Removal of Inorganic Contaminants from Simulated Stormwater by Three Sorbents in Columns Under Intermittent Runoff Condition

Combined removal of inorganic contaminants from a synthetic stormwater was investigated by their sorption on hydrous ferric oxide (HFO) (5%), HFO + Ca(OH)₂(6%), and HFO + Ca(OH)₂ + MnO₂ (7%) in columns containing 93–95% anthracite, conducted under seven intermittent runoffs, each of 8 h duration with a 40 h (drying) period between them. At the initial period when Ca(OH)₂ produced elevated pHs, the HFO column removed less metals but more Se than the HFO + Ca(OH)₂ columns. With increased time when the pH effect of Ca(OH)₂ became insignificant, the MnO₂ in the column increased the removal of all contaminants. The removal efficiencies (%) at the flow rate of 0.75 m/h for Cd, Cu, Ni, Zn by the HFO + Ca(OH)₂ + MnO₂ column were 88–100%, and Se by the HFO column were 92–94% for the 1st and 3rd runs. The corresponding values for the 5th and 7th runs were 51–88% and 82–88%, respectively.     

Removal of inorganic pollutants in rainwater by a peat-derived porous material

Although roof-top runoff water has been considered as an alternative water resource, the harvested rainwater needs to be treated for further use because it usually contains various contaminants such as heavy metals and microbes. The degree of the harvested rainwater quality depends upon its end use such as drinking water and irrigation. Especially, when harvested rainwater is to be used as gray water, a cost effective treatment system is required. Accordingly, the main purpose of this study was to examine the adsorption characteristics of peat, cost-effective biosorbent, for various inorganic pollutants such as ammonium, copper, cadmium and lead from roof-top runoff water. As part of efforts to investigate the sorption properties of peat, batch isotherm tests were carried out under various pH conditions. The characterization of peat was carried out with powder X-ray diffraction, Brunauer–Emmett–Teller, and scanning electron microscope measurements. Both heat-treated peat and non-treated peat appeared to have high sorption capacity for all inorganic contaminants (NH₄ ⁺, Cu²⁺, Cd²⁺, and Pb²⁺). An interesting finding is that the amount of NH₄ ⁺ sorbed on the sorbents was slightly higher compared to the other cations. Also, the sorption capacity of the peat sorbents increased with an increase of pH. On the other hand, kinetic data were well described by pseudo-second kinetic model, indicating that removal mechanism of cations by peat-derived sorbents is likely due to chemisorptions. The results of this study suggested that peat-derived porous materials can be used as effective sorbents for removal of cationic inorganic contaminants from harvested rainwater.     

Fluoride Sorption from Aqueous Solutions and Drinking Water by Magnesium,Cobalt, and Nickel Hydrotalcite-Like Compounds in Batch and Column Systems

Magnesium, nickel, and cobalt hydrotalcite-like compounds (MgAlHT, NiAlHT, and CoAlHT) were used to remove fluoride ions from aqueous solutions and drinking water in batch and column systems. Mg, Ni, and Co hydrotalcite like compounds with similar M²⁺:Al³⁺ ratios were synthesized. F^? ions were determined in the remaining solutions using a fluoride ion selective electrode. Kinetic of the fluoride sorption from aqueous solutions by hydrotalcite-like compounds (HT) was best described by the pseudo-second-order model and the equilibrium was reached in less than 200 minutes for all cases (MgAlHT, NiAlHT and CoAlHT); however, this behavior was not observed for fluoride sorption from drinking water by NiAlHT. The sorption isotherms of the fluoride ion by hydrotalcite like compounds could be best fitted to the Langmuir and Freundlich models. NiAlHT showed the highest efficiency for the removal of fluoride ions from aqueous solutions in batch system. The removal of fluoride ions by NiAlHT from aqueous solutions was more efficient than from drinking water in both batch and column systems.     

