (SFA [Leenheer, J.A., 1994. In: Baker, L.A. (Ed.), Chemistry of Dissolved Organic Matter in Rivers, Lakes and Reservoirs. Advances in Chemistry Series, vol. 237. American Chemical Society]) was energy minimized in various deprotonation states using semi-empirical methods. The structures were minimized in the isolated SFA phase and SFA with 60 water molecules to mimic the first solvation sphere. The relative energies of deprotonation were calculated at four carboxylic acid sites with Hartree-Fock (HF/6-31G(d)) and density functional theory (B3LYP/6-31G(d)) methods. Comparisons were made between the theoretical methods and states of solvation. Isolated and solvated models resulted in different relative deprotonation orders. The energy changes calculated for removing a H+ from a given carboxylic acid group as a function of overall model molecule charge are large enough to explain the large variations of carboxyl group pKas in dissolved natural organic matter. Analysis of the SFA structure as a function of molecular charge is also discussed.  相似文献   

2.
高岭石表面的酸碱性质   总被引:5,自引:0,他引:5  
魏俊峰  吴大清 《矿物学报》2002,22(3):207-210
采用双位模式(即假定高岭石表面存在>AIOH和>SiOH基团)拟合高岭石表面的酸碱滴定数据并描述表面上发生的质子化反应,Al位和Si位的表观常数拟合值分别为pKal,Al=1.78、pKa2,Al=8.47和pKa2,Si=5.12,它们的酸性比对应的(氢)氧化物表面位的更强。高岭石的总表面位密度远大于氧化铝和二氧化硅,其原因很可能是溶液中的质子或羟离子能够渗入高岭石的层间,与层间的羟基发生反应。此外,Al位密度也比Si位大近一个数量级,这种与理论化学式偏离的现象可受多种因素的影响。高岭石表面总体在pH低于4.0时带正电荷,在pH高于4.0时带负电荷。正电荷仅由>AlOH基团通过质子化作用形成>AlOH2^ 表面化合态来提供,而负电荷则由>AlOH和>SiOH基团的去质子化作用产生,分别形成>AlO^-和>SiO^-表面化合态。  相似文献   

3.
The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO3–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al2SiO5 polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.  相似文献   

4.
The interstitial water contained in the microporosity of highly compact clay-rich media does not obey the classical condition usually used to derive the ionic composition of a solution. This is because the requirement for global electroneutrality of a charged microporous body (one having a significant fraction of pores with dimensions of the same order of size as the diffuse double layer) implies that the net charge density of the pore water must balance the deficiency (or the excess) of electrical charge carried by the solid matrix. In order to determine the solution composition in the micropores of a clay-rock, we first generalize the Donnan equilibrium conditions for the case of a multi-ionic electrolyte, with partitioning of the charge compensating counterions between the Stern and the diffuse layers A material-specific geochemical equilibrium model, incorporating an electrical triple layer model for adsorption reactions, is used to calculate the partition coefficient for the compensating ion charge (i.e., the fraction of charge in the Stern layer). This is then used to calculate the osmotic pressure and ionic composition of the pore water in the micropores. The material considered in this study is the argillite clay-rock sampled from the Callovo-Oxfordian geological formation under consideration in France for a deep geological disposal facility for radioactive waste.  相似文献   

5.
Density functional theory is used to compute the effect of protonation, deprotonation, and dehydroxylation of different reactive sites of a goethite surface modeled as a cluster containing six iron atoms constructed from a slab model of the (1 1 0) goethite surface. Solvent effects were treated at two different levels: (i) by inclusion of up to six water molecules explicitly into the quantum chemical calculation and (ii) by using additionally a continuum solvation model for the long-range interactions. Systematic studies were made in order to test the limit of the fully hydrated cluster surfaces by a monomolecular water layer. The main finding is that from the three different types of surface hydroxyl groups (hydroxo, μ-hydroxo, and μ3-hydroxo), the hydroxo group is most active for protonation whereas μ- and μ3-hydroxo sites undergo deprotonation more easily. Proton affinity constants (pKa values) were computed from appropriate protonation/deprotonation reactions for all sites investigated and compared to results obtained from the multisite complexation model (MUSIC). The approach used was validated for the consecutive deprotonation reactions of the [Fe(H2O)6]3+ complex in solution and good agreement between calculated and experimental pKa values was found. The computed pKa for all sites of the modeled goethite surface were used in the prediction of the pristine point of zero charge, pHPPZN. The obtained value of 9.1 fits well with published experimental values of 7.0-9.5.  相似文献   

