Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions

In this research, the possibility of simultaneous removal of lead, cadmium and copper divalent ions from water samples through the use of Sepia pharaonis endoskeleton powder (SPEB) as bio‐material, was investigated. The bio‐sorbent was characterised by Fourier transform infrared spectrum (FT‐IR), atomic force microscopy (AFM) and X‐ray fluorescence (XRF). The different factors affecting the bio‐sorption process were studied. Langmuir and Freundlich isotherm models were applied to analyse the experimental data. The kinetic studies showed that the pseudo‐second order model kinetics were compatible with the investigated systems. It was found that under optimal conditions, this bio‐sorbent was efficient in the uptake of these heavy metal ions from both mono and multi‐metal solutions, and high removal percentages were achieved. This study verified the potential ability of SPEB as an efficient natural adsorbent for removal of Pb(II), Cd(II) and Cu(II) ions from river, tap and mineral water samples.     

Pb(II)、Cu(II)、Cd(II)在黄土上二元竞争吸附特性研究

铅、铜、镉是3种具有代表性的重金属污染物,可用于模拟多重离子复合污染情况。研究了离子浓度、土水比等因素对3种元素在黄土上二元竞争吸附特性的影响。等温吸附模型Langmuir、Freundlich和D-R模型都能在一定程度上解释Pb(II)-Cu(II)、Pb(II)-Cd(II)、Cu(II)-Cd(II)在黄土上的竞争吸附性能。黄土对Pb(II)、Cu(II)、Cd(II)的选择顺序为Pb(II)>Cu(II)>Cd(II)。相比单一吸附,黄土对每种离子的吸附容量均有不同程度的下降。溶液的初始浓度越大,3种离子在单位黄土上的最大吸附量也随之增大,吸附效率随之降低;适当增大土水比可提高离子的去除效率。试验结果为黄土作为防污屏障和污水处理材料提供了依据。     

Removal of Co(II) and Pb(II) from aqueous solutions by Zn/Al-layered double hydroxide intercalated with hexacyanoferrate (II)-ions

We have studied the possibility of using zinc–aluminum layered double hydroxide intercalated hexacyanoferrate (II)-ions for sorption removal of Cu(II), Co(II) and Pb(II) from aqueous solutions. The article showed high efficiency of a sorbent for removal from aqueous solutions of Cu(II) and P(II). It was found that a model of kinetics of the pseudosecond order the most precisely describes the sorption process of studied ions of heavy metals (R ² > 0.99).     

Removal of free and complexed heavy-metal ions by sorbents produced from fly (Musca domestica) larva shells

Fly larva shells (FLS) are formed as a side product in the biological treatment of organic wastes, and chitin and chitosan produced from the FLS have been used as sorbents for heavy-metal ions. Sorbents are characterised by FT-IR measurements and pH-potentiometric titration and by determination of their surface area, and the content of main elements (C, N, P, S) and ashes. Free metal ions are sorbed best (up to 0.5-0.8 mmol g(-1)) onto chitin and chitosan. The sorption ability for free metal ions of chitin decreases in the order Fe(III) > Cu(II) (Pb(II) > Zn(II). > Ni(II) > Mn(II) and that of chitosan decreases in the order Cu(II) > Mn(II) > Ni(II) > Zn(II) > Pb(II) > Fe(III). The complexed metal ions are sorbed by the FLS up to 0.2-0.4mmol g(-1). The sorption ability for metal ions and ligands depends on pH, concentration of complexed metal ions and the ligand species in the solution. Glycine has the retarding effect on the sorption of Ni(II) and Cu(II) ions, and EDTA enhances the Cu(II) ion sorption. Ni(II) and glycine sorption obeyed the Langmuir isotherm. The observed sorption data show the promising potentialities of the FLS for the heavy-metal removal from the solutions, containing strong complexing agents. Mechanisms for the removal of free and complexed metal ions by chitin, chitosan and the FLS have been discussed.     

Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic studies

Natural Jordanian sorbent (consisting of primary minerals, i.e., quartz and aluminosilicates and secondary minerals, i.e., calcite and dolomite) was shown to be effective for removing Zn(II), Pb(II) and Co(II) from aqueous solution. The major mineral constitutions of the sorbent are calcite and quartz. Dolomite was present as minor mineral and palygorskite was present as trace mineral. The sorbent has microporous structure with a modest surface area of 14.4 m(2)g(-1). pH(zpc) (pH of zero point charge) of the sorbent was estimated by alkaline-titration methods and a value of 9.5 was obtained. The sorption capacities of the metals were: 2.860, 0.320, 0.076 mmol cation g(-1) for Zn(II), Pb(II) and Co(II) at pH 6.5, 4.5 and 7.0, respectively. The shape of the experimental isotherm of Zn(II) was of a "L2" type, while that of Pb(II) and Co(II) was of a "L1" type according to Giles classification for isotherms. Sorption data of metals were described by Langmuir and Freundlich models over the entire concentration range. It was found that the mechanism of metal sorption was mainly due to precipitation of metal carbonate complexes. The overall sorption capacity decreased after acid treatment, as this decreased the extent of precipitation on calcite and dolomite. The effect of Zn(II) ions concentration on sorption kinetics was investigated. Kinetic data were accurately fitted to pseudo-first order and external diffusion models which indicated that sorption of Zn(II) occurred on the exterior surface of the sorbent and the contribution of internal diffusion mechanism was insignificant. Furthermore, the sorption rate of Zn(II) was found to be slow, where only 10-20% of the maximum capacity was utilized in the first 30 min of interaction.     

Displacement mechanism of binary competitive adsorption for aqueous divalent metal ions onto a novel IDA-chelating resin: isotherm and kinetic modeling

Adsorptive properties for Cu (II), Pb (II) and Cd (II) onto an iminodiacetic acid (IDA) chelating resin were systematically investigated at the optimal pH-value in both single and binary solutions using batch experiments. The Langmuir isotherm model and the pseudo second-order rate equation could explain respectively the isotherm and kinetic experimental data for sole-component system with much satisfaction. The maximum adsorption capacity in single system for Cu (II), Pb (II) and Cd (II) was calculated to be 2.27 mmol/g, 1.27 mmol/g and 0.65 mmol/g individually. The initial adsorption rate followed the order as Cu (II) > Pb (II) > Cd (II) at the fixed initial concentration, and for each metal the initial sorption rate increased as the initial concentration increased. In addition, the modified Langmuir model could describe the binary competitive adsorption behavior successfully, with which the interaction coefficient was obtained to follow the order as Cu (II) < Pb (II) < Cd (II). Furthermore, in every case of the investigated three binary systems, the reduction in both the uptake amounts and distribution coefficients testified the antagonistic competitive phenomena. Obviously, this novel IDA-chelating resin possessed of a good selectivity toward Cu (II) over Pb (II) and Cd (II) for the obtained highest separation factor values were up to 21.30 and 133.91 in the range of tested. This interaction mechanism between the favorable component and other metal ions could mainly contribute to the direct displacement impact which be herewith illustrated schematically.     

Stabilization of Cu (II) wastes by C3S hydrated matrix

Cement is the most adaptable binder currently available for the immobilization of heavy metals. C₃S, tricalcium silicate, is one of the main phases in OPC and many of its properties were related to C₃S. In the present work the stabilization of Cu (II) wastes by C₃S during its early hydration (from 3 h – 7 days) was studied. Copper ions here either doped inside C₃S during its preparation or present in the water of hydration. Levels of Cu (II) used were 1 and 3 wt.% of C₃S. The chemically combined water and free Ca(OH)₂ contents were determined after 3, 6 h and 1, 3 and 7 days of hydration. X-ray diffraction examination was performed for some selected samples. The results showed that the presence of Cu (II) ions retard the early hydration of C₃S. This is due to the precipitation of the less soluble Cu(OH)₂ which retards the precipitation of Ca(OH)₂ as a result of the reduction in pH. Immobilization percentage of Cu (II) ions inside the C₃S hydrated matrix was examined by the determination of the leached copper by using atomic absorption spectroscopy. Most of the investigated samples showed high degree of immobilization of Cu (II) ions and the doped mixes showed better immobilization results than mixes hydrated in water containing wastes. The rate of leached Cu (II) ions from the matrix of hydrated C₃S was investigated by the application of diffusion equation derived for a plane source model.     

Adsorption of Cu(II) and Pb(II) onto a grafted silica: isotherms and kinetic models

The isotherms and kinetics of adsorption of lead(II) and copper(II) onto a grafted silica are studied at 20 degrees C. A commercial silica is grafted with an ethylediamine derivative, N-[3-(trimethoxysilyl)propyl]-ethylenediamine. From the Langmuir isotherms, maximum adsorption capacities of the grafted silica towards Pb(II) and Cu(II) are determined (0.184 mmol Pb(II)g-1 and 0.261 mmol Cu(II)g-1) and compared to those of non-modified silica (respectively, 0.019 and 0.036 mmol g-1). Four kinetic models, i.e., pseudo-first order, pseudo-second order, Langmuir and double-exponential are applied to fit the experimental kinetic data. The kinetic parameters are determined which allow to calculate the theoretical metal uptake as a function of time. The results are discussed and indicate the best fit is obtained with the double-exponential model. A discussion on the adsorption mechanism with respect to the double-exponential model leads to two possible interpretations: the metal uptake may follow a diffusion-controlled mechanism or a two-site adsorption process.     

