Comparative of the removal of Pb2+, Cd2+ and Ni2+ by nano crystallite hydroxyapatite from aqueous solutions: Adsorption isotherm study

Release of heavy metal onto the water and soil as a result of agricultural and industrial activities may pose a serious threat to the environment. In this study, the adsorption behavior of nano hydroxyapatite with respect to Pb²⁺, Cd²⁺ and Ni²⁺ has been studied in order to consider its application to purity metal finishing wastewater. The batch method has been employed, using metal concentrations in solution ranging from 100 to 400 mg/L. The uptake capacity and distribution coefficients (K_d) were determined for the adsorption system as a function of sorbate concentration. The Langmuir, Freundlich, and Dubinin–Kaganer–Radushkevich (DKR) isotherms applied for sorption studies showed that the amount of metal sorbed on nano hydroxyapatite. It was found that the adsorption phenomena depend on charge density and hydrated ion diameter. According to the equilibrium studies, the selectivity sequence can be given as Pb²⁺ > Cd²⁺ > Ni²⁺. These results show that nano hydroxyapatite holds great potential to remove cationic heavy metal species from industrial wastewater.     

Removal of heavy metal ions from water by using poly(ethyleneglycol dimethacrylate-co-acrylamide) beads

Poly(ethyleneglycol dimethacrylate-co-acrylamide) (poly(EDGMA-co-AAm)) copolymer beads have been prepared for use in the separation Pb(II), Hg(II), and Cd(II), metal ions in aqueous solution by a batch equilibration technique. Adsorption capacity were increased with pH for Pb(II), Cd(II) and Hg(II) and then reached almost plateau value around 6.0. The high initial rate of metal ions uptake (<10 min) suggests that the adsorption occurs mainly at the bead surface. The metal uptake results show that poly(EGDMA-co-AAm) can be used for the adsorption of the following metals in the indicated order: Pb(II) > Cd(II) > Hg(II) expressed on a molar basis. However, when the uptake was expressed in terms of the amount of metal removed from solution was as follows: Pb(II) > Hg(II) > Cd(II). The beads still showed preference toward Pb(II) when this metal was in a mixture with Hg(II) and Cd(II). A linearized form of the Freundlich and the Langmuir isotherm model fits the experimental equilibrium concentration data of Hg(II) and Cd(II) better than isotherm type model of Pb(II). The recovery of the metal ions after adsorption and the regeneration of the adsorbent can be carried out by treatment of the loaded beads with either 0.5 M NaCl, or 1 M HNO₃.     

Arsenic sorption by modified clinoptilolite–heulandite rich tuffs

Recent works show that modified natural zeolites improve the remotion of anionic or non-polar organic pollutants from water. In this work the arsenic sorption from aqueous solutions onto clinoptilolite–heulandite rich tuffs modified with lanthanum, hexadecyltrimethylammonium or iron was investigated considering the arsenic chemical species and the pH of the arsenic solutions. Clinoptilolite–heulandite rich tuffs were characterized by scanning electron microscopy and X-ray diffraction analysis. The elemental composition of the zeolitic samples was also determined. According to the Langmuir isotherm model the arsenic (V) sorption capacity of the zeolites was 75.4 μg As/g at pH 3, 3.9 μg As/g at pH 5 and 53.6 μg As/g at pH 6, for the lanthanum, HDTMA and iron modified clinoptilolite–heulandite rich tuff from Chihuahua (México), respectively. In general, the results suggested that the arsenic retention depends on the precedence of zeolitic material, the nature of arsenic chemical species, pH as well as the characteristics of modified natural zeolites. In this work the arsenic adsorption mechanisms are also discussed.     

