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.     

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.     

齐齐哈尔碾子山麦饭石物化性能及其对Pb2+、Cd2+、Cr3+的吸附行为研究

以齐齐哈尔碾子山麦饭石为研究对象,通过比表面积及孔隙分析、阳离子交换容量(CEC)测试以及p H值缓冲能力测试等,对碾子山区麦饭石的结构和性能进行表征,并进一步研究麦饭石对Pb~(2+)、Cd~(2+)、Cr~(3+)的吸附行为。结果显示:碾子山区麦饭石具有海绵体大孔结构,阳离子交换容量(CEC)13~20 mmol/100 g。碾子山麦饭石对酸碱溶液都具有较好的调节能力,尤其对酸液的调节更高效。重金属吸附性能方面,对Pb~(2+)、Cd~(2+)、Cr~(3+)这3种离子吸附关系为:Pb~(2+)Cr~(3+)Cd~(2+)。     

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。     

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).     

蒙脱石/胡敏酸复合体对重金属离子吸附实验研究

主要研究了蒙脱石吸附胡敏酸后形成的复合体对Cu2 、Cd2 、Cr3 3种重金属离子的吸附.实验结果表明:用胡敏酸对蒙脱石改性后能提高其对3种重金属离子的吸附性能,胡敏酸浓度越大,吸附性能提高程度越大,3种重金属离子的Langmuir吸附等温线线性相关都能达到0.99以上.蒙脱石/胡敏酸复合体对3种重金属离子的吸附量都随pH值的升高而增加,随离子强度的增加而减小.另外还对其吸附动力学进行了研究,发现可用Elovicb方程和双常数方程对吸附过程进行较好地拟合.     

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。     

球状交联壳聚糖树脂的制备及对金属离子吸附研究

以戊二醛为交联剂,利用悬浮聚合法合成了新型壳聚糖树脂,考虑了操作条件对合成树脂性能的影响,通过显微镜显示,树脂的表面结构随着交联剂浓度提高而改善;提高油水体积比,可显著提高树脂粒径;随着搅拌速度的提高,树脂的粒径减小。利用5%壳聚糖溶液,以戊二醛为交联剂可合成较高强度、粒径较小的球状树脂。通过树脂对铜离子的吸附实验可得出树脂具有较好的吸附性能,其最佳吸附pH为5.0,静态吸附容量为2.39mg/g,吸附率为95.3%,拓展了该天然高分子材料在金属离子的富集与回收,以及在工业废水处理领域的应用前景。     

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.     

改性沸石对重金属离子竞争吸附特性研究

以钠型改性沸石为吸附剂,以含有单一的镉、锌、铅溶液以及镉、锌、铅的混合溶液为吸附质,开展了改性沸石中重金属离子的竞争吸附及其影响因素等实验研究。结果表明,当溶液中有多种二价重金属离子存在时,各离子之间存在竞争吸附,竞争能力为Pb2+>Cd2+>Zn2+;Zn2+-Cd2+表现出显著的协同吸附效应,而Zn2+-Pb2+、Cd2+-Pb2+表现出拮抗吸附。     

Modification of PPTA-based polymeric waste and adsorption properties for metal ions

Novel composite adsorbents PPTA-AOx were synthesized by grafting polyacrylonitrile onto poly(p-phenylene terephthalamide) (PPTA) followed by converting the acrylonitrile into the amidoxime (AO) groups. Their structures were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, transmission electron microscopy, etc. Scanning electron microscopy analysis and pore structure analysis manifested that PPTA-AOx adsorbents are all composed of nanoparticles aggregation. The as-synthesized PPTA-AOx adsorbents showed good adsorption capacity for Hg²⁺ with a maximum adsorption capacity of 2.50 mmol g^?1. The pseudo-second-order model can reasonably describe the adsorption kinetics of the three adsorbents for Hg²⁺. Langmuir model provided better fit for the isothermal adsorption of Hg²⁺ on PPTA-AO₁ and PPTA-AO₂, while the Freundlich model was better for PPTA-AO₃. The adsorption process might involve both chemisorption and physisorption. According to the calculated thermodynamic parameters, it can be concluded that the adsorption is an endothermic, spontaneous and entropy-driven process.     