Impact of polyhexamethylene guanidine on filtering of Pb(II) and Cd(II) hydroxides from aqueous solutions

The paper presents results of investigations aimed at optimizing the process of Pb(II) and Cd(II) removal using polyhexamethylene guanidine (PHMG) from aqueous solutions. The formation of compounds of chemisorption-type ions of the above metals with PHMG was established by using the methods of polarography, infrared spectroscopy, and pH-metry. The investigations revealed a positive impact of PHMG on the sedimentation and filtering of the precipitation of Pb(II) and Cd(II) hydroxides.     

Determination of polycyclic aromatic hydrocarbons in sea water using solid‐phase microextraction

Solid‐phase microextraction (SPME) technique with poly(dimethylsiloxane)‐coated fiber has been employed for the rapid determination of sixteen polycyclic aromatic hydrocarbons (PAHs) present in natural water. The method is solvent‐less with the analytes being adsorbed and then desorbed thermally at the injector port of a gas chromato‐graph (GC) prior to mass spectrometric (MS) analysis in selective ion monitoring (SIM) mode. The influences of the injector port temperature, desorption time and initial oven temperature on the thermal desorption of PAHs from the fiber were investigated. Then the optimum SPME conditions were applied for the qualitative and quantitative determination of PAHs in environmental samples. The recoveries of the 16 PAHs being spiked into sea water at 50 ng/mL level were 75.3%. The levels of PAHs in the Singapore coastal sea water are between 0.02–8.50 ng/mL using SPME(PDMS).     

Removal of metal ions by modified Pinus radiata bark and tannins from water solutions

Pinus radiata bark and tannins, chemically modified with an acidified formaldehyde solution were used for removing metal ions from aqueous solutions and copper mine acidic residual waters. The adsorption ability to different metal ions [V(V), Re(VII), Mo(VI), Ge(IV), As(V), Cd(II), Hg(II), Al(III), Pb(II), Fe(II), Fe(III), Cu(II)] and the factors affecting their removal from solutions were investigated. Effect of pH on the adsorption, desorption, maximum adsorption capacity of the adsorbents, and selectivity experiments with metal ion solutions and waste waters from copper mine were carried out. The adsorbents considerably varied in the adsorption ability to each metal ion. The adsorption depends largely upon the pH of the solution. Modified tannins showed lower adsorption values than the modified bark. For the same adsorbent, the maximum capacity at pH 3 for the different ions were very different, ranging for modified bark from 6.8 meqg⁻¹ for V to 0.93 meqg⁻¹ for Hg. Waste waters were extracted with modified bark as adsorbent and at pH 2. The ions Cu(II) (35.2 mgL⁻¹), Fe(III) (198 mgL⁻¹), Al(III) (83.5 mgL⁻¹) and Cd(II) (0.15 mgL⁻¹) were removed in 15.6%, 46.9%, 83.7% and 3.3%, respectively, by using 1 g of adsorbent/10 mL of waste water. In general, a continuous adsorption on a packed column gave higher adsorbed values than those observed in the batchwise experiment.     

Occurrence of emerging contaminants, priority substances (2008/105/CE) and heavy metals in treated wastewater and groundwater at Depurbaix facility (Barcelona, Spain)

The presence of 170 pharmaceuticals, personal care products, priority substances according to the 2008/105EU Directive and four metals (Cd, Ni, Hg, Pb) have been investigated at the Llobregat delta, south of Barcelona (Spain). In the area, reclaimed water is destined to satisfy environmental uses, irrigation and the construction of a hydraulic barrier against seawater intrusion in the deep aquifer of the delta. A monitoring survey was undertaken of water samples from a tertiary wastewater treatment plant (Depurbaix), treated waste water with an additional treatment of ultrafiltration, reverse osmosis, and UV disinfection (WWATP, for the hydraulic barrier injection). Groundwater samples from the aquifer receiving recharge were also investigated. The pharmaceutical group of substances was detected in sampled waters at concentrations rarely exceeding a few μg/L, among the compounds Caffeine, Nicotine and Galaxolide (musk fragrance) were found to be present in more than 60% of the samples. Diuron was the only priority substance detected. The four metals were always present in a variable concentration. After the WWATP treatment the majority of analytes are removed from tertiary treated wastewater or their concentration is reduced below 0.1 μg/L. Monitoring revealed a widespread occurrence of analysed compounds in groundwater. Among them Codeine (analgesic), Ibuprofen (anti-inflammatory), Iopamidol, Iopromide (contrast agent) and Paraxanthine (metabolite of caffeine) have only been detected in groundwater, and are not present in water currently being injected in the deep aquifer.     

