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1.
《Applied Geochemistry》1995,10(2):197-205
The adsorption of Zn (total concentration 10−6 M) to colloidal quartz, hydrargillite and goethite (50, 300 and 70 mg/l, respectively) was studied by a batch technique at a constant ionic strength (0.01 M) but with variation of pH (3–10) and fulvic acid (FA) concentration (0, 2 or 20 mg/l). The adsorption had similar pH-dependence in all systems in the absence of FA giving a pH50 (pH of 50% adsorption) of 7.6 under these conditions. The presence of the FA reduced the overall adsorption to quartz (pH50 of 7.9 at 2 mg FA/I and 9.3 at 20 mg/1) and shifted the adsorption curves downwards (pH50 of 6.8) in the hydrargillite and goethite systems at 2 mg FA/l. At 20 mg FA/l, the adsorption in the two latter systems was increased at pH <6.5 and reduced at pH >6.5. The results reflect the affinity of the surfaces for FA as well as the formation of Zn–FA complexes (in solution and on solid surfaces). 相似文献
2.
The adsorption of plutonium IV and V on goethite 总被引：1，自引：0，他引：1
The adsorption of Pu(IV) and Pu(V) on goethite (αFeOOH) from NaNO3 solution shows distinct differences related to the different hydrolytic character of these two oxidation states. Under similar solution conditions, the adsorption edge of the more strongly hydrolyzable Pu(IV) occurs in the pH range 3 to 5 while that for Pu(V) is at pH 5 to 7. The adsorption edge for Pu(V) shifts with time to lower pH values and this appears to be due to the reduction of Pu(V) to Pu(IV) in the presence of the goethite surface. These results suggest that redox transformations may be an important aspect of Pu adsorption chemistry and the resulting scavenging of Pu from natural waters.Increasing ionic strength (from 0.1 M to 3 M NaCl or NaNO3 and 0.03 M to 0.3 M Na2SO4) did not influence Pu(IV) or Pu(V) adsorption. In the presence of dissolved organic carbon (DOC), Pu(V) reduction to Pu(IV) occurred in solution. Pu(IV) adsorption on goethite decreased by 30% in the presence of 240 ppm natural DOC found in Soap Lake, Washington waters. Increasing concentrations of carbonate ligands decreased Pu(IV) and Pu(V) adsorption on goethite, with an alkalinity of 1000 meq/l totally inhibiting adsorption.The Pu-goethite adsorption system provides the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. From the model calculations we determined equilibrium constants for the adsorption of Pu(IV) hydrolysis species. The model was then applied to Pu adsorption in carbonate media to see how the presence of CO3?2 could influence the mobility of Pu. The decrease in adsorption appears to be due to formation of a Pu-CO3 complex. Model calculations were used to predict what the adsorption curves would look like if Pu-CO3 complexes formed. 相似文献
3.
Katsuhiro Tsukimura Hiromoto Nakazawa Tadashi Endo Osamu Fukunaga 《Physics and Chemistry of Minerals》1992,19(4):203-212
This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)9S8. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol–1, 20.52 J K–1 mol–1, and 6.99 × 10–6 m3 mol–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 102
T
–1+8.41 x 10–7
T
–1
P, where K = (Fe/Ni)octahedral /(Fe/Ni)tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol–1. 相似文献
4.
In order to better understand the influence and mechanism of soil-derived humic acid (SHA) on adsorption of P onto particles in soils, the amounts of PO4 adsorbed by synthetic goethite (α-FeOOH) were determined at different concentrations of SHA, pH, ionic strength and order of addition of adsorbents. Addition of SHA can significantly reduce the amount of PO4 adsorption as much as 27.8%. Both generated electrostatic field and competition for adsorption sites were responsible for the mechanism by which SHA inhibited adsorption of PO4 by goethite. This conclusion was supported by measurement of total organic C (TOC), infrared spectral features and Zeta potential. Adsorption of PO4 onto goethite was inversely proportional to pH. Order of addition of PO4 and SHA can influence adsorption of PO4 as follows: prior addition of PO4 ⩾ simultaneous addition > prior addition of SHA. Iron and SHA apparently form complexes due to prior addition of SHA. Observations made during this study emphasized that PO4 forms different types of complexes on the surface of goethite at different pH, which dominated the interaction of SHA and PO4 adsorption on goethite. Based on these observations, the possible modes of SHA inhibition of PO4 adsorption on goethite were proposed. 相似文献
5.
