Sorption of heavy metal ions by a hydrous manganese oxide

Sorption of Co, Zn, Ca and Na by δ-MnO₂ was studied at 24.0 ± 0.5°C and pH 4. During the sorption of Co and Zn, Mn was released to the solution phase; however, Mn release was not detected during the sorption of Ca and Na. On the basis of crystal field theory, it is proposed that Zn may interchange with Mn²⁺ in the δ-MnO₂ structure, whereas Co may interchange with both Mn²⁺ and Mn³⁺. It is suggested that the interchangeable Mn²⁺ and Mn³⁺ sites were in the disordered layers in the δ-MnO₂ structure.Sorption of Co, Zn and Ca at pH 4 fitted single-site Langmuir isotherm expressions at all Ca concentrations, but only at concentrations greater than 10^?4 M for Co and Zn. Mn release by δ-MnO₂ at pH 4 during Co and Zn sorption also fitted single-site Langmuir isotherms. An expression for the case of multisite Langmuir sorption was derived and applied to the cases of Co and Zn sorption and to the case of Mn release during Co sorption. The data of these cases were used to calculate statistically the coefficients of multiple regression equations from which the sum of the capacities of all sites in each case were obtained. From all of these derived capacities, it is proposed that there was only one site where Ca interchanged with surface bound H. Zn was postulated to interchange not only with these bound H sites, but also with another site where it interchanged with structural Mn²⁺. Co was postulated to interchange with both of these sites, and additionally, with a third site where it interchanged with structural Mn³⁺.Using a pH-stat set at pH 4, it was determined that approximately 2 moles of H were released per mole of Co or Zn sorbed at bound H sites.     

沉积CaCO3与金属离子界面反应动力学研究

金属离子与沉积碳酸盐之间２同反应动力学模拟实验表明,由于ＣａＣＯ３快速溶解和溶液ＰＨ急剧上升,大部分Ｐｂ＾２＋、Ｚｎ＾２＋离子与溶液中ＣＯ３＾２－和ＯＨ＾－离子反应生成白铅矿ＰｂＣＯ３、水白铅矿Ｐｂ３（ＯＨ）２（ＣＯ３）２,或Ｚｎ（ＯＨ）３和锌矿Ｚｎ（ＯＨ）６（ＣＯ３）２沉淀于体相溶液中,仅有少部分Ｐｂ＾２＋、Ｚｎ＾２＋通过扩散与ＣａＣＯ３表面发生离子交换反应。２５℃时,Ｐｂ＾２＋溶液中以白铅矿沉     

Proton release during adsorption of heavy metal ions by a hydrous manganese dioxide

During the adsorption of Pb, Cu, Mn or Zn by birnessite, 1 mol of H⁺ is released from the surface for each mole of metal ion sorbed. The potassium appearing in solution during adsorption is not directly involved in the reaction. This resolves some apparently conflicting published results.     

The interaction of cobalt with hydrous manganese dioxide

Adsorption of cobalt on synthetic hydrous manganese dioxide was studied as a function of pH and surface area in NaCl solutions and solutions containing sea water concentrations of Na, Ca and Mg. The amount of cobalt adsorbed increased sharply at pH 6, a significantly lower pH than that required for significant hydrolysis of Co(II) or precipitation of Co(OH)₂(S) in bulk solution. Sea water concentrations of Na, Ca and Mg have little effect on adsorption until the cobalt concentration is less than 10^?7 M.Micro-electrophoresis experiments from 1 × 10^?3 M to 1 × 10^?5 M to Co(II) show three charge reversals. The first is the pH of zero point charge of hydrous manganese dioxide. The second correlates well with the abrupt increase in adsorption at pH 6 and may reflect both specific adsorption of Co(II) and precipitation of Co(OH)₂ on the surface. The third agrees well with literature values for the pH of zero point of charge of Co(OH)₂.An adsorption isotherm was constructed for cobalt and these data were used to test the hypothesis that the enrichment of cobalt in the suspended matter of the Black Sea is due to adsorption of cobalt from sea water by manganese dioxide. The calculations indicate that adsorption is a feasible explanation for this example.     