Microscopic and macroscopic approaches of Cu(II) removal by FSM-16

The removal of Cu(II) by a mesoporous material, FSM-16, was studied using electron paramagnetic resonance (EPR) spectroscopy and surface complexation modeling (SCM). Free copper ions, adsorbed and precipitated Cu(II) species were qualitatively identified by in situ EPR spectroscopy of Cu-FSM-16 suspensions at room temperature and at 77 K. In addition, the adsorbed species was identified as a Cu(II) species with an axial symmetry from an analysis of the EPR spectra of "dry" Cu-FSM-16 at 77 K. On the basis of the EPR results, the removal of Cu(II) as a function of pH under various experimental conditions was successfully simulated by assuming two removal mechanisms such as surface complexation and surface precipitation. In the acidic pH range (< pH 6), free copper ions were predominant, and surface complexed then surface precipitated species became dominant as the pH increased.     

Fabrication and optimization of Cu(II) ion selective membrane electrode

In this study, the fabrication, performance characteristics and application of a Cu(II) ion selective pyridine based thorium(IV) phosphate membrane electrode are studied. The membrane electrode exhibited a fast response time of 10 s, the wide linear response in the concentration of 1 × 10^–1 to 1 × 10^–7 M of Cu (II) ions with a slope of 27.60 mV/decade change in concentration and a lifetime of 4 months. The potentiometric response revealed that the potentials are independent of pH in the wide range of 3.0–6.5. It was also used as an indicator electrode in the potentiometric titration of Cu(II) ions using ethylenediamine tetraacetic acid, disodium salt.     

Chemical substitution reaction between Cu(II) and Hg(II) and hydrous CdS(s)

The chemical reaction between hydrous CdS(s) and Cu(II) and Hg(II) were studied by electrophoretic mobility measurements and adsorption experiments. The results show that cation exchange, following readsorption of the released Cd(II) ions onto the freshly-formed CuS(s) and cadmium hydroxide precipitation reactions occur when CdS particles come into contact with these metal ions which have sulfide precipitates less soluble than CdS(s). The effect of organic ligands on the ion exchange reaction, exemplified by EDTA (a strong complexing ligand) and phthalic acid (a weak complexing ligand), was also investigated. Both organic compounds have little effect on the lattice ion exchange reaction unless a large amount of strong complexing agent is present in the system. The dissolution of CdS(s), however, is slightly hindered in the presence of weak complex former such as phthalic acid and greatly enhanced in the presence of strong complex former such EDTA.     

Anthropogenic platinum group element (Pt, Pd and Rh) concentrations in road dusts and roadside soils from Perth, Western Australia

The emission of platinum group elements (PGE) from automobile catalytic converters has led to rapid increases in Pt, Pd and Rh concentrations in roadside media. This article represents the first detailed study to assess PGE levels in road dusts and roadside soils in Australia. Road dust and roadside soil samples were analysed by ICP-MS following microwave digestion and cation exchange. All samples show elevation of PGE above average upper crust values, with maximum values of 420 ng g(-1) Pt, 440 ng g(-1) Pd and 91 ng g(-1) Rh. PGE ratios in road dusts and soils are consistent with known catalytic converter compositions and while Pt and Rh abundances are comparable with European studies, Pd levels are substantially higher in Australian samples. PGE in these samples are not correlated with Pb, though positive correlations with Ce, Cu and Y are evident. No straightforward relationship between traffic volume and PGE abundance is evident and factors such as driving style, topography, road drainage and potentially climate exert considerable influences.     

Lead and cadmium contents in cereals and pulses in north-eastern China

It is known that, unlike Japanese, Koreans or southern Chinese who depend on rice as a major source of energy for daily life, people in north-eastern China rely not only on rice, but on wheat and other cereals and to a lesser extent also on pulses. Cereal and pulse samples were collected from open markets in north-eastern China, and analyzed by inductively-coupled plasma spectrometry (ICP-MS) for two potentially hazardous heavy metals — lead (Pb) and cadmium (Cd). The average Pb level in cereals (31.3 ng Pb/g as a geometric mean) and that of pulses (25.7 ng Pb/g) were similar to each other with no significant difference. Among the cereals, Pb contents were higher in foxtail millet (54.3 ng/g) and lower in maize (35.4 ng Pb/g; grain and flour in combination), wheat flour (28.8 ng Pb/g) and rice flour (22.7 ng Pb/g). Lead levels in two important types of pulses, kidney bean and soybean (24.6 and 30.8 ng Pb/g, respectively), were comparable to the levels in rice and wheat. In contrast, Cd levels were substantially higher in pulses (55.7 ng Cd/g) than in cereals (9.2 ng Cd/g), and among the pulses, Cd in soybean (55.7 ng Cd/g) was significantly higher than that in kidney bean (23.8 ng Cd/g). The possible public health implication of the Pb and Cd levels, especially the high Pb level in foxtail millet (54.3 ng Pb/g) and the high Cd level in soybean (73.5 ng Cd/g), is discussed.     