6.
We have conducted a computational study to investigate a number of possible routes for the incorporation of carbon into apatites. Using density functional theory (DFT) we have calculated geometry optimised structures for fluor- and hydroxy-apatites with and without various substitutions. We have studied several different carbonate substitutions, pure carbonate and pure formate apatites, neutral carbon atoms occupying interstices, and carbon dioxide and acetylene absorbed in oxyapatite.  相似文献   

7.
Bond-valence methods for the prediction of (hydr)oxide solution monomer and surface functional group acidity constants are examined in light of molecular structures calculated using ab initio methods. A new method is presented that is based on these calculated structures, and it is shown that previously published methods have neglected one or more of four essential features of a generalized model. First, if the apparent pKa values of solution monomers are to be used to predict intrinsic pKa values of surface functional groups, similar electrostatic corrections must be applied in both cases. In surface complexation models, electrostatic corrections are applied by representing a charged surface as a uniform plane of charge density, and an analogous correction can be made to solution monomers by treating them as charged spheres. Second, it must be remembered that real surfaces and real monomers are not homogeneous planes or spheres. Rather, charge density is distributed rather unevenly, and a further electrostatic correction (which is often quite large) must be made to account for the proximity of electron density to the point of proton attachment. Third, the unsaturated valence of oxygen atoms in oxyacids, hexaquo cations, and oxide surfaces is strongly correlated with acidity after electrostatic corrections are made. However, calculation of unsaturated valence for oxyacids and oxide surfaces must be based on realistic MeO bond lengths (taking into account bond relaxation), which can be obtained from ab initio structure optimizations. Finally, unsaturated valence must be divided between possible bonds (four for oxygen atoms) to reflect the fact that O-H bonds are localized to particular regions of the O atoms.Empirical models that take all these factors into account are presented for oxyacids and hexaquo cations. These models are applied to the gibbsite (100), (010), (001), and cristobalite (100) surfaces, and it is demonstrated that the model for oxyacids predicts reasonable intrinsic pKa values for oxide surfaces. However, the prediction of surface pKa values is complex, because the protonation state of one functional group affects the pKa values of neighboring groups. Therefore, calculations of larger periodic systems, progressively protonated and reoptimized, are needed.  相似文献   

8.
A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe2+ and Fe3+ ions and optically induced electronic transitions which are assigned to Fe2+→Fe3+ intervalence charge transfer. In this paper, the mechanism of electron delocalization (i.e., polarons versus itinerant electrons) and the nature of optically induced intervalence charge-transfer in minerals are investigated using molecular orbital theory. SCF-Xα-SW molecular orbital calculations were done for several mixed-valence (Fe2O10)15? clusters corresponding to edgesharing Fe2+ and Fe3+ coordination polyhedra. A spinunrestricted formalism was used so that the effect of ferromagnetic versus antiferromagnetic coupling of adjacent Fe2+ and Fe3+ cations could be determined. The molecular orbital results can be related to the polaron theory of solid state physics and the perturbation theory formalism used by Robin and Day (1967) and others to describe electron transfer in mixed valence compounds. Intervalence charge-transfer results from the overlap of Fe(3d) orbitals across the shared edges of adjacent FeO6 polyhedra to give weak Fe-Fe bonds. Electron delocalization, however, requires that adjacent Fe cations be ferromagnetically coupled. Antiferromagnetic coupling results in distinguishable Fe2+ and Fe3+ cations. Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations.  相似文献   

