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.     

低聚合羟基铁-蒙脱石复合体吸附铬酸根的实验研究

摘要：在模拟的酸性土壤条件下，利用制备的低聚合羟基铁蒙脱石复合体对铬酸根进行吸附实验。重点研究了吸附条件对复合体铬吸附能力的影响，对比了蒙脱石和含水氧化铁。结果表明，实验条件下复合体有较强的铬吸附能力，其铬吸附量低于铁沉积物而明显高于蒙脱石。铬初始质量浓度是影响复合体铬吸附量的最主要因素，离子强度次之。吸附时间(12h以上)、温度、pH值对复合体铬吸附量的影响很小；说明在酸性土壤条件下，复合体有强且稳定的铬吸附能力。     

Equilibrium studies on removal of lead (II) ions from aqueous solution by adsorption using modified red mud

In the present experimental study, solid waste was used as an adsorbent and the effectiveness of the adsorbent was increased by novel treatment methods. Red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were used for the removal of lead (II). The structural and functional groups were identified to confirm the removal of lead (II) by powder X-ray diffraction and Fourier transform infrared spectroscopy analyses. The enhancement of surface area was confirmed by Brunauer–Emmett–Teller analysis. Batch adsorption experiment was also conducted, and various parameters such as the effect of adsorbent dosage, pH, contact time and initial ion concentration were analyzed and reported. Adsorption equilibrium data were investigated using Langmuir, Freundlich and Dubinin–Radushkevich isotherm models with three parameters, and the rate of reaction was examined through kinetic models. The results indicate that in particular a novel modified form of red mud, namely iron oxide-coated acid-treated activated red mud was well fitted in lead (II) removal compared with reported adsorbents. The Langmuir isotherm shows that the maximum adsorption of adsorbate per gram was greater than other adsorbents (27.02 mg/g). In Freundlich isotherm, the Freundlich constant n values lie between 1 and 10 indicate the favorable adsorption. The calculated n values for normal red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were found to be 1.9, 2.1 and 2.0 respectively. The correlation coefficient value was higher and the rate of reaction follows the pseudo-second-order kinetic model.     

Influence of operating conditions on the removal of Cu, Zn, Cd and Pb ions from wastewater by adsorption

Nile Rose Plant was used to study adsorption of several cations (Cu²+, Zn²+, Cd²+ and Pb²+) from wastewater within various experimental conditions. The dried leaves of Nile Rose Plant were used at different adsorbent/ metal ion ratios. The influence of pH, contact time, metal concentration, and adsorbent loading weight on the removal process was investigated. Batch adsorption studies were carried out at room temperature. The adsorption efficiencies were found to be pH dependent, increasing by increasing the pH in the range from 2.5 to 8.5 exept for Pb. The equilibrium time was attained within 60 to 90 min. and the maximum removal percentage was achieved at an adsorbent loading weight of 1.5 g/50 mL mixed ions solution. Isothermal studies showed that the data were best fitted to the Temkin isotherm model. The removal order was found to be Pb²⁺> Zn²⁺> Cu²⁺> Cd²⁺. The surface IR-characterization of Nile rose plant showed the presence of many functional groups capable of binding to the metal cations.     

Radioactive removal by adsorption on Yesan clay and zeolite

The adsorption of Cs, Sr, Ni, and Co radioactive substitutes onto Yesan clay and zeolite was studied through batch and column tests using Cs, Sr, Ni, and Co as substitutes for radioactive isotopes. Adsorption values of 0.189–1.865 μg/g onto Yesan clay and 0.595–9.055 μg/g onto zeolite were observed, with the radioactive substitutes being almost 100 % adsorbed from the onset of column testing. Adsorption was achieved through ionic bonding. These materials demonstrated suitability for use as backfill or foundation materials for nuclear power plants, radioactive waste disposal facilities, and other radioactive facilities.     