Heavy metals in benthic foraminifera from the highly polluted sediments of the Naples harbour (Southern Tyrrhenian Sea, Italy)

A systematic investigation evaluated the concentrations of a selected number of trace elements (Cd, Co, Cu, Li, Ni, Pb, V and Zn) in carbonates of the benthic foraminifera Ammonia tepida collected from surface sediments of the highly polluted harbour of Naples. Application of cleaning procedures, combined with Scanning Electron Microscopy investigation (SEM) of the analysed shells allowed reliable quantification of the elements in the carbonate lattice. Adoption of biogenic carbonate/seawater distribution coefficients reported in the literature provided the ranges of variability of total dissolved trace elements in the studied marine environment. Very high concentrations of Zn, Cd, and Cu calculated in seawater (from 100 to 10,000 times higher than those reported for uncontaminated Mediterranean seawaters) testify to intense effects of anthropogenic impact on the harbour mainly related to the industrial and commercial activities carried out in the neighbouring area. The ensemble of the obtained results emphasizes the high potential of measurements of trace elements in the biogenic carbonates of benthic foraminifera as tracers of anthopogenic pollution of seawater and reliable proxies of potentially bioavailable forms (as free ions and/or more labile organic complexes) of seawater dissolved metals.     

Lead and Cu in contaminated urban soils: extraction with chemical reagents and bioluminescent bacteria and yeast

Twenty urban soil samples, with a wide range of Pb (14-5323 mg/kg) and Cu (8-12987 mg/kg), were used to compare the operational speciation of a five-step sequential leach with the bioavailability determined with bioluminescent Pb (RN4220(pTOO24)) and Cu (MC1061(pSLcueR/pDNPcopAluc)) specific bacterial biosensors and a Cu specific yeast sensor. The bioavailable Pb concentrations were all similar or lower than the first sequential leach step (1M NaOAc). In contrast, in some samples the bioavailable concentrations of Cu clearly exceeded even the second sequential leach step (0.1 M Na4P2O7). With the yeast sensor 12/20 samples were below detection, however, the yeast sensor was capable of detecting all high Cu concentrations. The biosensors used in this study are not capable of detecting the natural soil concentrations of Pb and Cu in the studied area.     

Sorption of cadmium(II) and zinc(II) ions from aqueous solutions by cassava waste biomass (Manihot sculenta Cranz)

The sorption of two divalent metal ions, Cd(II) and Zn(II), onto untreated and differentially acid-treated cassava waste biomass over a wide range of reaction conditions was studied at 30°C. The metal ion removal from the spent biomass was also measured. The batch experiments show that pH 4.5–5.5 was the best range for the sorption of the metal ions for untreated and acid-treated biomass. Time-dependent experiments for the metal ions showed that for the two metals examined, binding to the cassava waste biomass was rapid and occurred within 30 min and completed within 1 h. High sorption capacities were observed for the two metals. The binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 86.68 mg/g Cd, 55.82 mg/g Zn and 647.48 mg/g Cd, 559.74 mg/g Zn for untreated and acid-treated biomass, respectively. It was further found that the rate of sorption was particle-diffusion controlled, and the sorption rate coefficients were determined to be 2.30×10⁻¹ min⁻¹ (Cd²⁺), 4.0×10⁻³ min⁻¹ (Zn²⁺) and 1.09×10⁻¹ min⁻¹ (Cd²⁺), 3.67×10⁻² min⁻¹ (Zn²⁺) for 0.5 and 1.00 M differential acid treatment, respectively. Desorption studies showed that acid treatment inhibited effective recovery of metal ions already bound to the biomass as a result of stronger sulfhydryl-metal bonds formed. Less than 25% of both metals were desorbed as concentration of acid treating reagent increases. However, over 60% Cd and 40% Zn were recovered from untreated biomass during the desorption study. The results from these studies indicated that both untreated and acid-treated cassava waste biomass could be employed in the removal of toxic and valuable metals from industrial effluents.