9.
The effect of silicate liquid structure upon mineral-liquid partitioning has been investigated by determining element partitioning data for coexisting immiscible granitic and ferrobasaltic magmas. The resulting elemental distribution patterns may be interpreted in terms of the relative states of polymerization of the coexisting magmas. Highly charged cations (REE, Ti, Fe, Mn, etc.) are enriched in the ferrobasaltic melt. The ferrobasaltic melt is relatively depolymerized due to its low SiO ratio. This allows highly charged cations to obtain stable coordination polyhedra of oxygen within the ferrobasaltic melt. The granitic melt is a highly polymerized network structure in which Al can occupy tetrahedral sites in copolymerization with Si. The substitution of Al+3 for Si+4 produces a local charge imbalance in the granitic melt which is satisfied by a coupled substitution of alkalis, thus explaining the enrichment of low charge density cations, the alkalis, in the granitic melt. P2O5 increases the width of the solvus and, therefore, the values of the distribution coefficients of the trace elements. This effect is attributed to complexing of metal cations with PO4?3 groups in the ferrobasaltic melt.The values of ferrobasalt-granite liquid distribution coefficients are reflected in distribution coefficients for a mineral and melts of different compositions. The mineral-liquid distribution coefficient for a highly charged cation is greater for a mineral coexisting with a highly polymerized melt (granite) than it is for that same mineral and a depolymerized melt (ferrobasalt). The opposite is true for low charge density cations. Mineralliquid and liquid-liquid distribution coefficients determined for the REE's indicate that fractionated REE patterns are due to mineral selectivity and not the state of polymerization of the melt.  相似文献   

10.
We have investigated the presolar grain inventories of two CR chondrites, QUE 99177 and MET 00426, which are less altered than most members of this meteorite group. Both meteorites contain high abundances of O-anomalous presolar grains, with concentrations of 220 ± 40 and 160 ± 30 ppm for QUE 99177 and MET 00426, respectively. The presolar grain inventories are dominated by ferromagnesian silicates with group 1 oxygen isotopic compositions, indicative of origins in low mass red giant or asymptotic giant branch stars. Grains with pyroxene-like compositions are somewhat more common than those with olivine-like compositions, but most grains are non-stoichiometric with compositions intermediate between these two phases, consistent with recent work suggesting that amorphous interstellar silicates have stoichiometries between olivine and pyroxene type silicates. Although structural data are not available, one grain contains only Si and O, and has a stoichiometry consistent with SiO2.Our presolar grains are much more Fe-rich than predicted by astronomical observations. Although secondary alteration may play a role in enhancing the Fe contents of presolar grains, it seems unlikely that the large and ubiquitous Fe enrichments observed in the grains from this study can be due only to secondary processing, particularly given the highly primitive nature of these two meteorites. Grain condensation in the stellar outflows where these grains formed likely proceeded under rapidly changing kinetic conditions that may have enhanced the incorporation of Fe into the grains over that expected based on equilibrium condensation theory.Both QUE 99177 and MET 00426 appear to contain unusually low abundances of oxide grains and have higher silicate/oxide ratios than other primitive meteorites analyzed to date. We explore various possibilities for this discrepancy, but note that most scenarios are not likely to result in the preferential destruction of oxides relative to silicates. Thus, the highest silicate/oxide ratios, such as those observed in the CR chondrites, should reflect the true initial proportions of presolar silicate and oxide grains in the parent molecular cloud from which the solar nebula evolved.  相似文献   

11.
Periodic ab initio Hartree-Fock LCAO calculations have been carried out on the two dimensional sheet of SiO4 tetrahedra, representing one of the basic constituting units of layer silicates, using Huzinaga's DZP basis sets. The influence of the basis set on the chemical bonding picture is characterized by Mulliken atomic charges and by electron density maps. Silicon atomic charges +1.6 ¦e¦ are more realistic than those +2.4 ¦e¦ reported for smaller basis sets. The silicon d orbital population is found to be 0.6 in close agreement with molecular data. Electron density maps indicate the absence of charge density in the center of the ditrigonal cavity. The charge buildup of nonbonding basal oxygen orbitals is directed mainly downwards perpendicular to the sheet plane.  相似文献   

