Adsorption phenomena in hydrometallurgy, 2. Electrophoretic behavior of oxides in aqueous ammoniacal solutions of copper,nickel and cobalt

The electrophoretic mobilities of finely divided oxides in aqueous ammoniacal solutions of copper, nickel, and cobalt have been measured. The solids used were rutile, alumina, quartz, and hematite. The effects of pH, ammonia-ammonium concentration, and metal-ion concentration on the electrophoretic behavior were investigated. The experimental results indicate that oxide colloids may undergo as may as five charge reversals in aqueous ammoniacal solutions of hydrolyzable ammine-forming metal ions.     

Silver losses from ammoniacal solutions on complex sulphide and chalcopyrite ammonia leach residues

Extraction and subsequent loss of silver from leach liquor during oxidative ammonia leaching of complex sulphide and chalcopyrite concentrates have been observed. The lost silver value from the leach liquor was unrecoverable when the residues were treated with ammonia-ammonium sulphate buffer (pH=9.5) solutions at 27°C. However, when the same slurry was heated to 75°C in an autoclave under an atmosphere of oxygen, almost all the silver value could be redissolved. The leach residues lost their silver absorbance property from ammoniacal solutions on repeatedly heating and cooling the leached slurries in the presence of oxygen. In this work, silver losses from ammoniacal solutions on various leach residues, synthetic iron oxides, and freshly precipitated Fe(II) and Fe(III) hydroxides are reported. None of the major constituents present in the leach residues were responsible for the silver losses but small amounts of Fe(II) associated with the residues could take up silver from the leach solutions.     

Ternary interactions in a humic acid–Cd–bacteria system

Humic acid adsorption onto the bacterial surface of Bacillus subtilis was measured with and without Cd, as a function of pH and humic–bacteria–Cd ratios. These experiments tested for the existence of ternary interactions in a bacteria–humic–metal system. We determine both the effects of humic acid on the bacterial adsorption of Cd, as well as the effects of the aqueous metal cation on the bacterial adsorption of humic acid. The presence of Cd does not affect the extent of humic acid adsorption onto the bacterial surface, indicating that there is no competition for sorption sites between humic acid and Cd under the experimental conditions, and that changes in the charging properties of the bacterial surface, as a result of the Cd adsorption, are not significant enough to affect humic acid adsorption.

The presence of humic acid does diminish Cd adsorption onto the bacterial surface, suggesting the presence of an aqueous Cd–humate complex under mid to high pH conditions. However, we also observe that the solubility of humic acid is unaffected by the presence of aqueous Cd. This apparently inconsistent behavior of an aqueous Cd–humate complex affecting Cd adsorption but not affecting humic acid solubility is not observed with simpler ionizable organic molecules. We propose that the solubility of humic acid is controlled by the solubility of a less soluble fraction of the acid. Cd forms an aqueous complex with the more soluble fraction of humic acid and there is no interdependence between the aqueous activities of the more and less soluble fractions. That is, the solubility of one humic acid fraction is unaffected by the presence of an aqueous Cd–humate complex involving another humic acid fraction. These experimental results constrain the relative importance of surface ternary and aqueous metal–humate complexes on the bacterial adsorption of both humic acid and metal cations.     

The effect of aqueous metal-chlorophenolate complexation on contaminant transport in groundwater systems

Aqueous metals and chlorophenols are common co-contaminants of groundwater systems. However, the importance of aqueous metal-chlorophenolate complexation cannot be accurately assessed because the stability constants for environmentally important aqueous metal-phenolate and metal-chlorophenolate complexes have not been measured. In order to determine the role these complexes play in contaminant transport, this study applies a correlation technique to the limited data that do exist to estimate the stabilities of metal-chlorophenolate complexes of environmental interest. Speciation calculations that are based on these estimated stability constants indicate that aqueous metal-chlorophenolate complexation may significantly affect both aqueous metal and dissolved chlorophenolate species distributions. Therefore, aqueous metal-chlorophenolate complexation may affect the extent of adsorption of both metals and chlorophenolates onto mineral surfaces. In addition, aqueous complexation may significantly enhance dissolution of aquifer aluminosilicate minerals. This study suggests that aqueous complexation between metals and chlorophenolates can significantly affect the mobility of metal and phenolic contaminants.     