Thorium(IV) sorption onto hematite (-Fe2O3) was examined as a function of pH and ionic strength. Sorption behaved Langmuirian over an eleven order of magnitude range in adsorption densities, : 10–12 to 10–1 moles Th sorbed per mole hematite sites, indicating that the overall free energy of Th adsorption is independent of adsorption density. Modeling of Th sorption was conducted with the Triple Layer Model of Davis and Leckie; reactions considered included solution-phase hydroxy and carbonato complexes of thorium, and carbonate/hematite surface complexes. The entire Th sorption isotherm can be modeled with a single surface complex formation reaction
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6.
7.
Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO3 and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X−). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K(X2Me) and log K(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals. 相似文献
8.
The subsurface mobility of Np is difficult to predict in part due to uncertainties associated with its sorption behavior in geologic systems. In this study, we measured Np adsorption onto a common gram-positive soil bacterium, Bacillus subtilis. We performed batch adsorption experiments with Np(V) solutions as a function of pH, from 2.5 to 8, as a function of total Np concentration from 1.29 × 10−5 M to 2.57 × 10−4 M, and as a function of ionic strength from 0.001 to 0.5 M NaClO4. Under most pH conditions, Np adsorption is reversible and exhibits an inverse relationship with ionic strength, with adsorption increasing with increasing pH. At low pH in the 0.1 M ionic strength systems, we observed irreversible adsorption, which is consistent with reduction of Np(V) to Np(IV). We model the adsorption reaction using a nonelectrostatic surface complexation approach to yield ionic strength dependent NpO2+-bacterial surface stability constants. The data require two bacterial surface complexation reactions to account for the observed adsorption behavior: R-L1− + NpO2+ ↔ R-L1-NpO2° and R-L2− + NpO2+ ↔ R-L2-NpO2°, where R represents the bacterium to which each functional group is attached, and L1 and L2 represent the first and second of four discrete site types on the bacterial surface. Stability constants (log K values) for the L1 and L2 reactions in the 0.001 M system are 2.3 ± 0.3 and 2.3 ± 0.2, and in the 0.1 M system the values are 1.7 ± 0.2 and 1.6 ± 0.2, respectively. The calculated neptunyl-bacterial surface stability constants are not consistent with values predicted using the linear free energy correlation approach from Fein et al. (2001), suggesting that possible unfavorable steric interactions and the low charge of NpO2+ affects Np-bacterial adsorption. 相似文献
9.
We studied selenite () retention by magnetite () using both surface complexation modeling and X-ray absorption spectroscopy (XAS) to characterize the processes of adsorption, reduction, and dissolution/co-precipitation. The experimental sorption results for magnetite were compared to those of goethite (FeIIIOOH) under similar conditions. Selenite sorption was investigated under both oxic and anoxic conditions and as a function of pH, ionic strength, solid-to-liquid ratio and Se concentration. Sorption onto both oxides was independent of ionic strength and decreased as pH increased, as expected for anion sorption; however, the shape of the sorption edges was different. The goethite sorption data could be modeled assuming the formation of an inner-sphere complex with iron oxide surface sites (SOH). In contrast, the magnetite sorption data at low pH could be modeled only when the dissolution of magnetite, the formation of aqueous iron-selenite species, and the subsequent surface complexation of these species were implemented. The precipitation of ferric selenite was the predominant retention process at higher selenite concentrations (>1 × 10−4 M) and pH < 5, which was in agreement with the XAS results. Sorption behavior onto magnetite was similar under oxic and anoxic conditions. Under anoxic conditions, we did not observe the reduction of selenite. Possible reasons for the absence of reduction are discussed. In conclusion, we show that under acidic reaction conditions, selenite retention by magnetite is largely influenced by dissolution and co-precipitation processes. 相似文献
10.
The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2 总被引：2，自引：1，他引：1
Josep M. Soler Marco Boi Jos Luis Mogolln Jordi Cama Carlos Ayora Peter S. Nico Nobumichi Tamura Martin Kunz 《Applied Geochemistry》2008,23(12):3579-3588
Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H2SO4, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L−1, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO4–H+ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H+ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO4–H+ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H+ solutions. 相似文献
11.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K). 相似文献
12.
Takahiro Nagata 《Geochimica et cosmochimica acta》2010,74(21):6000-6013
Aqueous iodine species occur mainly as iodide (I−) and iodate (IO3−), depending on redox conditions. The adsorption of IO3− on naturally occurring oxides under oxic conditions is of environmental concern. The adsorption behaviors of IO3− by hydrous ferric oxide (HFO), α-FeOOH, and γ-Al2O3 were examined in this study as functions of pH, ionic strength, and solid concentration. Adsorption data were analyzed using an extended triple-layer model (ETLM) for surface complexation modeling to infer IO3− adsorption reactions and equilibrium constants. Results of ETLM analysis suggest that adsorption of IO3− is both an outer-sphere and an inner-sphere process, as expressed by the following complexation reactions, which are consistent with the independent pressure jump kinetic results and adsorption enthalpy measurements
13.