Reactions of metal ions at surfaces of hydrous iron oxide

Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10^?8.00 or 10^?9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn₃O₄ can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn⁴⁺ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10^?9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems.     

The impacts of common ions on the adsorption of heavy metal

Researches on the impact of common ions onto sediments are of great importance for the study of the heavy metal adsorption mechanisms. Considering the surface sediments from the relatively clean reach in the Baotou section of the Yellow River as the adsorbent, this work presents the impacts of common ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, Cl⁻, SO₄ ²⁻, and NH₄ ⁺) on heavy metals (Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺) adsorption. The experimental results reveal that the adsorptive capacities of the heavy metals are controlled by different adsorption mechanisms in different ion concentration ranges. With the increase of the ionic strength, the adsorption of the heavy metals increases for the compression of the electric double layer, whereas decreases for the decreasing of the ionic activities of the heavy metals. The competitive adsorption and complexations between the heavy metals and common ions are also important factors controlling the heavy metal adsorption. According to the experimental results and the real concentration of common ions in the Baotou section of the Yellow River, the increase of the concentrations of Na⁺, Mg²⁺, K⁺, and Ca²⁺ would cause the increase of Zn²⁺ adsorption and reduce the Zn pollution. The NH₄ ⁺ from the industrial discharge of the tributaries has a strong impact on the heavy metal adsorption.     

On the distribution of iron and manganese at the sediment/water interface: thermodynamic versus kinetic control

Iron and manganese solubility at the sediment/water interface has been studied at a water depth of 20 m in Kiel Bight, Western Baltic. By means of an in situ bell jar system enclosing 3.14 m² sediment surface and 2094 l water a complete redox turn-over in the bottom water was simulated in an experiment lasting 99 days. The concentration of dissolved Fe in the bell jar water never exceeded 0.041 μmol · dm^?3during the first 50 days of the experiment and then rose abruptly as the Eh fell from +600 to ?200 mV. The concentration of dissolved Fe under oxic and anoxic conditions seems to be limited by equilibria with solid Fe-phases (hydroxides and amorphous sulphide, respectively). In contrast to Fe, manganese was released continuously from the bottom during the first 50 days of the experiment leading to exponentially increasing manganese concentrations in the bell jar water. During this time dissolved O₂ had become ready depleted and pH had dropped from 8.3 to 7.5. Contrary to iron, manganese being solubilized in reduced sediment layers can penetrate oxic strata in metastable form due to slow oxidation kinetics; when the redoxcline moves upwards Mn²⁺ is enriched in bottom waters. The maximum concentration of dissolved Mn under anoxic conditions is controlled by a solid phase with solubility properties similar to MnCO₃ (rhodochrosite). Bottom water enrichment in dissolved Mn²⁺ could be traced to originate from excess solid manganese within the top 3 cm of the sediment.     

The influence of metal content on the physical and mineralogical properties of pelagic manganese nodules

Deep sea manganese nodules are considered as important natural resources for the future because of their Ni, Cu and Co contents. Their different shapes cannot be correlated clearly with their chemical composition. Surface constitution, however, can be associated with the metal contents. A classification of the nodules is suggested on the basis of these results. The iron content of the nodules strikingly shows relations to the physical properties (e.g. density and porosity). The method of density-measurement is the reason for this covariance. The investigation of freeze-dried nodular substance does not give this result. The Fe-rich nodules lose more hydration water than the Fe-poor ones during heat drying. The reason for this effect is the different crystallinity, respectively the particle size. The mean particle size is calculated on the basis of geometrical models. The X-ray-diffraction analysis proves the variation of crystallinity in connection with the Fe-content, too. The internal nodular textures also show characteristic distinctions.     

Sorptive flotation for metal ions recovery

In this study, the abstraction of nickel, copper and zinc ions from aqueous solutions has been investigated in a laboratory batch scale mode. A combined two-stage process is proposed as an alternative of the heavy metals removal from aqueous solutions. The first stage is the sorption of heavy metals onto non-living microorganisms followed by dispersed-air flotation of the loaded biomass. Three types of strains were used: Penicillium chrysogenum, Saccharomyces carlsbergensis and Streptomyces rimosus. The main parameters studied were solution pH, biomass concentration, surfactant concentration and flocculant concentration. The biomass reuse after elution was also examined. Remediation is a possible application of flotation being cost-effective and with readily available equipment and know-how. The application of this process looks promising.     