Determination of some heavy metal cations in molten snow by transient isotachophoresis/ capillary zone electrophoresis

Online combination of transient ITP and CZE is employed for the determination of Cd(II), Pb(II), Cu(II), Ni(II), and Zn(II). Acetic acid is used for creating the transient isotachophoretic state. alpha-Hydroxyisobutyric acid and 4-aminopyridine are used as BGEs for the separation and indirect UV detection. At optimum conditions, the method allows to determine the metals at levels of 40-120 microg/L, about 50 times more sensitive than conventional CZE. In combination with a 20-fold evaporative concentration, the method is suitable for environmental monitoring of the heavy metals in snow samples.     

Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review

The feasibility of using two important and common clay minerals, kaolinite and montmorillonite, as adsorbents for removal of toxic heavy metals has been reviewed. A good number of works have been reported where the modifications of these natural clays were done to carry the adsorption of metals from aqueous solutions. The modification was predominantly done by pillaring with various polyoxy cations of Zr4+, Al3+, Si4+, Ti4+, Fe3+, Cr3+or Ga3+, etc. Preparation of pillared clays with quaternary ammonium cations, namely, tetramethylammonium-, tetramethylphosphonium- and trimethyl-phenylammonium-, N'-didodecyl-N, N'-tetramethylethanediammonium, etc, are also common. Moreover, the acid treatment of clays often boosted their adsorption capacities. The adsorption of toxic metals, viz., As, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Zn, etc., have been studied predominantly. Montmorillonite and its modified forms have much higher metal adsorption capacity compared to that of kaolinite as well as modified-kaolinite.     

Novel modified pectin for heavy metal adsorption

Modified pectin cross-linked with adipic acid, was synthesized and used for heavy metal removal from wastewater. SEM and FTIR were used to investigate its structure and morphology. The modified pectin had a rough, porous phase covered with carboxy groups, resulting a high adsorption capacity. And at the room temperature, the saturated loading capacity for Pb^2＋, Cu^2＋ and Zn^2＋ reached 1.82 retool/g, 1.794 mmol/g and 0.964 retool/g, respectively. The results proved its potential application to remove of the heavy metal.     

Amorphous molybdenum sulfide mediated EDTA with multiple active sites to boost heavy metal ions removal

The rational design of strong affinity adsorbents for heavy metal ions removal remains a critical challenge for water treatment. In this study, amorphous molybdenum sulfide composites (EDTA-MoS_x (x = 2, 3)) were fabricated via a facile hydrothermal method mediated by EDTA, which was applied to heavy metal ions (Cu²⁺, Cd²⁺, Pb²⁺, Zn²⁺ and Ni²⁺) removal from aqueous solutions. A case study for Cu²⁺ ions showed that the adsorption capacity of EDTA-MoS_x (x = 2, 3) was superior to crystalline phase MoS₂ at pH 6.0 with an initial concentration of 200 mg/L. Adsorption mechanisms of different sulfide groups and COOH of EDTA-MoS_x (x = 2, 3) were verified systematically via a series of experiments, characterizations, and density functional theory (DFT) calculations. Both bridging S₂²⁻ and COOH covalently bonded with Cu²⁺ ions were ascribed to the critical factors for this enhanced removal efficiency on the surface of EDTA-MoS_x (x = 2, 3). This work offers a new method to enhance the adsorption performance of molybdenum sulfide-based materials by controlling crystallinity mediated with an organic complex small molecule.     

Comparison of lead, cadmium, copper and cobalt adsorption onto metal oxides and organic materials in natural surface coatings

Selective extraction techniques followed by adsorption experiment and statistical analysis were employed to estimate and compare the relative roles of metal oxides and organic substance in adsorption of Pb, Cd, Cu and Co onto surface coatings. Results indicated that metal oxides were very important sorbents for all of metal ions involved in this study, especially for Pb and Co. Furthermore, manganese oxides contributed to the absolute majority of Co adsorption regardless of concentration. But for Cu and Cd, organic materials are also very important sorbent phases, particularly for Cu, organic materials contributed to most of the Cu adsorption regardless of concentration. In addition, the analysis suggested the extraordinary predominance of Mn oxides for metal adsorption at the low concentrations. Considering the low concentration in natural water environments, Mn oxides might exert the greatest influence on the behavior of heavy metals.     