Amidoximation of Cyano Group for Chelating Ion Exchange of Some Heavy Metal Ions from Wastewater

Ion exchange behavior of some heavy metal ions, Pb²⁺, Ni²⁺, and Cd²⁺, onto amidoximated polyacrylonitrile based Ce(IV) phosphate was investigated. Polyacrylonitrile based Ce(IV) phosphate was prepared and followed by functionalization of the cyano group to amidoxime group with hydroxylamine. The amidoximated resin was characterized using FT-IR and SEM. Removal of Pb²⁺, Ni²⁺, and Cd²⁺ ions from aqueous solution was examined by studying some factors using the batch technique such as effect of pH, contact time, initial metal ion concentration, and temperature. Some kinetic and isotherm models had been applied. The calculated amount of the sorbed values in case of the pseudo-second-order model are closer to the experimental data than that of the pseudo-first-order model, and with a correlation coefficients R² > 0.99. Therefore, the sorption of the three metal ions can be approximated more favorably by the pseudo-second-order model. The sorption process obeys the Freundlich isotherm model. The sorption has an endothermic nature which is indicated by the positive value of the enthalpy change, ΔH, the high positive values of the entropy change, and ΔS show the increased randomness at the solid/solution interface. The obtained negative values of free energy change, ΔG, indicate the feasibility and the spontaneous nature of the sorption process.     

HEAVY METALS REMOVAL FROM AQUEOUS SOLUTIONS USING TiO2, MgO,AND Al2O3 NANOPARTICLES

This study investigated the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ from aqueous solutions using nanoparticle sorbents (TiO₂, MgO, and Al₂O₃) with a range of experimental approaches. The maximum uptake values (sum of four metals) with multiple component solutions were 594.9, 114.6, and 49.4 mg g^?1, for MgO, Al₂O₃, and TiO₂, respectively. The sorption equilibrium isotherms were described using the Freundlich and Langmuir models. The best interpretation for experiment data was given by the Freundlich model for Cd²⁺, Cu²⁺, and Ni²⁺ in single- and multiple-component solutions. A first-order kinetic model adequately described the experimental data using MgO, Al₂O₃, and TiO₂. SEM-EDX both before and after metal sorption and soil solution saturation indices (SI) in MgO nanoparticles indicated that the main sorption mechanism for heavy metals was attributable to adsorption and precipitation, whereas heavy metal sorption by TiO₂ and Al₂O₃ adsorbents was due to adsorption. These nanoparticles may potentially be used as efficient sorbents for heavy metal removal from aqueous solutions. MgO nanoparticles were the most promising sorbents because of their high metal uptake.     

Chelating polymer bearing triazolylazophenol moiety as the functional group

The chelating polymer-bearing triazolylazophenol moiety as the functional group was synthesized, its metal adsorption properties for 6 divalent heavy metal ions; Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ were investigated. The capacity of the polymer for Cu²⁺ achieved 8.7 mEq/g in pH 5.3 solution. The polymer showed remarkable color changes from orange to red violet or blue violet with its chelations to the heavy metal ions. The metal adsorption rates of the polymer were rapid in performing complete capacity saturation of heavy metal ions in about 30 min. The capacities varied little the presence of alkali or alkaline earth metal ions in solutions. The perfect elimination of metals from the polymer–M²⁺ chelates were performed with mineral acid solutions. The metal ions; Cu²⁺ and Ni²⁺ in plating-process solutions were effectively removed by the chelating polymer, and the polymer can be practically used for the removal of these ions from waste water.     

Characterization of Adsorptive Capacity and Investigation of Mechanism of Cu2+, Ni2+ and Zn2+ Adsorption on Mango Peel Waste from Constituted Metal Solution and Genuine Electroplating Effluent