12.
We report on the thermochemistry of proton hydration by water in the gas phase both experimentally using high-pressure mass spectrometry (HPMS) and theoretically using multilevel G3, G3B3, CBS-Q, CBS-QB3, CBS/QCI-APNO as well as density functional theory (DFT) calculations. Gas phase hydration enthalpies and entropies for protonated water cluster equilibria with up to 7 waters (i.e., n ? 7H3O+·(H2O)n) were observed and exhibited non-monotonic behavior for successive hydration steps as well as enthalpy and entropy anomalies at higher cluster rank numbers. In particular, there is a significant jump in the stepwise enthalpies and entropies of cluster formation for n varying from 6 to 8. This behavior can be successfully interpreted using cluster geometries obtained from quantum chemical calculations by considering the number of additional hydrogen bonds formed at each hydration step and simultaneous weakening of ion-solvent interaction with increasing cluster size. The measured total hydration energy for the attachment of the first six water molecules around the hydronium ion was found to account for more than 60% of total bulk hydration free energy.  相似文献   

13.
In this work, the Bader’s topological analysis of the electron density, coupled with Thom’s catastrophe theory, was used to characterize the pressure-induced transformations in α-quartz. In particular, ab initio calculations of the α-quartz structures in the range 0–105 Gpa have been performed at the HF/DFT exchange–correlation terms level, using Hamiltonians based on a WC1LYP hybrid scheme. The electron densities calculated throughout the ab initio wave functions have been analysed by means of the Bader’s theory, seeking for some catastrophic mechanism in the sense of Thom’s theory. The analysis mainly showed that there is a typical fold catastrophe feature involving an O–O interaction at the quartz–coesite transition pressure, while the amorphization of α-quartz is coincident with an average distribution of the gradient field of the electron density around the oxygen atom which is typically observed in the free atoms. This approach is addressed to depict a phase transition from a novel viewpoint, particularly useful in predicting the stability of a compound at extreme conditions, especially in the absence of experimental data.  相似文献   

14.
The deprotonation and iron complexation of the hydroxamate siderophore, desferrioxamine B (desB), and a model hydroxamate ligand, acetohydroxamic acid (aHa), were studied using infrared, resonance Raman and UV-vis spectroscopy. The experimental spectra were interpreted by a comparison with DFT calculated spectra of aHa (partly hydrated) and desB (reactive groups of unhydrated molecule) at the B3LYP/6-31G* level of theory. The ab initio models include three water molecules surrounding the deprotonation site of aHa to account for partial hydration. Experiments and calculations were also conducted in D2O to verify spectral assignments. These studies of aHa suggest that the cis-keto-aHa is the dominant form, and its deprotonation occurs at the oxime oxygen atom in aqueous solutions. The stable form of iron-complexed aHa is identified as Fe(aHa)3 for a wide range of pH conditions. The spectral information of aHa and an ab initio model of desB were used to interpret the chemical state of different functional groups in desB. Vibrational spectra of desB indicate that the oxime and amide carbonyl groups can be identified unambiguously. Vibrational spectral analysis of the oxime carbonyl after deprotonation and iron complexation of desB indicates that the conformational changes between anion and the iron-complexed anion are small. Enhanced electron delocalization in the oxime group of Fe-desB when compared to that of Fe(aHa)3 may be responsible for higher stability constant of the former.  相似文献   