Calorimetric investigations of urease inhibition by heavy metal ions

The subject of this publication is calorimetric investigations on the inhibitor effect of heavy metal ions on the enzyme urease. The obtained results allow quantification of the inhibitors (Cd²⁺-, As³⁺-, Zn²⁺-, Pb²⁺-ions) via the initial reaction rate of enzymatically catalysed urea hydrolysis. The interpretation potential of the calorimetric measurements is underlined by the determination of the inhibiting mechanisms for the example of Cd²⁺- and As³⁺-ions, the findings on the time regime of the inhibition process, and the detection of heavy metal ions in the ppm range. The use of several different buffer substance revealed the influence of the latter on the intensity of heavy metal inhibition. This opens the path to both the selective analysis of heavy metals via pattern recognition and to the improvement of detection sensitivity.     

Recent developments in the adsorptive removal of heavy metal ions using metal-organic frameworks and graphene-based adsorbents

Clean and potable water is a growing concern around the globe. Among the different water pollutants, heavy metal ions pose a serious health concern to all living beings. The quest for new adsorbents to remove heavy metal ions received a boost with the development in the field of metal-organic framework (MOF). The advancement in synthetic strategies and designing of MOF enabled the researchers to tune the adsorption characteristics and tailor the material specific to a heavy metal ion. Similar to MOF, graphene-based two-dimensional and three-dimensional materials are also promising due to the diverse functionalization possibilities and cost-effectiveness. There had been growing interest in applying MOF and graphene-based materials for the removal of heavy metal ions in the past decade. This review summarizes these developments in detail.     

Sorption of transition metal cations on natural heulandite

The cation exchange equilibrium in the systems of natural heulandite-binary aqueous solutions of NaCl, NiCl₂, CuCl₂, ZnCl₂, and MnCl₂ was studied. The corrected coefficients of the selectivity (k ^a _M/Na) and thermodynamic constants (K _M/Na) of the cation exchange of Na⁺ cations for transition metal cations were determined. The selectivity of the cation exchange on natural heulandite increases in the following order: Ni²⁺ < Cu²⁺ < Zn²⁺ < Na²⁺ < Mn²⁺.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1101–1103, May, 1996.     

络合吸附伏安法同时测定多种重金属离子

在络合剂亚硝基苯胲 乙醇 乙酸铵体系中,Cr(Ⅵ)、Cd2 、Cu2 、Pb2 、Ni2 等离子都能在汞电极上产生灵敏的阴极络合吸附波,其二次导数伏安峰电流均与离子质量浓度有良好的线性关系,可用于这些离子的定量检测,测定线性范围为Cr(Ⅵ)0.0017～0.67μg mL、Cd2 0.0017～0.117μg mL、Cu2 0.0083～5 8μg mL、Pb2 0.083～1.25μg mL、Ni2 0.17～150μg mL,RSD分别为5.7%、1 3%、1.4%、2 5%和1.6%。方法为工业废水、地表水及生活用水等样品中重金属离子的同时测定提供了可靠、灵敏的检测方法。     

New terpolymer-matrix microcomposites for heavy metal removal

Terpolymer/kaolinite microcomposites were synthesized by 2:2:1 molar ratio of the selected monomers, respectively using various proportions of kaolinite clay via in situ oxidative terpolymerization. The outcomes were confirmed by FT-IR and UV-Vis spectra of terpolymers/kaolinite microcomposites. The thermal behaviour of the terpolymer microcomposites was examined and compared with the pristine terpolymer. SEM of terpolymer microcomposite was recorded at varied magnifications and was affirmed microcomposite granules spread out through the area including sizes from 0.06?μm to 0.70?μm. From DLS results, narrow PDI value of the terpolymer in the microcomposites suggests the narrow molecular weight distribution. This study demonstrates that terpolymers/kaolinite microcomposites particles could be represented as potential adsorbents for dangerous and perilous metal ions from water. Each of Cd(II), Cu(II) and Pb(II) caused a serious health problem in our day-to-day life.     