Abstract

The present study reports the potential of mango peel waste (MPW) as an adsorbent material to remove Cu²⁺, Ni²⁺, and Zn²⁺ from constituted metal solutions and genuine electroplating industry wastewater. Heavy metal ions were noted to be efficiently removed from the constituted solution with the selectivity order of Cu²⁺ > Ni²⁺ > Zn²⁺. The adsorption process was pH-dependent, while the maximum adsorption was observed to occur at pH 5 to 6. Adsorption was fast as the equilibrium was established within 60 min. Maximum adsorption of the heavy metal ions at equilibrium was 46.09, 39.75, and 28.21 mg g for Cu²⁺, Ni²⁺, and Zn²⁺, respectively. Adsorption data of all the three metals fit well the Langmuir adsorption isotherm model with 0.99 regression coefficient. Release of alkali and alkaline earth metal cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and protons H⁺ from MPW, during the uptake of Cu²⁺, Ni²⁺, and Zn²⁺, and EDX analysis of MPW, before and after the metal sorption process, revealed that ion exchange was the main mechanism of sorption. FTIR analysis showed that carboxyl and hydroxyl functional groups were involved in the sorption of Cu²⁺, Ni²⁺, and Zn²⁺. MPW was also shown to be highly effective in removing metal ions from the genuine electroplating industry effluent samples as it removed all the three metal ions to the permissible levels of discharge legislated by environment protection agencies. This study indicates that MPW has the potential to effectively remove metal ions from industrial effluents.     

Effect of light metal ions on the sorption of heavy metal ions on natural polymers

Dried ground formaldehyde-treated peanut skins, white ash bark, and So. Wisconsin red maple bark are efficient substrates for removal of many heavy metal ions from waste streams, but possible interference by common light metal cations has never been determined. The influence of Ca²⁺, Mg²⁺, or Na⁺ on the removal of the heavy metal ions Pb²⁺, Cu²⁺, Cd²⁺, and Zn²⁺ by the above substrates was studied in both batch and packed-column experiments. It was found that Pb²⁺ and Cu²⁺ were minimally affected by the presence of these light metal ions in solution, while the uptake of Cd²⁺ and Zn²⁺ was significantly reduced. Calcium ion produced the greatest effect of the light metals tested.     

Evaluation of ion exchange resins for recovery of metals from electroplating sludge

In the present study, the recovery of metal ions from industrial solid residues from a galvanoplasty industry (Rio de Janeiro, Brazil) was investigated by cationic and anionic ion exchange resins. The electroplating residues were composed of the metals Cu²⁺, Fe³⁺, Al³⁺, Ni²⁺, and Cr³⁺. The studies of sorption were conducted under batch and column conditions. Based on these studies, the sorption parameters and the breakthrough curves for both resins were determined. Studies of the sorption equilibrium and kinetics were also performed. The maximum sorption capacities q _e (mg g^?1) of the cationic resin were: Cu²⁺: 1.9, Fe³⁺: 0.6 and Al³⁺: 0.4. For the anionic resin, the maxim values of q _e were Cu²⁺: 0.4 and Fe³⁺: 0.1. The Freundlich model was more adequate to describe the ion exchange equilibrium and the sorption mechanism fit the pseudo second-order kinetic model for both resins. The breakpoint of Cu²⁺ (100 ppm) occurred after passing 1,860 and 2,220 cm³ of residue solution through 20.0 g of the resins (column with h:6.0 cm and d:4.3 cm, flow rate: 60 cm³ min^?1). The column regeneration was carried out for five sorption–desorption cycles using H₂SO₄ 2.4 mol L^?1 (cationic) and HCl 2.0 mol L^?1 (anionic).     

Oxidized cellulose: An application in the form of sorption filter materials

Oxidized cellulose (oxycellulose) was very effectively used in the form of filter sheets to remove some metal ions from water and from aqueous solutions. Furthermore, oxycellulose was applied in an ion‐exchange column and in a batch process. The mechanisms of the sorption process inside oxycellulose as well as the kinetics of sorption were studied. A comparison of oxycellulose and other adsorption components such as zeolites and ion‐exchange resins was made. The affinity of oxycellulose to metal ions was determined to be in the following order: Cd²⁺, Zn²⁺ > Ni²⁺ ? Ca²⁺ > Mg²⁺ ? Na⁺. The use of oxycellulose was very effective, especially in the form of sorption filters, because this allowed us to use a simple filtration process. Moreover, the specific loading amount of the filter cake was higher for filtration than for the column process under comparable conditions. Oxycellulose in a glass column behaved similarly to an ion‐exchange resin. It showed approximately constant efficiency until the sorption capacity of the adsorbent was exhausted, and then it suddenly dropped. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Highly porous,water-swellable,and reusable chelating polymeric gels for heavy metal ion removal from aqueous waste