Heavy metal adsorption by sulphide mineral surfaces

The adsorption of aqueous Hg²⁺, Pb²⁺, Zn²⁺ and Cd²⁺ complexes on a variety of sulphide minerals has been studied as a function of the solution pH and also as a function of the nature of the ligands in solution. Sulphide minerals are excellent scavengers for these heavy metals. The adsorption is strongly pH dependent, i.e. there is a critical pH at which the adsorption increases dramatically. The pH dependence is related to the hydrolysis of the metal ions. Indirect evidence suggests that the hydrolyzed species are adsorbed directly on the sulphide groups, probably as a monolayer. The results also suggest the presence of MCI_n²⁻ⁿ species physisorbed on the adsorbed monolayer. A positive identification of the adsorbed species was not possible using ESCA/XPS.     

Distribution of sulphur, and sulphide-iron and copper in bedrock associated with porphyry copper deposits, highland valley, British Columbia

A selective leach based on extraction with potassium chlorate-hydrochloric acid was used to investigate distribution of sulphide-iron and copper associated with the JA and Valley Copper deposits. Results emphasize patterns related to sulphide, versus total metal, and are shown to be consistent with mineralogical zoning in the deposits.     

Removal of heavy metal ions from aqueous solutions with multi-walled carbon nanotubes: Kinetic and thermodynamic studies

Multi-walled carbon nanotubes were used successfully for the removal of Copper(II), Lead(II), Cadmium(II), and Zinc(II) from aqueous solution. The results showed that the % adsorption increased by raising the solution temperature due to the endothermic nature of the adsorption process. The kinetics of Cadmium(II), Lead(II), Copper(II), and Zinc(II) adsorption on Multi-walled carbon nanotubes were analyzed using the fraction power function model, Lagergren pseudo-first-order, pseudo-second-order, and Elovich models, and the results showed that the adsorption of heavy metal ions was a pseudo-second-order process, and the adsorption capacity increased with increasing solution temperature. The binding of the metal ions by the carbon nanotubes was evaluated from the adsorption capacities and was found to follow the following order: Copper(II) > Lead(II) > Zinc(II) > Cadmium(II). The thermodynamics parameters were calculated, and the results showed that the values of the free energies were negative for all metals ions, which indicated the spontaneity of the adsorption process, and this spontaneity increased by raising the solution temperature. The change in entropy values were positives, indicating the increase in randomness due to the physical adsorption of heavy metal ions from the aqueous solution to the carbon nanotubes’ surface. Although the enthalpy values were positive for all metal ions, the free energies were negative, and the adsorption was spontaneous, which indicates that the heavy metal adsorption of Multi-walled carbon nanotubes was an entropy-driving process.     

A novel adsorbent for heavy metal remediation in aqueous environments

The objective of this study was to investigate the possibility of using maize tassel as an alternative adsorbent for the removal of chromium (VI) and cadmium (II) ions from aqueous solutions. The effect of pH, solution temperature, contact time, initial metal ion concentration and adsorbent dose on the adsorption of chromium (VI) and cadmium (II) by tassel was investigated using batch methods. Adsorption for both chromium (VI) and cadmium (II) was found to be highly pH dependent compared to the other parameters investigated. Obtained results gave an adsorption capacity of 79.1 % for chromium (VI) at pH 2, exposure time of 1h at 25 °C. Maximum capacity of cadmium of 88 % was obtained in the pH range of 5-6 at 25 °C after exposure time of 1 h. The adsorption capacities of tassel for both chromium (VI) and cadmium (II) were found to be comparable to those of other commercial adsorbents currently in use for the removal of heavy metals from aqueous wastes. These results have demonstrated the immense potential of maize tassel as an alternative adsorbent for toxic metal ions remediation in polluted water and wastewater.     