溶液介质条件对重金属离子与石英表面反应的影响

实验研究表明,随着溶液ＰＨ值的升高石芟夺Ｃｕ＾２＋、Ｐｂ＾２＿、Ｃｄ＾２＋等重金属离子的吸附量和表面吸附覆盖率逐渐增大,而表面反应产物的结合开矿相应地出现由单核化合物、多核化合物〖ＳＯＣｕ４（ＯＨ）３＾４＋〗,直至表面沉淀（ＳＯＨ…Ｃｕ（ＯＨ）２（ｓ）〗。随着温度升高,石英对Ｃｕ＾２＋、Ｐｂ＾２＋、Ｃｄ＾２＋等重金属离子的吸附量逐渐减是随着溶液离子强度的增大,石英对Ｃｕ＾２＋离子的吸附量和表面离了     

Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption

Background

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (<a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batch geochemical experiments in conjunction with X-ray absorption spectroscopy.

Results

In both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is more thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h.

Conclusion

This experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.

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Graphical abstract Effects of background anions (sulfate and nitrate) on the Cr(VI) surface coverage at the magnetite-waterinterface at pH 4 and 9

     

Experimental Study on Surface Reactions of Heavy Metal Ions With Quartz—Aqueous Ion Concentration Dependence

Adsorption of divalent metal ions, including Cu²⁺, Pb²⁺, Zn²⁺, Cd²⁺ and Ni²⁺, on quartz surface was measured as a function of metal ion concentration at 30°C under conditions of solution pH= 6. 5 and ion strength I = 0. 1mol/L. Results of the experimental measurements can be described very well by adsorption isotherm equations of Freudlich. The correlation coefficients (r) of adsorption isotherm lines are > 0. 96. Moreover, the experimental data were interpreted on the basis of surface complexation model. The experimental results showed that the monodentate-coordinated metal ion surface complex species (SOM⁺) are predominant over the bidentate-coordinated metal ion surface complex species [(SO)₂M] formed only by the ions Cu²⁺, Zn²⁺ and Ni²⁺. And the relevant apparent surface complexation constants are lgK_M = 2.2–3.3 in order of K_Cd≥K_Pb > K_Zn > K_Ni≥K_Cu, and lgβ_M = 5.9-6.8 in order of β_Ni > β_Zn > β_Cu. Therefore, the reactive ability of the ions onto mineral surface of quartz follows the order of Cd > Pb > Zn > Ni> Cu under the above-mentioned solution conditions. The apparent surface complexation constants, influenced by the surface potential, surface species and hydrolysis of metal ions, depend mainly on the Born solvation coefficient of the metal ions. This project was financially supported by the National Natural Science Foundation of China (No. 49572091).     

The adsorption of aqueous heavy metals on inorganic minerals

Two models have been used to explain the in-situ control of heavy metals: (1) solubility controls, where precipitation of a solid phase occurs under varying metal and ligand concentrations, and (2) surface chemical controls, where adsorption or exchange occurs at the solid/solution interface. Based on experiments presented in this paper, surface chemical controls can account for the removal of heavy metals, particularly Zn(II), from metal solutions which are undersaturated with respect to the hydroxide, oxide, or other controlling solid phases. Adsorption isotherms are presented for varying solution pHs, total metal ion concentrations, ionic strengths, and mineral substrates. The minerals chosen for illustration are SiO₂, TiO₂, FeOOH, Al₂O₃, MnO_x and HgS which range widely in surface acidity, electrical double layer properties, specific surface areas, and surface functional groups.     

介微孔复合沸石分子筛对重金属离子吸附性能的实验研究

以介微孔复合沸石分子筛MCM-41／ZSM-3为吸附剂，采用静态吸附方法初步研究了其对重金属离子Cu^2 、Zn^2 、Pb^2 、Cd^2 的吸附性能。结果表明：对于配置的60mg／dm^3重金属离子溶液，使用分子筛用量为10g／dm^3时，在较宽的pH范围内MCM-41／ZSM-3对Cu^2 、Zn^2 、Pb^2 、Cd^2 的吸附率可达90％以上；对等温吸附曲线的回归分析得出Cu^2 、Zn^2 、Pb^2 、Cd^2 在实验浓度范围内符合Langmuir单吸附位吸附曲线且具有较大的吸附容量。     

Effect of electrode configuration on pH distribution and heavy metal ions migration during soil electrokinetic remediation