Sequestration and removal of heavy metal ions from aqueous solutions pose multiple challenges. Ease of synthesis, high adsorption capacity and ease of regeneration are important considerations in the design of polymeric adsorbent materials developed for this purpose. To meet this objective, a new approach was used to design and synthesize a highly porous polystyrene-based resin (IDASR15) bearing iminodiacetate functional groups in every repeat unit by free radical polymerization with N, N'-methylenebisacrylamide as crosslinker followed by base hydrolysis. The physiochemical chemical properties of the resin were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, equilibrium swelling value (ESV) and thermogravimetric analysis. Metal uptake capacity of IDASR15 towards low concentrations of various toxic heavy metal ions such as Cu²⁺, Cd²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, Co³⁺, Cr³⁺, Fe²⁺, Fe³⁺, and Al³⁺ were investigated from their aqueous solution by batch method and found to be 0.943–2.802 mmol/g. The maximum capacity was 2.802 mmol/g obtained for Cu²⁺ ion at pH 5. The potential for regeneration and reuse has been demonstrated with Cu²⁺ ion by batch and column methods. The reported results suggest that IDASR15 is a highly efficient and porous complexing agent for commonly found toxic metal ions in aqueous streams with a high ESV of 68.55 g of water/1.0 g of IDASR15. It could also be reused ~99.5% of adsorption efficiency which is very promising and holds significant potential for waste-water treatment applications.     

Application of insoluble cellulose xanthate for the removal of heavy metals from aqueous solution

Insoluble cellulose xanthate (ICX), O-alkyl dithiocarbonate of cellulose, was synthesized and used for the removal of heavy metal ions from aqueous solutions. ICX possessed carbon disulfide (CS₂) as a functional group, which was obtained by esterification of the hydroxyl group on cellulose polymer matrix with CS₂. CS₂ could form complexes with divalent transition metal ions, and the resulting ICX-metal complex was water-insoluble and settled easily. The optimum composition for ICX synthesis was cellulose/NaOH/CS₂=1: 2: 2.3 in mole base, which showed the highest removal capacity. The selectivity and binding capacity of ICX for heavy metals were in the order of Pb²⁺> Cd²⁺> Ni²⁺ and Cd²⁺> Pb²⁺> Ni²⁺, respectively. More than 90 % of the initial amount of heavy metals was removed within 30 min. The optimum pH was neutral or slightly alkaline, and more than 40 % of initial heavy metals was removed even in the acidic range of pH 2 to 3.     

The use of dyestuff-treated rice hulls for removal of heavy metals from waste water

Rice hulls, when coated with the reactive dye of Procion Red or Procion Yellow, was found to be highly effective for removal of many metal ions from aqueous solutions both in batch and column method. When 120–130 ppm solutions were used, quantitative removal could be achieved with Pb²⁺, Cd²⁺, and Hg²⁺. After the adsorption of metal ions, the substrate could be recovered almost completely by treating with dilute hydrochloric or nitric acid solution, and used repeatedly.     

Adsorptive Removal of Nitrate and Phosphate from Water by a Purolite Ion Exchange Resin and Hydrous Ferric Oxide Columns in Series

Elevated concentrations of nitrate and phosphate in surface and ground waters can lead to eutrophication, and nitrate can also cause health hazards to humans. The adsorption process is generally considered to be an efficient technique in removing these ions provided that the adsorbent is highly selective for these ions. Removal of nitrate and phosphate from a synthetic water (50 mg N/L as nitrate, 15 mg P/L as phosphate) and a wastewater (12.9 mg N/L as nitrate, 5.9 mg P/L as phosphate) using a Purolite A500P anion exchange resin and a hydrous ferric oxide (HFO) columns (60 cm height, 2 cm diameter, flow rate 1 m/h) in series containing 1–10% (w/w) of these adsorbents and the remainder anthracite (90–99%) were studied. Data from batch adsorption experiment at various concentrations of adsorbents satisfactorily fitted to Langmuir adsorption isotherm for nitrate and phosphate on Purolite with adsorption maxima of 64 mg N/g and 7 mg P/g and only for phosphate on HFO with adsorption maxima of 14 mg P/g. Both batch and column experiments showed that Purolite selectively removed nitrate and HFO selectively removed phosphate. The Purolite column BTC time was greater for nitrate than for phosphate. At the highest percentage by weight of Purolite almost all nitrate was removed in batch study and up to 1000 min in column study, but it was not able to remove a comparatively high percentage of phosphate. However, when the effluent from the Purolite column was passed through the HFO column almost all phosphate was removed. The two columns when set up in series also removed almost all nitrate and phosphate from the wastewater.     