有机质在大厂锑矿成矿中的作用

有机质在大厂锑矿成矿中的作用王华云，施继锡（贵州省地矿局地质科学研究所．贵阳５５０００４）（中国科学院地球化学研究所．贵阳５５０００２）关键词有机质，锑矿，成矿作用大厂锑矿是黔西南金、锑、汞矿带中的一个重要成矿单元。该矿带明显受盆地和盆缘构造演化的控...     

Evaluation of Experimental Procedures and Discussion of Two Different Modelling Approaches with Respect to Long-term Kinetics of Metal Cation Sorption onto (Hydr)oxide Surfaces

Experimental procedures as well as literature data and modelling of long-term kinetics of metal ion adsorption processes onto thermodynamically stable (hydr)oxide surfaces from aqueous solution are evaluated. It is concluded that when experimental uptake data are obtained by the solution depletion method precise information on experimental procedures is crucial. This is true both for preliminary kinetics studies (which intend to fix an equilibration time used for subsequent thermodynamic studies) and for true kinetic studies. For the usually given adsorption versus time curves the corresponding (possibly changing) values of pH should be added. The use of sorption pH edges measured at different times to obtain kinetics curves at constant pH may not correspond to the actual behaviour of the system but be rather an artificial construct.Concerning the models two basically different mechanisms have been used to account for the slow sorption step, which occurs in long-term studies: intraparticle diffusion of the adsorbing metal cation and slow redistribution of surface species. It is shown that the two mechanisms cannot be distinguished using macroscopic uptake data alone: data, which have been interpreted using one approach, may equally well be interpreted using the other one.     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

Cadmium and lead interaction with diatom surfaces: A combined thermodynamic and kinetic approach

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii, TW; Skeletonema costatum, SC) and two freshwater periphytic species (Achnanthidium minutissimum, AMIN; Navicula minima, NMIN) by combining adsorption measurements with surface complexation modeling. Adsorption kinetics was studied as a function of pH and initial metal concentration in sodium nitrate solution and in culture media. Kinetic data were consistent with a two-step mechanism in which the loss of a water molecule from the inner coordination sphere of the metal is rate limiting. Reversible adsorption experiments, with 3 h of exposure to metal, were performed as a function of pH (2-9), metal concentration in solution (10⁻⁹-10⁻³ M), and ionic strength (10⁻³-1.0 M). While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. Measurements of electrophoretic mobilities (μ) revealed negative surface potential for AMIN diatom, however, the absolute value of μ decreases with increase of [Pb²⁺]_aq suggesting the metal adsorption on negative surface sites. These observations allowed us to construct a surface complexation model (SCM) for cadmium and lead binding by diatom surfaces that postulates the Constant Capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. In the full range of investigated Cd concentration, the SCM is able to describe the concentration of adsorbed metal as a function of [Cd²⁺]_aq without implying the presence of high affinity, low abundance sites, that are typically used to model the metal interactions with natural multi-component organic substances. At the same time, Cd fast initial reaction requires the presence of “highly reactive sites” those concentration represents only 2.5-3% of the total amount of carboxylic sites. For reversible adsorption experiments, the dominating carboxylic groups, whose concentration is allowed to vary within the uncertainty of experimental acid-base titrations, are sufficient to reproduce the metal adsorption isotherms. Results of this study strongly suggest that laboratory experiments performed in a wide range of metal to biomass ratios, represent robust and relatively simple method for assessing the distribution of metals between aqueous solution and planktonic and periphytic biomass in natural settings.     

Adsorption of lead using a new green material obtained from Portulaca plant

In the present study the potential of a new green material obtained from Portulaca oleracea plant was investigated. The material was used without any chemical treatment to study the adsorption behavior of lead ions from aqueous solution. Various batch experiments were carried out using different experimental conditions such as pH, contact time, adsorbent concentration, and metal ion concentration to identify the optimum conditions. The influence of these parameters on the adsorption capacity was studied. Results showed the optimum initial pH for adsorption as 6. Adsorption equilibrium was reached in 120?min. The adsorption data were modeled using both the Langmuir and Freundlich classical adsorption isotherms. Results show ~78% removal of lead from aqueous solution. The kinetic data corresponded well with pseudo second-order equation. From the initial results, the green material obtained from the waste of Portulaca seems to be a potential low-cost adsorbent for removal of lead ions from water.     