15.
In this paper the validity of the classical ionic model, using a Madelung term and a Born-Mayer repulsive term, is investigated quantatively for systems with a considerable overlap of the electron clouds of neighbouring ions, such as silicates with a high degree of polymerisation. A modified ionic model is presented which takes into account the spatial extent of the ions within the approximation of spherical atoms. Both models are tested against quantum mechanical electron densities and energies for SiO 4 4- -clusters. The data demonstrate the validity of the spherical atom approximation, producing a fit of 99.995%, and the importance of manybody effects maintaining the spherical symmetry of the electron clouds as contraction/expansion of the ions and charge transfer between ions. Although the new interaction potential is physically more plausible than the classical Born-Mayer model, both models reproduce the quantum mechanical potential surface with numerical accuracies of the same order of magnitude. The new model provides an improved tool for judging between ionic and non-ionic effects and for analysis of the quantum mechanical electron densities and interaction energies.  相似文献   

16.
The topological properties of the electron density distributions for more than 20 hydroxyacid, geometry optimized molecules with SiO and GeO bonds with 3-, 4-, 6- and 8-coordinate Si and Ge cations were calculated. Electronegativities calculated with the bond critical point (bcp) properties of the distributions indicate, for a given coordination number, that the electronegativity of Ge (∼1.85) is slightly larger than that of Si (∼1.80) with the electronegativities of both atoms increasing with decreasing bond length. With an increase in the electron density, the curvatures and the Laplacian of the electron density at the critical point of each bond increase with decreasing bond length. The covalent character of the bonds are assessed, using bond critical point properties and electronegativity values calculated from the electron density distributions. A mapping of the (3, −3) critical points of the valence shell concentrations of the oxide anions for bridging SiOSi and GeOGe dimers reveals a location and disposition of localized nonbonding electron pairs that is consistent with the bridging angles observed for silicates and germanates. The bcp properties of electron density distributions of the SiO bonds calculated for representative molecular models of the coesite structure agree with average values obtained in X-ray diffraction studies of coesite and danburite to within ∼5%. Received: 18 August 1997 / Revised, accepted: 19 February 1998  相似文献   

17.
Molecular dynamics (MD) computer simulations of liquid water held in one-dimensional nano-confinement by two parallel, electrostatically neutral but hydrophilic surfaces of brucite, Mg(OH)2, provide greatly increased, atomistically detailed understanding of surface-related effects on the spatial variation in the structural ordering, hydrogen bond (H-bond) organization, and local density of H2O molecules at this important model hydroxide surface. NVT-ensemble MD simulations (i.e., at constant number of atoms, volume and temperature) were performed for a series of model systems consisting of 3 to 30 Å-thick water layers (containing 35 to 360 H2O molecules) confined between two 19 Å-thick brucite substrate layers. The results show that the hydrophilic substrate significantly influences the near-surface water structure, with both H-bond donation to the surface oxygen atoms and H-bond acceptance from the surface hydrogen atoms in the first surface layer of H2O molecules playing key roles. Profiles of oxygen and hydrogen atomic density and H2O dipole orientation show significant deviation from the corresponding structural properties of bulk water to distances as large as 15 Å (∼5 molecular water layers) from the surface, with the local structural environment varying significantly with the distance from the surface. The water molecules in the first layer at about 2.45 Å from the surface have a two-dimensional hexagonal arrangement parallel to brucite layers, reflecting the brucite surface structure, have total nearest neighbor coordinations of 5 or 6, and are significantly limited in their position and orientation. The greatest degree of the tetrahedral (ice-like) ordering occurs at about 4 Å from the surface. The translational and orientational ordering of H2O molecules in layers further from the surface become progressively more similar to those of bulk liquid water. A quantitative statistical analysis of the MD-generated instantaneous molecular configurations in terms of local density, molecular orientation, nearest neighbor coordination, and the structural details of the H-bonding network shows that the local structure of interfacial water at the brucite surface results from a combination of “hard wall” (geometric and confinement) effects, highly directional H-bonding, and thermal motion. This structure does not resemble that of bulk water at ambient conditions or at elevated or reduced temperature, but shares some similarities with that of water under higher pressure.  相似文献   