Binding of heavy metal ions by formaldehyde-polymerized peanut skins

Peanut skin, when treated with formaldehyde to polymerize tannins, is a highly efficient substrate for removal of many heavy metal ions from aqueous waste solutions. The ions Ag¹⁺, Cd²⁺, Cr⁶⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, as well as Ca²⁺ and Mg²⁺, were contacted with formaldehyde-treated peanut skin. Quantitative removal could be achieved with Ag¹⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺, and Zn²⁺. Capacity of the substrate for ions was promising for Pb²⁺ (2.1 meq/g substrate), Cu²⁺ (3.0 meq/g), and Cd²⁺ (1.3 meq/g). Sorption from a solution containing Cd²⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, on a packed column of formaldehyde-treated peanut skin indicated that Hg²⁺, Pb²⁺, and Cu²⁺ were rapidly and completely bound to the packing, while Cd²⁺, Ni²⁺, and Zn²⁺ were poorly bound until the preferred ions had been removed from solution.     

Removal of metal ions using lignite in aqueous solution—Low cost biosorbents

Turkish lignite can be used as a new adsorption material for removing some toxic metals from aqueous solution. The adsorption of lignite (brown young coals) to remove copper (Cu²⁺), lead (Pb²⁺), and nickel (Ni²⁺) from aqueous solutions was studied as a function of pH, contact time, metal concentration and temperature. Adsorption equilibrium was achieved between 40 and 70 min for all studied cations except Pb²⁺, which is between 10 and 30 min. The adsorption capacities are 17.8 mg/g for Cu²⁺, 56.7 mg/g for Pb²⁺, 13.0 mg/g for Ni²⁺ for BC₁ (Ilg?n lignite) and 18.9 mg/g for Cu²⁺, 68.5 mg/g for Pb²⁺, 12.0 mg/g for Ni²⁺ for BC₂ (Beysehir lignite) and 7.2 mg/g for Cu²⁺, 62.3 mg/g for Pb²⁺, 5.4 mg/g for Ni²⁺ for AC (activated carbon). More than 67% of studied cations were removed by BC₁ and 60% BC₂, respectively from aqueous solution in single step. Whereas about 30% of studied cations except Pb²⁺, which is 90%, were removed by activated carbon. Effective removal of metal ions was demonstrated at pH values of 3.8–5.5. The adsorption isotherms were measured at 20 °C, using adsorptive solutions at the optimum pH value to determine the adsorption capacity. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The rise in temperature caused a slight decrease in the value of the equilibrium constant (K_c) for the sorption of metal ions. The mechanism for cations removal by the lignite includes ion exchange, complexation and sorption. The process is very efficient especially in the case of low concentrations of pollutants in aqueous solution, where common methods are either economically unfavorable or technically complicated.     

Unconventional ion exchange resins and their retention properties for Hg2+ ions

Synthesis of two unconventional ion exchange resins and their behaviour on the mercury sorption experiments were investigated.The ion exchange resins were obtained by the quaternization reaction of 4-vinylpyridine:divinylbenzene copolymer, gel-type, by two ways namely, the nucleophilic substitution of the pyridine matrix with 2-chloroacetamide and the nucleophilic addition of protonated copolymer to acrylamide.Comparative sorptions of Hg²⁺ ions on the synthesized pyridine resins by batch experiments in mono- and binary system were analyzed. Mercury retention experiments aimed to study the influence of the solution concentration, contact time and solution pH. The removal of Hg²⁺ ions from aqueous solutions depends on the pH values, the amount of the retained mercury increased with the pH value.The studied strong base pyridine anion exchange resins presented a good selectivity for the Hg²⁺ ions during the competitive sorption of Hg²⁺/Cu²⁺, Hg²⁺/Zn²⁺ and Hg²⁺/Fe³⁺ at metal cations ratio of 1:1.     

