Adsorption of heavy metals by a porous bioadsorbent from lignocellulosic biomass reconstructed in an ionic liquid

A novel porous bioadsorbent for metal ion binding (Pd(2+) and Cd(2+)) was successfully prepared from lignocellulosic biomass in ionic liquid by homogeneous succinoylation and sequent chemical cross-linking. The morphology of the bioadsorbent and the interaction between bioadsorbent and metal ions was revealed by scanning electron microscopy and Fourier transform infrared spectroscopy. Results showed that the adsorption mechanism of the bioadsorbent was an ion exchange. A lower dose of cross-linker or higher carboxyl content increased the adsorption capacities of Pd(2+) and Cd(2+). The adsorption capacities of Pd(2+) and Cd(2+) remarkably increased as the pH of metal ion solutions increased. The pores in the bioadsorbent greatly favored the diffusion and adsorption of metal ions, and the adsorption equilibrium time was about 50 min. The adsorption of metal ions could be well explained by the Langmuir model, and the maximum adsorption capacities of Pd(2+) and Cd(2+) were 381.7 and 278.6 mg/g.     

Computer simulation of the interactions of glyphosate with metal ions in phloem

Essential nutrients such as trace metal ions, amino acids, and sugars are transported in the phloem from leaves to other parts of the plant. The major chelating agents in phloem include nicotianamine, histidine, cysteine, glutamic acid, and citrate. A computer model for the speciation of metal ions in phloem has been used to assess the degree to which the widely used herbicide glyphosate binds to Fe(3+), Fe(2+), Cu(2+), Zn(2+), Mn(2+), Ca(2+), and Mg(2+) in this fluid over the pH range of 8 to 6.5. The calculations show that glyphosate is largely unable to compete effectively with the biological chelating agents in phloem. At a typical phloem pH of 8, 1.5 mM glyphosate binds 8.4% of the total Fe(3+), 3.4% of the total Mn(2+), and 2.3% of the total Mg(2+) but has almost no effect on the speciation of Ca(2+), Cu(2+), Zn(2+), and Fe(2+). As the pH decreases to 6.5, there are some major shifts of the metal ions among the biological chelators, but only modest increases in glyphosate binding to 6% for Fe(2+) and 2% for Zn(2+). The calculations also indicate that over 90% of the glyphosate in phloem is not bound to any metal ion and that none of the metal-glyphosate complexes exceed their solubility limits.     

THE SPECIFIC ADSORPTION OF DIVALENT Cd, Co, Cu, Pb, AND Zn ON GOETHITE

The specific adsorption of divalent Cd, Co, Cu, Pb, and Zn on goethite is measured as a function of pH. For each mole of heavy metal adsorbed approximately two moles of H+ ions are displaced from the interface. Using these results the heavy metal adsorption data are expressed as functions of the solution concentrations of both H+ and metal ions, and the interfacial reaction is described by the equation, ₂SH+M²⁺= S₂M+₂H⁺. The adsorption data are consistent with an electrochemical model of the simultaneous adsorption of H⁺ ions and divalent metal ions on to the oxide. The intrinsic affinities of the metal ions for the oxide surface increase in the order, Cd < Co < Zn < Pb < Cu. However, besides the affinity of the metal ion for the surface, the adsorption curves are considered to be influenced by surface charge, the adsorption density of the metal ions and their size. The analysis of the data in terms of H⁺ and M²⁺ ion adsorption is considered to be complementary to the hydrolysis model for heavy metal adsorption.     

Metal ions restore the proteolytic resistance of denatured conglutin gamma, a lupin seed glycoprotein, by promoting its refolding

The susceptibility to trypsin of conglutin gamma, a lupin seed glycoprotein affected by this enzyme only when in a non-native conformation, was used to study the effect of Zn(2+) and other metal ions on the structural dynamics of the protein. When acid-treated trypsin-susceptible conglutin gamma was incubated at neutral pH in the presence of Zn(2+), it became resistant to tryptic attack, contrary to the protein treated in the absence of Zn(2+). The time course of this refolding event has been quantitatively evaluated by SDS-PAGE. Amino acid sequencing of the major polypeptide fragments, produced by trypsin before completion of the refolding process, indicated that only a few cleavable bonds were accessible to the enzyme. This suggested that the presence of metal ions affected the pathway of degradation of the protein, by inducing its folding. Among the other metal ions tested, Ni(2+) also promoted the adoption of a trypsin-resistant conformation of conglutin gamma, whereas Mn(2+) and Ca(2+) had only much lower effects. The relevance of these findings for a deeper understanding of the in vivo degradation of plant food proteins and how it is affected by metal ions are discussed.     