18.
Mn2+(aq) oxidation as promoted by hematite in the presence of molecular oxygen has been studied as a function of hematite particle size. This system is a good candidate to serve as a test of the change of particle reactivity as a function of size due not only to its importance in Earth/environmental processes, but also because it involves electronic coupling between the hematite and adsorbed manganese. The properties of nanoscale hematite, including size quantization of the electronic structure and the relative proportions of terrace vs. edge/kink sites, are expected to change significantly with the particle size in this size range. Experimental results from this study suggest that the heterogeneous manganese oxidation rate is approximately one to one and a half orders of magnitude greater on hematite particles with an average diameter of 7.3 nm than with those having an average diameter of 37 nm, even when normalized to the surface areas of the particles. The acceleration of electron transfer rate for the reactions promoted by the smallest particles is rationalized in the framework of electron transfer theory. According to this theory, for a reaction such as heterogeneous Mn oxidation, the rate depends on three factors: the electronic coupling between initial and final electronic states, the substantial reorganization energy for solvent and coordinated ligands between initial and final states, and the free energy of reaction (corrected for work required to bring reactants together). The adsorbed Mn is electronically coupled with the solid during the electron transfer, and changes in the electronic structure of the solid would be expected to influence the rate. The Lewis base character of surface oxygen atoms increases as the electronic structure becomes quantized, which should allow increased coupling with adsorbed Mn. Finally, as demonstrated previously by in situ AFM observations, the reaction proceeds most readily at topographic features that distort the octahedral Mn2+ coordination environment. This has the effect of lowering the reorganization energy, which effectively controls the magnitude of the transition state barrier. Previous studies of <10 nm diameter hematite nanoparticles have demonstrated a decrease of symmetry in the average coordination environment of surface atoms, supporting the idea that smaller sizes should correspond to a decrease in reorganization energy.  相似文献   

19.
The effect of the group IA and VIIA ions, as well as Mg2+, and the molecules H2O, CO2, H3O+ and OH? on the energy of the Si-O bond in a H6Si2O7 cluster has been calculated using semiempirical molecular orbital calculations (CNDO/2). Three types of elementary processes, i.e. substitution, addition, and polymerization reactions have been used to interpret data on the dynamic viscosity, surface tension and surface charge, hydrolytic weakening, diffusivity, conductivity, freezing point depression, and degree of polymerization of silicates in melts, glasses, and aqueous solutions. As a test of our calculational procedure, observed X-ray emission spectra of binary alkali silicate glasses were compared with calculated electronic spectra. The well known bondlength variations between the bridging bond [Si-O(br)] and the non-bridging bond [Si-O(nbr)] in alkali silicates are shown to be due to the propagation of oscillating bond-energy patterns through the silica framework. A kinetic interpretation of some results of our calculations is given in terms of the Bell-Evans-Polanyi reaction principle.  相似文献   

20.
Two modified polymer flocculants of PDADMA salts, PDADMA nitrate (PDADMAN) and PDADMA sulfate (PDADMAS), were prepared from the most widely used commercial product of polydiallyldimethylammonium chloride (PDADMAC). Solution properties such as conductivity and viscosity were investigated, showing that the conductivity follows the order of PDADMAS > PDADMAC > PDADMAN, while the reduced viscosity increases in the order of PDADMAS < PDADMAC < PDADMAN. The results indicate that, compared with PDADMAC, PDADMAN has a more cationic density and a more extended polymer chain, whereas PDADMAS exhibits a smaller coiled polymer size because of the stronger charge affinity of sulfate ion to the polycation of PDADMA. Flocculation experiments were performed on kaolin suspensions. It was found that PDADMAN is the most efficient in turbidity removal, while PDADMAS has wider optimum dosages, larger floc size and more rapid settling rate. Atomic force microscopy (AFM) was employed for imaging the adsorption structures of the three polymers on the negatively charged mica surface. Remarkable differences in molecular conformation were observed. Compared with the pearl necklace-like aggregation of hemispheroids of PDADMAC polymer, PDADMAN takes a sponge-like thin layer structure and PDADMAS exhibits a uniform hemispherical structure.  相似文献   

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