REMOVAL OF TOXIC Pb2+ IONS BY SYNTHETIC HYDROXYAPATITES

The removal behavior of toxic Pb²⁺ ions from aqueous and nonaqueous solutions by two synthetic hydroxyapatites (S-1 and S-2) has been investigated by using both batch and column methods.

It was found that Pb²⁺ ions in the both solutions were easily removed to the apatite samples mainly by cation-exchange reactions between the Pb²⁺ ions in the solutions and Ca²⁺ ions of the samples at room temperature. Further, in the system of aqueous PbF₂ solutions, anion-exchange reactions between F^? ions in the solutions and OH ^? ions of the samples occurred simultaneously and the liberated OH ^? and Ca²⁺ ions influenced removal behavior of Pb²⁺ and F^? ions. The maximum removal amount of Pb²⁺ ions from the aqueous solutions was 400?mg per g of S-1. Pb^? ions in the waste water from lead plating factories were completely removed to the apatite samples. In this manner, it was found that the apatites, especially S-1 can be employed as a new removal agent for the treatment of poisonous Pb²⁺ ions in waste water.     

Functionalized nanostructured silica by tetradentate-amine chelating ligand as efficient heavy metals adsorbent : Applications to industrial effluent treatment

Organofunctionalized nanostructured silica SBA-15 with tri(2-aminoethyl)amine tetradentate-amine ligand was synthesized and applied as adsorbent for the removal of Cu²⁺, Pb²⁺, and Cd²⁺ from both synthetic wastewater and real paper mill and electroplating industrial effluents. The prepared materials were characterized by XRD, N₂ adsorption-desorption, TGA, and FT-IR analysis. The Tren-SBA-15 was found to be a fast adsorbent for heavy metal ions from single solution with affinity for Cu²⁺, Pb²⁺, than for Cd²⁺ due to the complicated impacts of metal ion electronegativity. The kinetic rate constant decreased with increasing metal ion concentration due to increasing of ion repulsion force. The equilibrium batch experimental data is well described by the Langmuir isotherm. The maximum adsorption capacity was 1.85 mmol g^?1 for Cu²⁺, 1.34 mmol g^?1 for Pb²⁺, and 1.08 mmol g^?1 for Cd²⁺ at the optimized adsorption conditions (pH=4, T=323 K, t=2 h, C₀=3 mmol L^?1, and adsorbent dose=1 g L^?1). All Gibbs energy was negative as expected for spontaneous interactions, and the positive entropic values from 103.7 to 138.7 J mol^?1 K^?1 also reinforced this favorable adsorption process in heterogeneous system. Experiment with real wastewaters showed that approximately a half fraction of the total amount of studied metal ions was removed within the first cycle of adsorption. Hence, desorption experiments were performed by 0.3M HCl eluent, and Tren-SBA-15 successfully reused for four adsorption/desorption cycles to complete removal of metal ions from real effluents. The regenerated Tren-SBA-15 displayed almost similar adsorption capacity of Cu²⁺, Pb²⁺, and Cd²⁺ even after four recycles. The results suggest that Tren-SBA-15 is a good candidate as an adsorbent in the removal of Cu²⁺, Pb²⁺, and Cd²⁺ from aqueous solutions.     

Removal of Lead from Water Samples by Sorption onto Powdered Limestone

Abstract

Bench scale batch adsorption experiments were performed, aiming at the removal of the Pb²⁺ ions from aqueous solutions and water samples by fine powdered Limestone (LS) as an effective inorganic sorbent, which is inexpensive, widespread, and cheap. The main parameters (i.e., solution pH, sorbent and lead concentrations, stirring times, and temperature) influencing the sorption process, in addition to the effect of some foreign ions, were investigated. The results obtained stated that the sorption of Pb²⁺ ions onto LS is well described by Freundlich model and deviated from that of Langmuir over the concentration range studied. Under the optimum experimental conditions employed, the removal of ca. 100% of Pb²⁺ ions was attained. The procedure was successfully applied to the removal of lead from aqueous and different natural water samples. Moreover, the adsorption mechanism is suggested.