Coprecipitation of alkali metal ions with calcium carbonate

The coprecipitation of alkali metal ions (Li⁺, Na⁺, K⁺ and Rb⁺) with calcium carbonate has been studied experimentally and the following results have been obtained:

• 1.(1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite.
• 2.(2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na⁺ which has approximately the same ionic radius as Ca²⁺.
• 3.(3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals.
• 4.(4) Our results support the hypothesis that
  • 4.1.(a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca²⁺ in the lattice, but
  • 4.2.(b) in aragonite, alkali metals substitute for Ca²⁺ in the crystal structure.
• 5.(5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li⁺, Na⁺, K⁺ and Rb⁺) coprecipitated with calcite but decrease those with aragonite.
• 6.(6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li⁺, K⁺ and Rb⁺) into the aragonite.

     

Experimental study on the competitive adsorption of metal ions onto minerals

The study on the competitive adsorption shows that the magnitude order of metal ions adsorbed onto oxide and silicate minerals in near-neutral solution with low ionic strength is in mole/nm² as follows: CaCO₃ > quarte > hydromuscovite > kaolinite > Ca-montmorillonite > goethite > gibbsite. These minerals can be divided into three groups according to their surface equilibrium constantsK _M of the adsorption reactions, which are the function of the dielectric constants ε of the absorbent minerals. The relationships between constantsK _M and mineral dielectric constants ε are described as follows: lgK _M ¹ = 7.813-26.15/ε lgK _M ² = 9.030-26.15/ε lgK _M ³ =11.63-26.15/ε for the adsorption reaction: >SO^- + Mⁿ⁺≥SOM^n-1)+ (n = 1, 2, 3) The first group of minerals include quartz, goethite, 1:1 phyllosilicates and other oxide minerals; the second: gibbsite, brucite and 2:1 phyllosilicates; the third: carbonate, sulphate and phosphorate minerals. The appearance reaction constants have a variation of magnitude ±0.5 for different metal ions with the same mineral. This project was financially supported by the National Natural Science Foundation of China (No. 49572091).     

pH effects in the adsorption of heavy metal ions by clays

The amount of hydroxonium or hydroxyl ion sorbed by the sodium form of clays (kaolin, illite or montmorillonite) has been found to increase in proportion with the amount added (i.e., data fits a Boedeker type equation). The adsorptive capacities, and bonding strengths (as evaluated from Langmuir isotherm plots) varied with clay type and nature of the adsorbing species (values for OH^? being greater than for H⁺).The presence of clay suspensions reduced the pH required for total precipitation of heavy metal ions (e.g., Cu, Pb, Cd, Zn), as hydroxy species, and this behaviour has been re-examined in terms of observed pM, pOH relationships and the effect of ligand additions.     

重金属离子在胡敏酸-高岭石复合体上的吸附

本文研究了胡敏酸存在下高岭石对重金属离子的吸附行为。实验结果表明:①胡敏酸和Cu2 溶液按先后顺序或同时加入高岭石中反应,在Cu2 平衡浓度<10mg/L时,3种加入顺序对Cu2 的吸附量基本相同,当Cu2 平衡浓度>10mg/L时,(K Cu) HA和(K Cu HA)两种加入顺序对Cu2 的吸附量比(K HA) Cu的略大。②在pH=5时,胡敏酸-高岭石复合体对Cu2 的吸附量明显大于纯高岭石。这是由于胡敏酸含有大量的羧基和酚羟基等活性基团,吸附在高岭石上的胡敏酸增加了其表面吸附位,在复合体表面形成了S—HA—Cu三元配合物,且Cu2 的吸附量与复合体中胡敏酸的含量在一定范围内成正相关;③溶液pH值在4～7之间变化可调控复合体对Cu2 的吸附机制。④在Cu2 和Cd2 共存时,随着金属离子初始浓度的增大,Cu2 的吸附量呈直线上升,而Cd2 的吸附量增加缓慢,表明复合体对Cu2 的吸附能力比对Cd2 强。     