Dimitri A. Sverjensky 《Geochimica et cosmochimica acta》2006,70(10):2427-2453
Despite the fact that the bulk compositions of most low temperature natural surface waters, groundwaters, and porewaters are heavily influenced by alkaline earths, an understanding of the development of proton surface charge in the presence of alkaline earth adsorption on the surfaces of minerals is lacking. In particular, models of speciation at the mineral-water interface in systems involving alkaline earths need to be established for a range of different minerals. In the present study, X-ray standing wave results for Sr2+ adsorption on rutile as a tetranuclear complex [Fenter, P., Cheng, L., Rihs, S., Machesky, M., Bedyzk, M.D., Sturchio, N.C., 2000. Electrical double-layer structure at the rutile-water interface as observed in situ with small-period X-ray standing waves. J. Colloid Interface Sci.225, 154-165] are used as constraints for all the alkaline earths in surface complexation simulations of proton surface charge, metal adsorption, and electrokinetic experiments referring to wide ranges of pH, ionic strength, surface coverage, and type of oxide. The tetranuclear reaction
4>SOH+M2++H2O=(>SOH)2(>SO-)2_M(OH)++3H+ 相似文献
14.
Dissolution and precipitation rates of brucite (Mg(OH)2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10−4 to 3 M), saturation index (−12 < log Ω < 0.4) and aqueous magnesium concentrations (10−6 to 5·10−4 M). Brucite surface charge and isoelectric point (pHIEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pHIEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m2) and lack of dependence on ionic strength predicts the dominance of >MgOH2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO− as pH increases to 10-12. Rates are proportional to the square of >MgOH2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity:
15.
The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is discussed for TiO2, γ-AlOOH (boehmite), γ-FeOOH (lepidocrocite), α-FeOOH (goethite) and HFO (ferrihydrite) in relation to the surface structure and surface sites. One type of surface complex is formed at TiO2 and γ-AlOOH, i.e. a surface-coordinated Fe2+ ion. At the TiO2 (Degussa) surface, the Fe2+ ion is probably bound as a quattro-dentate surface complex. The CD value of Fe2+ adsorbed to γ-AlOOH points to the formation of a tridentate complex, which might be a double edge surface complex. The adsorption of Fe(II) to ferric (hydr)oxides differs. The charge distribution points to the transfer of electron charge from the adsorbed Fe(II) to the solid and the subsequent hydrolysis of the ligands that coordinate to the adsorbed ion, formerly present as Fe(II). Analysis shows that the hydrolysis corresponds to the hydrolysis of adsorbed Al(III) for γ-FeOOH and α-FeOOH. In both cases, an adsorbed M(III) is found in agreement with structural considerations. For lepidocrocite, the experimental data point to a process with a complete surface oxidation while for goethite and also HFO, data can be explained assuming a combination of Fe(II) adsorption with and without electron transfer. Surface oxidation (electron transfer), leading to adsorbed Fe(III)(OH)2, is favored at high pH (pH > ∼7.5) promoting the deprotonation of two FeIII-OH2 ligands. For goethite, the interaction of Fe(II) with As(III) and vice versa has been modeled too. To explain Fe(II)-As(III) dual-sorbate systems, formation of a ternary type of surface complex is included, which is supposed to be a monodentate As(III) surface complex that interacts with an Fe(II) ion, resulting in a binuclear bidentate As(III) surface complex. 相似文献
16.
Groundwaters from crystalline and metamorphic rocks (hardrocks) and from Quaternary deposits, i.e., alluvial and glacial deposits (softrocks) from the counties of Nord-Trøndelag and Sør-Trøndelag were analyzed for major and minor elements and ions including fluoride. The median concentration of F– in water from the hardrock aquifers is 0.28 mg/l (14.7 eq/l) in contrast to water from softrock aquifers in which it is found to be 0.05 mg/1 (2.6 eq/l). More importantly, ca. 15% of the locations where water was abstracted from hardrock wells contain 1.5 mg/l (78.9 eq/l) F– or more. Thus, 15% of all hardrock wells returned F– results that are at or above the maximum recommended value for drinking water. Of the softrock wells, none are above 1 mg/l. Geologists would normally expect higher F–contents in groundwaters derived from acid rocks, e.g., in granitic or gneissic areas. When comparing the host lithology with the observed F–contents, however, no clear relationship between F– content and lithology is visible. The highest observed F– values actually occur in gneissic host rocks. However, wells drilled in amphibolites/greenstones, mica schists, calcareous rocks, and sedimentary rocks all returned some analytical results above 1.5 mg/l F–. These results suggest that all hardrock wells drilled should be tested for F– and the users informed about the results and advised to take any necessary precautions. When applying the recently proposed Norwegian drinking water limits to our data, 51% of all softrock well waters and 56% of all hardrock well waters are unfit for consumption without prior treatment, although we analyzed only for about half of the proposed elements/parameters. This result seriously questions the concept of fixed action levels—many of them with totally unproven health implications—for so many parameters/elements for hardrock groundwaters. 相似文献
17.