Determination of heavy metal ions by microchip capillary electrophoresis coupled with contactless conductivity detection

An integrated detection circuitry based on a lock-in amplifier was designed for contactless conductivity determination of heavy metals. Combined with a simple-structure electrophoresis microchip, the detection system is successfully utilized for the separation and determination of various heavy metals. The influences of the running buffer and detection conditions on the response of the detector have been investigated. Six millimole 2-morpholinoethanesulfonic acid + histidine were selected as buffer for its stable baseline and high sensitivity. The best signals were recorded with a frequency of 38 kHz and 20 V(pp). The results showed that Mn(2+), Cd(2+), Co(2+), and Cu(2+) can be successfully separated and detected within 100 s by our system. The detection limits for five heavy metals (Mn(2+), Pb(2+), Cd(2+), Co(2+), and Cu(2+)) were determined to range from about 0.7 to 5.4 μM. This microchip system performs a crucial step toward the realization of a simple, inexpensive, and portable analytical device for metal analysis.     

Adsorption of 1-olefin/n-paraffin liquid mixtures on NaX and NaY zeolites

The isotherm equation for adsorption of binary liquid mixtures of nonelectrolytes, involving differences in molecular sizes of components and quasi-Gaussian energy distribution of adsorption sites, is used to describe the excess adsorption data for 1-olefin/n-paraffin liquid mixtures on NaX and NaY zeolites at 293 K. This equation gives a good representation of the above adsorption data. Analysis of these data showed that the heterogeneity parameter is slightly dependent on the difference in molecular sizes of both components.     

Reactivity of sugar cane bagasse as a natural solid phase extractor for selective removal of Fe(III) and heavy-metal ions from natural water samples

This work introduces the feasibility of using sugar cane bagasse (SCB) – a sugar cane industry waste – as a selective solid phase extractor for Fe(III). The order of metal uptake capacities in μmol g^?1 for the extraction of six tested metal ions from aqueous solution using static technique is Fe(III) > Cu(II) > Pb(II) > Zn(II) > Cd(II) > Co(II). Since SCB exhibits remarkable binding characteristics for Fe(III), special interest was devoted for optimizing its uptake and studying its selectivity properties under static and dynamic conditions. In this respect, batch experiments were carried out at the pH range 1.0–4.0, initial concentration of metal ion (10–100 μmol), weight of phase (25, 50, 75, 100, 125 and 150 mg) and shaking time (10, 30, 45, 60, 90, 120 and 150 min). FT-IR spectra of SCB before and after uptake of Fe(III) were recorded to explore the nature of the functional groups responsible for binding of Fe(III) onto the studied natural biosorbent. The equilibrium data were better fitted with Langmuir model (r² = 0.985) than Freundlich model (r² = 0.934). Moreover, Fe(III) sorption was fast and completed within 60 min. The adsorption kinetics data were best fitted with the pseudo-second-order type. As a view to find a suitable application of SCB based on its unique property as a benign sorbent, it was found that, Fe(III) spiked natural water samples such as doubly distilled water (DDW), drinking tap water (DTW), natural drinking water (NDW), ground water (GW) and Nile River water (NRW) was quantitatively recovered (>95.0%) using batch and column experiments, with no matrix interferences.     

Removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions by adsorption onto natural bentonite