Polarized X-ray absorption spectroscopy of metal ions in minerals

We have made use of the nearly complete linear polarization of synchrotron radiation to study the polarization dependence of X-ray absorption near-edge structure (XANES) and extended fine structure (EXAFS) in oriented single crystals of gillespite (BaFe²⁺ Si₄O₁₀; Fe^{2 +} in square-planar coordination, point symmetry C ₄), anatase (TiO₂; Ti⁴⁺ in octahedral coordination, point symmetry D _2d), and epidote (Ca₂(Al, Fe³⁺)₃SiO₄)₃(OH); Fe³⁺ in distorted octahedral coordination, point symmetry (C _s). For gillespite, the Fe K-XANES spectrum varies strongly with E-vector orientation of the incident X-ray beam. When the E-vector lies in the plane of the FeO₄ group (i.e., perpendicular to the c-axis), multiple-scattering features at 7127 and 7131 eV intensify, whereas when the E-vector is perpendicular to the plane of the FeO₄ group (i.e., parallel to the c-axis), a strongly-polarized 1s to 4p bound state transition occurs at 7116 eV and a localized continuum resonance occurs at 7122 eV. The Fe-K-EXAFS spectrum of gillespite is also highly polarization dependent. When the E-vector is perpendicular to c, all four nearest-neighbor oxygens around Fe²⁺ contribute to the EXAFS signal; when E is parallel to c, the EXAFS signal from nearest-neighbors is reduced by at least 86%. The unpolarized Ti K-XANES spectrum of anatase has three relatively strong pre-edge features at 4967.1, 4969.9, and 4972.7 eV which have resisted definitive interpretation in past studies. The lowest energy feature has a strong xy polarization dependence, suggesting a large amount of 4p _x,y character, and it is also very sharp, indicating a well-defined transition energy. Both of these observations are consistent with an excitonic state with a binding energy of 2.8 eV. The two higher energy features, which are characteristic of octahedrally-coordinated Ti⁴⁺, show little polarization dependence and are probably due to 1s to 3d bound-state transitions, with a small degree of np character in the final state wavefunction. Interpretation of the polarization dependence of Fe K-XANES spectra for epidote is not as straightforward due to the lower space group symmetry (P2₁/m) relative to gillespite (P4/ncc) and anatase (I4₁/amd) and the lower point group symmetry (C _s) of the M(3) site which contains most of the Fe³⁺ in the epidote structure. However, the presence of a shoulder at 7121 eV in the E parallel to b spectrum and its absence in the E normal to bc spectrum are consistent with it being a 1s to 4p _z bound-state transition. Strong, weakly x, y polarized features near 7126 eV in both spectra are most likely due to localized continuum transitions. Also, the 1s to 3d pre-edge intensity varies in intensity with E-vector orientation which is consistent with displacement of Fe³⁺ from the center of the M(3) octahedral site. Analysis of EXAFS spectra of epidote in these two polarizations yields bond distances which are within 0.04 Å of previous single-crystal X-ray diffraction analysis. This study demonstrates the utility of polarized X-ray absorption spectroscopy in quantifying the energies and orbital compositions of final state wavefunctions associated with various X-ray induced transitions in transition-metal containing minerals. It also shows that reasonably accurate M-O distances can be obtained for individual bonds oriented in crystallographically non-equivalent directions.     

Boundary waves at the water-sea bottom interface

Doklady Earth Sciences -     

可变电荷土壤和恒电荷土壤与氢离子相互作用机理

研究了可变电荷土壤和恒电荷土壤与H相互作用的机理，并比较了它们之间的差别，研究结果表明，氢离子输入土壤后可以转化为表面正电荷，可溶性铝和可交换性酸，但是由于土壤的组成和性质不同，不同土壤中H＋三种去向的贡献不同。H＋转化为表面正电荷是由于土壤表面Fe-OH,Al-OH的质子化造成的，因此H＋转化为表面正电荷的能力与土壤中氧化铁的含量密切相关，从而可变电荷土壤中H＋转化为表面正电荷的贡献比恒电荷土壤中的大。H＋转化为可溶性铝的能力与土教育部 的矿物组成密切相关，随着H＋输入量的增加，土壤中可溶性铝的含量也增加。可变电荷土壤中可溶性铝增加的顺序为红壤＞赤红壤＞铁质砖红壤，在H＋的加入量小于15mmol/kg时，黄棕壤的可溶性铝介于红壤和赤红壤之间，当H＋的加入量大于约15mmol/kg时，黄棕壤的可溶性铝略小于赤红壤，棕壤的可溶性铝明显小于红壤和赤红壤，但比铁质砖红壤高，恒电荷土壤的可变性酸量明显大于可变电荷土壤，但从总的看来，H＋加入量的变化对可交换性酸量的影响不大。     