Generation, migration, and distribution of H⁺ and OH^? have remarkable influence on heavy metal removal from soil during electrokinetic remediation. A series of experiments were carried out to investigate the effects of electrode configuration and voltage on pH distribution and heavy metal migration, based on the preliminary exploratory experiments. In the first phase, three soil samples were used to observe the effect of electrode configuration on pH distribution. Then, three more soil samples were used to explore the effect of voltage on ion migration. Finally, three other soil samples were used to explore the effect of electrode configuration (i.e. angle CAC) on pH distribution and heavy metal migration. The results showed that the soil was divided into acid, base, and pH-jump zones and that heavy metals migrated under low pH conditions and were deposited at the pH-jump zone. Heavy metal distribution was fairly consistent with pH distribution. Under the optimal condition of $ \angle $ CAC 60º and voltage 2.33 V/cm, 4.22 mg copper and 0.51 mg zinc migrated from acid zone and deposited in pH-jump zone with 6.44 kJ energy consumption.     

Retention of heavy metal ions in bentonites from Grau Region (Northern Peru)

Experimental studies on the retention of metals (Cu, Co, Ni, and Zn) in bentonite samples from the Grau Region (Northern Peru) have been accomplished using monometallic, bimetallic, trimetallic, and tetrametallic solutions. Parameters such as pH and concentration of dissolved metals and organic compounds have been evaluated by means of batch adsorption experiments. Adsorption rates indicate the suitability of these bentonites in the environmental industry for heavy metals retention purposes. In addition to its quality as physical barrier to avoid the dispersion through the environment of polluted leachates, bentonite, due to its high cation exchange capacity, can act also as a chemical barrier, protecting the quality of surface and groundwater systems, while limiting the migration of heavy metals in solid residues or sludge stocked in security landfills. Adsorption rates of tested bentonites were proved to decrease when concentrations of both metal and organic compounds, as well as the number of ionic species, increase in solution; additionally, lower metal removal rates from solution were obtained when extremely acidic conditions were achieved.     

The effect of species diversity on metal adsorption onto bacteria

In this study, we measure proton, Pb, and Cd adsorption onto the bacteria Deinococcus radiodurans, Thermus thermophilus, Acidiphlium angustum, Flavobacterium aquatile, and Flavobacterium hibernum, and we calculate the thermodynamic stability constants for the important surface complexes. These bacterial species represent a wide genetic diversity of bacteria, and they occupy a wide range of habitats. All of the species, except for A. angustum, exhibit similar proton and metal uptake. The only species tested that exhibits significantly different protonation behavior is A. angustum, an acidophile that grows at significantly lower pH than the other species of this study. We demonstrate that a single, metal-specific, surface complexation model can be used to reasonably account for the acid/base and metal adsorption behaviors of each species. We use a four discrete site non-electrostatic model to describe the protonation of the bacterial functional groups, with averaged pK_a values of 3.1 ± 0.3, 4.8 ± 0.2, 6.7 ± 0.1, and 9.2 ± 0.3, and site concentrations of (1.0 ± 0.17) × 10⁻⁴, (9.0 ± 3.0) × 10⁻⁵, (4.6 ± 1.8) × 10⁻⁵, and (6.1 ± 2.3) × 10⁻⁵ mol of sites per gram wet mass of bacteria, respectively. Adsorption of Cd and Pb onto the bacteria can be accounted for by the formation of complexes with each of the bacterial surface sites. The average log stability constants for Cd complexes with Sites 1-4 are 2.4 ± 0.4, 3.2 ± 0.1, 4.4 ± 0.1, and 5.3 ± 0.1, respectively. The average log stability constants for Pb complexes with Sites 1-4 are 3.3 ± 0.2, 4.5 ± 0.3, 6.5 ± 0.1, and 7.9 ± 0.5, respectively. This study demonstrates that a wide range of bacteria exhibit similar proton and metal adsorption behaviors, and that a single set of averaged acidity constants, site concentrations, and stability constants for metal-bacterial surface complexes yields a reasonable model for the adsorption behavior of many of these species. The differences in adsorption behavior that we observed for A. angustum demonstrate that genetic differences do exist between the cell wall functional group chemistries of some bacterial species, and that significant exceptions to the typical bacterial adsorption behavior do exist.