Competitive heavy metals adsorption on natural bed sediments of Jajrood River,Iran

The presence of heavy metal concentrations was examined in natural sediments from four sites along the Jajrood river in northeast of Tehran, the capital of Iran. Besides determination of elemental concentrations (Pb, Cu, Zn, Cd, Ni and Cr), X-ray fluorescence and X-ray diffraction tests were carried out to determine other chemical components in these adsorbents. Also the ability of sediments to adsorb these heavy metal ions from aqueous solutions was investigated. Results show that the extent of adsorption increases with increase in adsorbent concentration. The amount of adsorbed Pb, Cu and Zn in sediments was much greater than that of the other metals, and Cr was adsorbed much less than others. The adsorbabilities of sediments to heavy metals increased in the order of Pb > Cu > Zn > Cd > Ni > Cr. Based on the adsorption data, equilibrium isotherms were determined at selected areas to characterize the adsorption process. The adsorption data followed Freundlich and Langmuir isotherms in most cases. Correlation and cluster analysis was performed on heavy metals adsorption and sediment components at each site to evaluate main adsorbing compounds in sediments for each metal. Results demonstrated that heavy metals sorption is mostly related to load of organic matter in the Jajrood river sediments.     

Adsorptive removal of Cu(II) and Pb(II) onto mixed-waste activated carbon: kinetic,thermodynamic, and competitive studies and application to real wastewater samples

This work aimed to investigate the adsorption characteristics, both kinetically and thermodynamically, of Cu(II) and Pb(II) removal from aqueous solutions onto mixed-waste activated carbon, as well as to study the competitive behavior found in mixed heavy metal solution systems. This study shows that activated carbon prepared from mixed waste is an effective adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions, with the aim of detoxifying industrial effluents before their safe disposal onto water surfaces. The adsorption process was characterized in terms of kinetic and thermodynamic studies. In addition, the influence of presence of Cu(II) and Pb(II) in a competitive system was investigated. The results showed that the maximum adsorption capacities were gained at a pH of 6 with a contact time of 180 min, a metal solution concentration of 300 ppm, and an adsorbent dose of 0.3 g/L. The adsorption process was found to follow a pseudo-first-order kinetic model. Thermodynamic parameters such as ΔG ^o, ΔH ^o, and ΔS ^o showed that the sorption process was spontaneous and endothermic in nature. A competitive study demonstrated the applicability of mixed-waste activated carbon to adsorb Cu(II) and Pb(II) from a solution of mixed metals. In addition, the adsorption capacity was found to be as effective as other adsorbents reported in the literature. The developed adsorptive removal procedure was applied for treatment of real wastewater samples and showed high removal efficiency.     

Cd adsorption onto Pseudomonas putida in the presence and absence of extracellular polymeric substances

The role of bacterial extracellular polymeric substances (EPS) in metal adsorption was determined by studying Cd adsorption onto the gram-negative bacterial species Pseudomonas putida with and without enzymatic removal of EPS from the biomass material. A range of experimental approaches were used to characterize the Cd adsorption reactions, including bulk proton and Cd adsorption measurements, FTIR spectroscopy, and fluorescence microscopy. The proton-reactivities of the biomass samples with EPS are not significantly different from those obtained for EPS-free biomass. Similarly, the presence of EPS does not significantly affect the extent of Cd removal from solution by the biomass on a mass-normalized basis, based on bulk Cd adsorption measurements conducted as a function of pH, nor does it appear to strongly affect the Cd-binding groups as observed by FTIR. However, fluorescence microscopy indicates that Cd, although concentrated on cell walls, is also bound to some extent to EPS. Together, the results from this study suggest that the P. putida EPS can bind significant concentrations of Cd from solution, and that the nature and mass-normalized extent of the binding is similar to that of the cell wall. Therefore, the EPS-bearing systems do not exhibit enhanced mass-normalized removal of Cd from solution relative to the EPS-free systems. The presence of the EPS effectively increases the viability of cells exposed to aqueous Cd, likely due to sequestration of the Cd away from the cells due to Cd-EPS binding.     