Fluoride contamination of groundwater in parts of eastern India and a preliminary experimental study of fluoride adsorption by natural haematite iron ore and synthetic magnetite

Incidence of high fluoride (F^?) in groundwater (>1.5 mg/L) in two tribal belts of eastern India, one around Chukru in the Palamau district of Jharkhand and the other around Karlakot in the Nuapada district of Odisha, has been studied. The maximum concentration of F^? in groundwater from dug wells and tube wells is 10.30 mg/L in Chukru and 4.62 mg/L in Karlakot. The groundwaters are mildly alkaline with pH ranges of 7.52–8.22 and 7.33–8.20 in Chukru and Karlakot, respectively. The F^? concentration is positively correlated with pH, electrical conductivity and SO₄ ^2? in both areas. The high F^? in groundwater resulted mainly from dissolution of biotite and fluorapatite in quartzofeldspathic gneiss. The ionic dominance pattern (in meq/L) is mostly in the order Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ among cations and HCO₃ ^? > SO₄ ^2? > < Cl^? > F^? among anions in the Karlakot groundwater. Preliminary adsorption experiments were conducted on natural haematite iron ore and synthetic magnetite to evaluate their potential for F^? removal from water. Effects of different parameters such as contact time, pH, adsorbent dose and initial F^? concentration on the adsorption capacity of these materials were investigated. Strong dependence of F^? removal on pH was observed for both the adsorbents. With natural haematite iron ore, the maximum F^? removal of 66 % occurred at an initial pH of 3.2 for a solution with F^? concentration of 3 mg/L, adsorbent dose of 7 g/L and overnight contact time. The haematite iron ore was observed to increase the pH of the F^? solution. Adsorption equilibrium was not achieved with this adsorbent even after a contact time of 45.2 h. In the case of synthetic magnetite, 84 % F^? removal was achieved after 2 min of contact time for a solution with F^? concentration of 6 mg/L, adsorbent dose of 10 g/L and initial pH of 7. The results indicate high potential of both natural haematite iron ore and synthetic magnetite as adsorbents of F^? in water.     

Selenite retention by nanocrystalline magnetite: Role of adsorption, reduction and dissolution/co-precipitation processes

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 (Fe^IIIOOH) 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.     

Density functional theory modeling of chromate adsorption onto ferrihydrite nanoparticles

Density functional theory (DFT) calculations were performed on a model of a ferrihydrite nanoparticle interacting with chromate (\( {\text{CrO}}_{4}^{2 - } \)) in water. Two configurations each of monodentate and bidentate adsorbed chromate as well as an outer-sphere and a dissolved bichromate (\( {\text{HCrO}}_{4}^{ - } \)) were simulated. In addition to the 3-D periodic planewave DFT models, molecular clusters were extracted from the energy-minimized structures. Calculated interatomic distances from the periodic and cluster models compare favorably with Extended X-ray Absorption Fine Structure spectroscopy values, with larger discrepancies seen for the clusters due to over-relaxation of the model substrate. Relative potential energies were derived from the periodic models and Gibbs free energies from the cluster models. A key result is that the bidentate binuclear configuration is the lowest in potential energy in the periodic models followed by the outer-sphere complex. This result is consistent with observations of the predominance of bidentate chromate adsorption on ferrihydrite under conditions of high surface coverage (Johnston Environ Sci Technol 46:5851–5858, 2012). Cluster models were also used to perform frequency analyses for comparison with observed ATR FTIR spectra. Calculated frequencies on monodentate, bidentate binuclear, and outer-sphere complexes each have infrared (IR)-active modes consistent with experiment. Inconsistencies between the thermodynamic predictions and the IR-frequency analysis suggest that the 3-D periodic models are not capturing key components of the system that influence the adsorption equilibria under varying conditions of pH, ionic strength and electrolyte composition. Model equilibration via molecular dynamics (MD) simulations is necessary to escape metastable states created during DFT energy minimizations based on the initial classical force field MD-derived starting configurations.     