Thomas J. Reich 《Geochimica et cosmochimica acta》2011,75(22):7006-7017
Adsorption of Cr(VI) on γ-alumina was investigated as a function of ionic strength (0.001, 0.01 and 0.1 M NaNO3), pH (4-10), Cr(VI) concentration (10−4 or 10−5 M with 5 g/L solid) and pCO2 (0, atmospheric, 2.5%). Cr(VI) sorption is significant at low pH and decreases with increasing pH, with 50% of the Cr(VI) adsorbed between pH ∼6.5 and 8. Adsorption varies little with ionic strength or pCO2 under most of the studied conditions. However, at low pH under high ionic strength and especially at high ionic strength and high pCO2, Cr(VI) sorption on γ-alumina is suppressed. The adsorption edge data were used to parameterize constant capacitance (CCM), diffuse double layer (DLM) and triple layer (TLM) surface complexation models. None of the models entirely captures the full range of observed adsorption dependence on ionic strength and sorbate/sorbent ratio. The best fits to the full dataset are produced by the CCM, mostly because it has ionic-strength dependent stability constants. The more sophisticated TLM, which requires the most fitting parameters, does not produce better fits than the simpler CCM or DLM approaches for the conditions tested in this study. 相似文献
18.
We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartz
19.
Tjisse Hiemstra Willem H. Van Riemsdijk André Rossberg Kai-Uwe Ulrich 《Geochimica et cosmochimica acta》2009,73(15):4437-19695
The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere complexes at sites that do not react chemically with carbonate ions. Uranyl is bound by singly-coordinated surface groups present at particular edges of Fe-octahedra of ferrihydrite while another set of singly-coordinated surface groups may form double-corner bidentate complexes with carbonate ions. The uranyl surface speciation strongly changes in the presence of carbonate due to the specific adsorption of carbonate ions as well as the formation of ternary uranyl-carbonate surface complexes. Data analysis with the CD model suggests that a uranyl tris-carbonato surface complex, i.e. (UO2)(CO3)34−, is formed. This species is most abundant in systems with a high pH and carbonate concentration. This finding differs significantly from previous interpretations made in the literature. At high pH and low carbonate concentrations, as can be prepared in CO2-closed systems, the model suggests the additional presence of a ternary uranyl-monocarbonato complex. The binding mode (type A or type B complex) is uncertain. At high uranyl concentrations, uranyl polymerizes at the surface of ferrihydrite giving, for instance, tris-uranyl surface complexes with and without carbonate. The similarities and differences between U(VI) adsorption by goethite and ferrihydrite are discussed from a surface structural point of view. 相似文献
20.
Peter J. Swedlund Jenny G. Webster Gordon M. Miskelly 《Geochimica et cosmochimica acta》2009,73(6):1548-43
Adsorption of Cu2+, Zn2+, Cd2+, and Pb2+ onto goethite is enhanced in the presence of sulfate. This effect, which has also been observed on ferrihydrite, is not predicted by the diffuse layer model (DLM) using adsorption constants derived from single sorbate systems. However, by including ternary surface complexes with the stoichiometry FeOHMSO4, where FeOH is a surface adsorption site and M2+ is a cation, the effect of SO42− on cation adsorption was accurately predicted for the range of cation, goethite and SO42− concentrations studied. While the DLM does not provide direct molecular scale insights into adsorption reactions there are several properties of ternary complexes that are evident from examining trends in their formation constants. There is a linear relationship between ternary complex formation constants and cation adsorption constants, which is consistent with previous spectroscopic evidence indicating ternary complexes involve cation binding to the oxide surface. Comparing the data from this work to previous studies on ferrihydrite suggests that ternary complex formation on ferrihydrite involves complexes with the same or similar structure as those observed on goethite. In addition, it is evident that ternary complex formation constants are larger where there is a stronger metal-ligand interaction. This is also consistent with spectroscopic studies of goethite-M2+-SO42− and phthalate systems showing surface species with metal-ligand bonding. Recommended values of ternary complex formation constants for use in SO4-rich environments, such as acid mine drainage, are presented. 相似文献
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