Heavy Metal Removal from Water by Adsorption Using Pillared Montmorillonite

Removal of Cu^2＋, Cr^3＋ and Cd^2＋ from aqueous solutions by adsorption on montmorillonite modified by sodium dodecylsulfate （SDS） and hydroxy-alumino-silicate （HAS） was investigated. Experiments were carried out as a function of solution pH, solute concentration, and time. The Langmuir model was adopted to describe the single-solute adsorption isotherm, in which the Langmuir parameters were directly taken from those obtained in single-solute systems. The kinetics of metal ions adsorption was examined and the pseudo-first-order rate constant was finally evaluated.     

Effect of hematite on thiosulphate leaching of gold

Hematite, as a typical iron oxide slime in sulphide ore slurries, was artificially added into the leaching systems of pure gold and a sulphide ore respectively, in an attempt to investigate the effect of iron oxide slimes on the ammoniacal thiosulphate leaching of gold. The presence of hematite significantly reduced the dissolution of gold and this detrimental effect became more pronounced with increasing hematite concentration. Hematite formed coatings on gold surfaces, which could prevent leach solution from diffusing to the gold surfaces and hence, inhibit gold dissolution. Hematite catalysed the oxidative decomposition of thiosulphate to polythionates with oxygen present. XPS studies indicated a thin layer of iron oxide coating as well as the deposition of some copper and sulphur species on gold surfaces. SEM images revealed a lesser extent of corrosion for gold after leaching in the presence of hematite. The gold extraction from the sulphide ore was reduced with the addition of hematite and this effect became more noticeable with an addition of hematite at a higher concentration. A natural guar type surfactant (Gempolym M47) reduced the detrimental effect of hematite on gold extraction likely due to the prevention of hematite coating on gold and mineral particles and the dispersion of the mineral slurry. Gempolym M47 stabilised thiosulphate by weakening the interaction between cupric ions and thiosulphate and by minimising the catalytic effect of hematite on thiosulphate decomposition.     

Single and binary adsorption of lead and cadmium ions from aqueous solution using the clay mineral beidellite

Beidellite, a low-cost, locally available and natural mineral was used as an adsorbent for the removal of lead and cadmium ions from aqueous solutions in batch experiments. The kinetics of adsorption process was tested for the pseudo first-order, pseudo second-order reaction and intra-particle diffusion models. The rate constants of adsorption for all these kinetic models were calculated. Comparison amongst the models showed that the sorption kinetics was best described by the pseudo second-order model. Langmuir and Freundlich isotherm models were applied to the experimental equilibrium data for different temperatures. The adsorption capacities (Q°) of beidellite for lead and cadmium ions were calculated from the Langmuir isotherm. It was found that adsorption capacity was in the range of 83.3–86.9 for lead and 42–45.6 mg/g for cadmium at different temperatures. Thermodynamic studies showed that the metal uptake reaction by beidellite was endothermic in nature. Binary metal adsorption studies were also conducted to investigate the interactions and competitive effects in binary adsorption process. Based on the optimum parameters found, beidellite can be used as adsorbent for metal removal processes.     

Saraca indica leaf powder for decontamination of Pb: removal, recovery, adsorbent characterization and equilibrium modeling

The present study explores the effectiveness of Saraca indica leaf powder, a surplus low value agricultural waste, in removing Pb ions from aqueous solution. The influence of pH, biomass dosage, contact time, particle size and metal concentration on the removal process were investigated. Batch studies indicated that maximum biosorption capacity for Pb was 95.37% at the pH 6.5. The sorption process followed the first order rate kinetics. The adsorption equilibrium data fitted best to both Langmuir and Freundlich isotherms. Morphological changes observed in scanning electron micrographs of untreated and metal treated biomass confirmed the phenomenon of biosorption. Fourier transform infrared spectroscopy of native and exhausted leaf powder confirmed lead biomass interactions responsible for sorption. Acid regeneration was tried for several cycles with a view to recover the sorbed metal ion and also to restore the sorbent to its original state. The findings showed that Saraca indica leaf powder can easily be envisaged as a new, vibrant, low cost biosorbent for metal clean up operations.