膨润土对重金属离子的竞争性吸附研究

通过间歇震荡平衡法研究了膨润土对4种重金属离子Cd2+、Zn2+、Cu2+、Pb2+的竞争性吸附特性及其机制。研究结果表明:与单一离子体系比较,膨润土在竞争体系中对Cd2+、Zn2+、Cu2+、Pb2+4种重金属离子的吸附量均呈下降趋势。竞争体系下,其它重金属离子的存在显著抑制了膨润土对Cd2+的吸附,降幅为19.20%~37.50%,而对Pb2+的吸附能力几乎没有影响,降幅仅为0.41%~2.83%。膨润土对4种重金属离子的富集系数,其大小顺序依次为Pb2+>Cu2+>Zn2+>Cd2+。该选择性吸附顺序与重金属离子的一级水解常数密切相关。     

香蕉纤维素-壳聚糖/聚丙烯酰胺双网络水凝胶的制备及吸附性能

纤维素、壳聚糖等天然多糖形成的水凝胶力学性能较弱,在应用中受到限制。该文利用香蕉纤维素-壳聚糖为第一层刚性网络,以聚丙烯酰胺为第二层柔性网络,通过"一锅法"制备了香蕉纤维素-壳聚糖/聚丙烯酰胺(cellulosechitosan/polyacrylamide, Ce-Cs/PAAM)双网络水凝胶,并采用傅里叶红外光谱(Fourier transform infrared spectroscopy,FTIR)、扫描电子显微镜(scanning electron microscope,SEM)、X射线衍射(X-ray diffractometer,XRD)等对双网络水凝胶结构进行了表征,并分析其力学性能、溶胀性能和吸附性能。结果表明,Ce-Cs/PAAM水凝胶是一种三维多孔、双网络状结构,具有优良的机械强度和韧性,在90%的压缩应变下,其最大压缩应力可以达到60 MPa;水中的溶胀度为9.56 mg/mg,在pH值为12的溶液中溶胀度为15.34 mg/mg;Ce-Cs/PAAM双网络水凝胶吸附Cu^2+试验结果表明,在Cu2+的初始浓度为350 mg/L、pH值为5.5、吸附时间为90 min时,最大吸附量为312.4 mg/g。该文制备的CeCs/PAAM双网络水凝胶方法简单、力学性能、吸附性能优良,在重金属离子吸附领域具有一定的应用前景。     

天然沸石对重金属离子的竞争性吸附研究

通过室内分析的方法研究了天然沸石对4种重金属离子Cd2 、Zn2 、Cu2 、Pb2 的竞争性吸附特性。研究结果表明,与单一离子体系比较,沸石在竞争体系中对Cd2 、Zn2 、Cu2 、Pb2 4种重金属离子的吸附量均呈下降的趋势。竞争体系下,其它重金属离子的存在显著地抑制了沸石对Cd2 的吸附,而对Pb2 的吸附几乎没有影响。天然沸石对4种重金属离子的富集系数,其大小顺序依次为Pb2 >Cu2 >Zn2 >Cd2 。该选择性吸附顺序可能与重金属离子的水合能、离子半径、有效水合离子半径等因素密切相关。     

Comparison of Heavy Metal Adsorptions by Thai Kaolin and Ballclay

The adsorption characteristics of heavy metals: cadmium(II), chromium(III), copper(II), nickel(II), lead(II), and zinc(II) ions by kaolin (kaolinite) and ballclay (illite) from Thailand were studied. This research was focussed on the pH, adsorption isotherms of single-metal solutions at 30–60 °C by batch experiments, and on ion selectivityin mixed and binary combination solutions. It was found that, except Ni, metal adsorption increased with increased pH of the solutions and their adsorption followed both Langmuir and Freundlich isotherms. Adsorption of metals in the mixture solutions by kaolin was: Cr > Zn > Cu ≈ Cd ≈ Ni > Pb, and for ballclay was: Cr > Zn > Cu > Cd ≈ Pb > Ni. The adsorption of metals was endothermic, with the exception of Cd, Pb and Zn for kaolin, Cu and Zn for ballclay. Kaolin and ballclay exhibited relatively hard Lewis base adsorption site. The presence of other metals may reduce or promote the adsorption of heavy metals. The presence of Cr³⁺ induced the greatest reduction of metal adsorptiononto kaolin, as did the presence of Cu²⁺ for ballclay.     