Effect of groundwater fulvic acid on the adsorption of arsenate by ferrihydrite and gibbsite

Adsorption studies have been conducted at pH 4, 6 and 8 to assess the effect of fulvic acid on arsenate adsorption to ferrihydrite and gibbsite. The studies compared the adsorption of arsenate on the mineral surfaces in the absence of fulvic acid, to those cases where increasing concentrations of fulvic acid (0.3–60 μM) were added to the mineral–arsenate suspensions. Experiments where arsenate was added to mineral–fulvate suspensions were also conducted. The results suggest that arsenate adsorption on both gibbsite and ferrihydrite decreases with increasing concentrations of fulvic acid. This effect was highest at pH 4, and decreased at pH 6 and 8. Ferrous ion concentrations were very low during the ferrihydrite experiments and support the view that fulvic acid can both displace arsenate from and inhibited its adsorption to mineral surfaces. The experiments also indicated that the amount of arsenate adsorbed was lower if fulvic acid was added before rather than after arsenate. This may reflect the relative size of arsenate and fulvic acid molecules and their ability to penetrate the crystal matrices of the minerals.     

Lead removal from aqueous solution by basaltic scoria: adsorption equilibrium and kinetics

Pb-contaminated water is a dangerous threat occurring near metallurgic and mining industries. This circumstance produces serious environment concern, due to Pb(II) high toxic effects. Several reactive materials have been reported for Pb(II) adsorption, but not all reached final Pb(II) suitable concentrations, or they are expensive and rejected in massive remediation technologies; hence, natural materials are good options. The adsorption behavior of a volcanic scoria (two sieved fractions 1425 and <425 µm) was studied toward synthetic Pb(II) water solutions in batch experiments (170.4–912.3 mg L^?1) with high removal efficiencies (97%). The Langmuir model fits both fractions with high linear correlation coefficients (0.9988 and 0.9949) with high maximum capacity values (588.23 and 555.55 mg g^?1). Separation factor R _L parameter varies with initial concentration, and the empirical equation predicts the limits of the material usefulness, a criterion proposed in this paper for conditions’ selection. The Lagergren pseudo-second-order analysis demonstrates chemisorption; calculated rate constant (416.66 mg g^?1 min^?1). Weber–Morris intraparticle model proves that the adsorption phenomena occur fast on the material surface (k _inst = 72 g mg^?1 min^?0.5). The characterization of the volcanic material afforded the elemental composition (X-ray fluorescence), and the empirical formula was proposed. X-ray diffraction patterns verify the material structure as basalt, with a plagioclase structure that matches anorthite and albite, mostly composed of quartz. The presence of oxides on the material surface explain the high Pb(II) adsorption capacity, observed on the surface by scanning electronic microscopy. The studied volcanic scoria has potential use as a Pb(II) adsorbent in water remediation technologies.     

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.     

Enhanced removal of dissolved metal ions in radioactive effluents by flocculation

Decontamination of radioactive effluents of low or intermediate level of radioactivity generated from different nuclear industries is done through the chemical precipitation route. The precipitates thus formed are of very fine sizes thereby requiring flocculation for faster settlement. The presence of polyacrylamide-based polymer not only enhances settling velocity but also increases removal of dissolved non-radioactive as well as radioactive metal ions from the liquid. About 99.5% of Cu²⁺ and Fe³⁺ ions are removed due to the presence of cationic Rishabh 611. Flocculation by either cationic or anionic flocculant has shown improvement in removal of radioactive strontium while turbidity of the liquid is reduced to a very low value (0.8 NTU). Decontamination factors (DF) of the effluents from different plants are improved by 3–5 times.     