In this study, the removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions using the adsorption process onto natural bentonite has been investigated as a function of initial metal concentration, pH and temperature. In order to find out the effect of temperature on adsorption, the experiments were conducted at 20, 50, 75 and 90 °C. For all the metal cations studied, the maximum adsorption was observed at 20 °C. The batch method has been employed using initial metal concentrations in solution ranging from 15 to 70 mg L⁻¹ at pH 3.0, 5.0, 7.0 and 9.0. A flame atomic absorption spectrometer was used for measuring the heavy metal concentrations before and after adsorption. The percentage adsorption and distribution coefficients (K _d) were determined for the adsorption system as a function of adsorbate concentration. In the ion exchange evaluation part of the study, it is determined that in every concentration range, adsorption ratios of bentonitic clay-heavy metal cations match to Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich (DKR) adsorption isotherm data, adding to that every cation exchange capacity of metals has been calculated. It is shown that the bentonite is sensitive to pH changes, so that the amounts of heavy metal cations adsorbed increase as pH increase in adsorbent-adsorbate system. It is evident that the adsorption phenomena depend on the surface charge density of adsorbent and hydrated ion diameter depending upon the solution pH. According to the adsorption equilibrium studies, the selectivity order can be given as Zn²⁺>Cu²⁺>Co²⁺. These results show that bentonitic clay hold great potential to remove the relevant heavy metal cations from industrial wastewater. Also, from the results of the thermodynamic analysis, standard free energy ΔG ⁰, standard enthalpy ΔH ⁰ and standard entropy ΔS ⁰ of the adsorption process were calculated.     

Effects of heavy metals and oxalate on the zeta potential of magnetite

Zeta potential is a function of surface coverage by charged species at a given pH, and it is theoretically determined by the activity of the species in solution. The zeta potentials of particles occurring in soils, such as clay and iron oxide minerals, directly affect the efficiency of the electrokinetic soil remediation. In this study, zeta potential of natural magnetite was studied by conducting electrophoretic mobility measurements in single and binary solution systems. It was shown that adsorption of charged species of Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), and Cd(2+) and precipitation of their hydroxides at the mineral surface are dominant processes in the charging of the surface in high alkaline suspensions. Taking Pb(2+) as an example, three different mechanisms were proposed for its effect on the surface charge: if pH<5, competitive adsorption with H(3)O(+); if 56, precipitation of heavy metal hydroxides prevails. Oxalate anion changed the associated surface charge by neutralizing surface positive charges by complexing with iron at the surface, and ultimately reversed the surface to a negative zeta potential. Therefore the adsorption ability of heavy metal ions ultimately changed in the presence of oxalate ion. The changes in the zeta potentials of the magnetite suspensions with solution pH before and after adsorption were utilized to estimate the adsorption ability of heavy metal ions. The mechanisms for heavy metals and oxalate adsorption on magnetite were discussed in the view of the experimental results and published data.     

Modification of solids with volatile organics III: Natural zeolites

Summary The effect of pre-adsorbed benzene and ethanol on the adsorptive properties of natural zeolite (clinoptilolite) has been studied by gas-solid chromatography. It has been shown that modification of the solid surface by volatile organics has a significant influence on the adsorptive properties. The modification is of the same order as the more difficult modification by inorganics, as illustrated here by clinoptilolite modification with Co²⁺. Energy distribution of surface adsorptive sites appears to be continuous and confirms previous finding that only a small proportion of active sites is responsible for most adsorbate retention. Part II reference [4]     

Feasibility of the use of disposable optical tongue based on neural networks for heavy metal identification and determination

This study presents the development and characterization of a disposable optical tongue for the simultaneous identification and determination of the heavy metals Zn(II), Cu(II) and Ni(II). The immobilization of two chromogenic reagents, 1-(2-pyridylazo)-2-naphthol and Zincon, and their arrangement forms an array of membranes that work by complexation through a co-extraction equilibrium, producing distinct changes in color in the presence of heavy metals. The color is measured from the image of the tongue acquired by a scanner working in transmission mode using the H parameter (hue) of the HSV color space, which affords robust and precise measurements. The use of artificial neural networks (ANNs) in a two-stage approach based on color parameters, the H feature of the array, makes it possible to identify and determine the analytes. In the first stage, the metals present above a threshold of 10⁻⁷ M are identified with 96% success, regardless of the number of metals present, using the H feature of the two membranes. The second stage reuses the H features in combination with the results of the classification procedure to estimate the concentration of each analyte in the solution with acceptable error. Statistical tests were applied to validate the model over real data, showing a high correlation between the reference and predicted heavy metal ion concentration.