The effect of pH on the retention of Cu,Pb, Zu and Cd by clay-humic acid mixtures

The amount of metal ion sorbed by the solids increased with increasing pH over the range 3 to 6, and with mixtures of clay-cellulose or illite-humic acid the uptake corresponded to the direct addition of individual substrate adsorption values. When the humic acid samples were admixed with Na⁺-form kaolinite or montmorillonite, there was some reduction in adsorption, attributable to component interactions, and this effect was most marked in the presence of Cu and Zn ions. In alkaline media there was competition between the ability of the organic material to form soluble metal humates and the tendency of the clays to strongly retain the sparingly soluble metal hydroxy species formed at pH > 6. In most systems studied retention by the solid phase predominated. In the presence of tannic acid there were distinct pH regions in which the four metal ions formed compounds of limited solubility, with the pH for maximum precipitation ranging from 4.5 (Cu) to 7 (Cd). The introduction of clay suspensions increased the amount precipitated/sorbed in these pH regions. The amount of Cu, Pb, Zn or Cd retained by mixed suspensions varied markedly with pH, nature of the clay and the chemical nature of organic components.     

Suitability of Mn-Oxihydroxides from Karst Caves as Filter Material for Drinking Water Treatment in Gunung Sewu,Indonesia (6 pp)

Background, Aim and Scope   Manganese oxides are widely known as highly efficient heavy metal adsorbing materials. Therefore the use of natural materials containing Mn-oxihydroxides for the treatment of drinking water containing heavy metals in developing countries could be a cheap but nevertheless practical method. In the Karst area of Gunung Sewu, Java, Indonesia, people use the underground water resources as drinking water, which are endangered by heavy metal pollution. Local household filters have been considered for heavy metal elimination, to guarantee high quality drinking water from the Karst water. The aim of this study was to examine the suitability of mineral deposits containing Mn-oxihydroxides found in the Karst cave Bribin as filter material. Materials and Methods: Batch experiments were performed with the selected divalent cations Cd2+, Zn2+ and Ni2+ to test the adsorption efficiency of the Mn-rich deposits from Bribin to immobilize dissolved heavy metals. Results: Maximum adsorption capacities of 285 μmol/g for Cd2+, 217 μmol/g for Zn2+, and 178 μmol/g for Ni2+ were achieved after 24 h reaction time. These values are higher than literature values of Ni, Cd and Zn adsorption to other synthetic and natural manganese oxides. Discussion: Kinetic data from the batch experiments suggest that metal fixation occur in two steps; fast surface adsorption followed by a slower intercalation of the metal ions into the Mn-oxihydroxide lattice. Multi-element analysis of blank samples and samples under competitive conditions implies no desorption of metals from Mn-oxihydroxides. Conclusions: The sorption kinetics and capacities achieved in these experiments suggest that Mn-oxihydroxides from Bribin could be an effective filter material for drinking water purification. Recommendations and Perspectives: Nevertheless, reducing conditions in a filter system must be avoided to prevent Mn-oxides being reductively dissolved and the sorbed heavy metals mobilized.     

Xylan-rich hemicelluloses-graft-acrylic acid ionic hydrogels with rapid responses to pH, salt, and organic solvents

Exploitation of biomaterials derived from renewable resources is an important approach to address environmental and resource problems in the world today. In this paper, novel ionic hydrogels based on xylan-rich hemicelluloses were prepared by free radical graft copolymerization of acrylic acid (AA) and xylan-rich hemicelluloses (XH) by using N,N-methylene-bis(acrylamide) (MBA) as cross-linker and ammonium persulfate/N,N,N',N'-tetramethylethylenediamine (APS/TMEDA) as redox initiator system. The network characteristics of the ionic hydrogels were investigated by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), as well as by determination of mechanical properties, swelling, and stimuli responses to pH, salts, and organic solvents. The results showed that an increase in the MBA/XH or AA/XH ratio resulted in higher cross-linking density of the network and thus decreased the swelling ratio. Expansion of the network hydrogels took place at high pH, whereas shrinkage occurred at low pH or in salt solutions as well as in organic solvents. The ionic hydrogels had high water adsorption capacity and showed rapid and multiple responses to pH, ions, and organic solvents, which may allow their use in several areas such as adsorption, separation, and drug release systems.     

Surface entrapment of toxic metals from electroplating waste and their possible recovery

Heavy metal ions such as Cr, Ni, Cu, Cd and Zn have been removed from the electroplating waste using Fe(III) hydroxide as adsorbent. The maximum removal of these metal ions (>90%) occurred at pH 8 to 9. Removal of SO ₄ ^2? (98%) occurred at pH 4. Anions were found to play a negative role in the adsorption phenomenon. Metal ion Sorption has been found to decrease with increasing anionic concentrations. The methodology proposed might provide an inexpensive and economical procedure for removal and recovery of toxic metals from electroplating wastes.     