Isopropylxanthate ions uptake by modified natural zeolite and removal by dissolved air flotation

This work describes a laboratory study concerning the adsorption of isopropylxanthate ions onto modified zeolites particles. The separation of the loaded carrier and their removal, from aqueous solutions, was conducted by flocculation followed by dissolved air flotation, DAF. The zeolite employed was a natural sample (approximately 48% clinoptilolite and 30% mordenite) which was previously treated with sodium ions (activation) and modified with copper ions (Cu–Z) before the xanthate ions uptake. Adsorption capacities (q_m) for Cu–Z were 0.34 meq g^− 1 for the powdered form, and 1.12 meq g^− 1 for the floc form. The adsorption capacity for the floc form appears to involve an enhanced electrostatic adsorption due to the positive sites on the floc surface. In all cases, the isopropylxanthate concentration in the treated water was found to be negligible (< 0.04 mg L^{− 1}). The flotation technique showed to be a fast process, requires a low recycle ratio (20%) in air saturated water, and the treated water ended up with a very low residual turbidity (6.8 NTU). It is believed that this adsorption–flotation technique, here named adsorptive particulate flotation, using activated and modified natural zeolite has a high potential as an alternative for pollutants removal (copper and isopropylxanthate ions) from waste mining effluents.     

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.     

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).     

火山渣吸附地下水中大肠杆菌噬菌体特性研究

为了分析火山渣吸附去除地下水中大肠杆菌噬菌体作用特性,通过室内实验,考察火山渣吸附地下水中vB_EcoM-ep3大肠杆菌噬菌体效果,同时用等量沸石与石英砂做对照,进一步分析地下水中水化学因素(Fe²⁺、Fe³⁺、Mn²⁺、 {\mathrm{SO}}_4^{2-}、 {\mathrm{NH}}_4^{+}、 {\mathrm{NO}}_3^{-}、 {\mathrm{NO}}_2^{-}、Ca²⁺、Mg²⁺、 {\mathrm{CO}}_3^{2-}、 {\mathrm{HCO}}_3^{-}和pH值)对其吸附效果影响;通过微观检测技术,分析大肠杆菌噬菌体生物学特性和火山渣吸附前后微观结构变化。研究结果表明:火山渣吸附效率优于沸石和石英砂,最大饱和吸附量达到2.245×10⁵ pfu/g;水化学因素对火山渣吸附效果影响存在差异性,其中Fe²⁺、Fe³⁺起到促进作用, {\mathrm{SO}}_4^{2-}、三氮和碱度起到抑制作用,低浓度Mn²⁺( C_{\mathrm{M}{\mathrm{n}}^{2+}}<10 mg/L)和Ca²⁺( C_{\mathrm{C}{\mathrm{a}}^{2+}}<100 mg/L)起到轻微促进作用,超过该浓度则表现为抑制作用;pH值对火山渣吸附效果影响较大,pH值越大,吸附效果越差。vB_EcoM-ep3大肠杆菌噬菌体头部为等边六角形,全身直径约为(53±2) nm,尾部长约为(107±3) nm,由尾管和尾丝组成,可伸缩。具有蜂窝状结构的火山渣吸附大肠杆菌噬菌体后表面孔隙大部分被填充。     

The influence of the major ions of seawater on the adsorption of simple organic acids by goethite

The adsorption of oxalic, phthalic, salicylic, and lactic acids on goethite from 0.53 M NaCl and from synthetic major ion seawater is examined to determine the effect of Mg, Ca, and SO₄ on the adsorption behavior of the organic compounds. The comparison shows that organic acid adsorption is suppressed in seawater relative to the NaCl system. Successive additions of SO₄, Mg, and Ca in their natural ionic proportions found in seawater to 0.53 M NaCl indicate that sulfate suppresses the adsorption of all the organic acids, especially in the low pH range. The addition of Mg also suppresses the adsorption of oxalic and phthalic acids while the addition of Ca suppresses lactic acid adsorption. The effect of SO₄, Mg, and Ca on the adsorption of the organic acids is due to competition for available binding sites and the formation of solution complexes which either do not adsorb or weakly adsorb.