The metal ions release and microstructure of coal gangue corroded by acid-based chemical solution

Cationic release, surface microstructure, and pore size distribution of coal gangue during the acid-based chemical solution corrosion were investigated. Results showed that during the interactions of gangue and chemical solution, the acidity and alkalinity of mixed solutions first decrease quickly, and then stabilize. The concentrations of released Ca, Mg, and Fe in gangue decrease with the decreasing acidity of the chemical solution, and produce a trend of increase-to-decrease with the increase in alkalinity. The release of Ca, Mg, and Fe is significantly influenced by the weathering of gangue. Ca and Mg achieve a concentrated release during the first day, whereas the release of Fe occurs gradually within the first 10 days. The microstructure detection result indicates that the surface structure of fresh gangue is exposed to obvious corrosion by acid-based chemical solutions, with higher extent of corrosion in acidic solution than that in alkaline solution. The micropore is relatively developed, and the secondary and middle pores increase gradually. The specific surface area is increased. Furthermore, the pore size distribution of abundance of micropore and middle pore shows a series of inconsistent spectra instead of a continuous wide-flat spectrum.     

Geochemical behaviour of iron and manganese ions in the Ningyo-Toge uranium deposit district, southwest Japan

The Ningyo-Toge uranium deposit is one of the typical sedimentary uranium deposits in Japan. In general, during weathering, U is removed from the basal granite through underground water. The underground water in this area is rich in U, and has a comparatively high concentration of Fe and Mn.

In this area, three types of Fe minerals can be recognized in different modes of occurrence: (1) in the oxide zone brownish Fe-hydroxide mineral with ferric ion, i.e. goethite (-FeOOH); (2) in the reduced zone of the mine gallery pale-blue Fe-hydroxide mineral with some ferrous ion, i.e. lepidocrocite (γ-FeOOH); and (3) Fe-sulphate minerals such as melanterite (FeSO₄·7H₂O), etc. Some uranyl sulphate minerals, uranopilite and zippeite, are closely associated with these Fe-sulphate minerals. Under weakly alkaline conditions of the oxidizing environment, Mn-hydroxide (MnOOH) coexists with goethite as alternative thin laminae with shale, or coprecipitates resembling a marine Mn nodule, in the size of 0.5 cm in diameter. Radioactive anomalies have been recognized frequently for these Mn sediments due to absorption of Ra by the sediments.     

混合重金属离子侵蚀饱和黏性土渗透特性试验研究

渗透特性是表征黏性土层防渗能力及防污性能的关键控制因素,黏土衬垫渗透系数的正确选择对保证垫层的防污效果具有极其重要的意义。采用柔性壁渗透仪,通过室内试验研究了混合重金属离子共存情况下侵蚀饱和黏性土的渗透特性变化规律。试验结果表明,将可溶性铜、铬离子混合与铜、锰离子混合溶液作为渗液,黏性土渗透性均随着掺入离子浓度比例的增大而逐渐增强,且相同试验条件下,铜、铬离子混合溶液作为渗液测得的黏土渗透系数值大于铜、锰离子混合溶液作为渗液测得的渗透系数值。混合重金属离子的存在削弱了黏土垫层作为工程防污屏障服役的能力,并对黏土层的水力传导性起到了劣化作用。试验土样微观结构分析表明,渗液特性的改变影响了土样内部的微观结构,随着渗液混合离子质量比的增大,土样中出现了凝聚体且有效输运孔隙通道增大,与宏观渗透特性的变化规律相吻合。研究结果能够为有效评估黏土防污屏障的防渗隔污能力及研究堆场渗液在黏土垫层中的运移机制提供参考。