Influence of humate-solute interactions on aqueous heavy metal ion levels

The extent to which heavy metal ions (Cu, Pb, Zn, Cd) are removed from aqueous solution by humic acid suspensions has been found to vary with solution pH, concentration of competing cations, nature of the organic material, and the complexing power of any ligands present. The amount adsorbed in acid media increased with pH until the threshold value required for partial dissolution of the solid, and formation of soluble metal humates, was exceeded The adsorption maximum pH, and the apparent capacity at lower values, varied with the substrate used and cation being sorbed. The affinity order sequence, as derived from adsorption isotherm studies, was Pb > Cu > Cd > Zn ? Ca > Mg. The retention of metal ion by the solid was reduced in the presence of ligands, with zero uptake occurring when the soluble complexes formed had a greater effective stability than those resulting from humic acid-metal ion interactions. With environmental systems having a high organic content, the humic acid component can play a dominant role in determining the final distribution of metal ions, and for predictive purposes, investigation of the effect of pH on uptake is more informative than measurement of adsorption isotherm parameters, since the observed trends reflect differences in functional group properties, relative affinities and solubility effects. The curves have minima which fall within the pH spreads encountered in natural systems, and small pH changes can cause significant variations in solution levels.     

铵饱和沸石对几种重金属离子的吸附解吸特性影响研究

通过室内分析的方法比较了天然沸石及铵饱和沸石对重金属离子Cd2+、Zn2+、Cu2+、Pb2+的吸附及解吸特性。研究结果表明:铵饱和沸石对4种重金属离子的吸附量大小顺序依次为Pb>Cu>Zn>Cd,而解吸量和解吸率的大小顺序为Cd>Zn>Cu>Pb,这主要与四种金属离子的水合离子半径和水合能密切相关。与天然沸石相比,铵饱和沸石一方面增加了对4种重金属离子的吸附,同时又降低了其解吸率。原因是铵饱和沸石的阳离子交换量和比表面积有所增加,同时铵饱和沸石的孔穴和通道也较天然沸石更加均一和畅通。因此,铵饱和沸石在农业生产实践中,特别是土壤污染治理方面具有广阔的应用前景。     

Adsorption,desorption and extractability of Zn in some Algerian soils under orange cultivation

The Zn adsorption/desorption in some Algerian soils, which are under orange cultivation, was studied and the results obtained were analyzed using Langmuir equation. The maximum amount of Zn adsorbed, in majority of cases, varies between 60 and 80 % of the cation exchange capacity. As regards sequential desorption, the EDTA desorbed about 80 %of the Zn adsorbed, whereas, the desorption through 1 N KCI averaged about 15 % only. The adsorption maximum (Sm) and desorption maximum (Rm) correlate significantly with various soils properties, like clay content, cation exchange capacity and pH. The calculation of distribution coefficient (Kd) and adsorption density of Zn (r) indicates that the metal above 2.5 · 10 ions/m2 is adsorbed through ion exchange, whereas below this value, the ion is most possibly adsorbed due to specific adsorption mechanisms.     

Antioxidative ability of lactic acid bacteria

Nineteen strains of lactic acid bacteria were investigated for antioxidative activity. These includedLactobacillus acidophilus B, E, N1, 4356, LA-1, and Farr; Lactobacillus bulgaricus 12 278, 448, 449, Lb, 1006, and 11 842; Streptococcus thermophilus 821, MC, 573, 3641, and 19 987; and Bifidobacterium longum B6 and 15 708. Intracellular cell-free extract of all strains demonstrated antioxidative activity with inhibition rates of ascorbate autoxidation in the range of 7-12%. Antioxidative mechanisms including metal ion chelating ability, scavenge of reactive oxygen species, enzyme inhibition, and reducing activity of intracellular cell-free extract of lactic acid bacteria were studied. S. thermophilus 821 had the highest metal ion chelating ability for Fe(2+), and B. longum 15 708 showed the highest Cu(2+) chelating ability among the 19 strains tested. All strains demonstrated reactive oxygen species scavenging ability. L. acidophilus E showed the highest hydroxyl radical scavenging ability, and B. longum B6 had the best hydrogen peroxide scavenging ability. Reducing activity was also found in all strains. Most of the strains tested demonstrated excellent reducing activity. B. longum B6 showed the highest reducing activity among the 19 strains tested. In enzyme inhibition, superoxide dismutase activity was not found in these 19 strains, and the activity of superoxide dismutase was not induced when metal ion Mn(2+), Fe(2+), or Cu(2+)Zn(2+) was present.     

Use of Gisenyi Volcanic Rock for Adsorptive Removal of Cd(II), Cu(II), Pb(II), and Zn(II) from Wastewater

Volcanic rock is a potential adsorbent for metallic ions from wastewater. This study determined the capacity of Gisenyi volcanic rock found in Northern Rwanda to adsorb Cd, Cu, Pb and Zn using laboratory scale batch experiments under a variety of experimental conditions (initial metal concentration varied from 1 to 50 mg/L, adsorbent dosage 4 g/L, solid/liquid ratio of 1:250, contact time 120 h, particle size 250–900 μm). The adsorbent had a surface area of 3 m²/g. The adsorption process was optimal at near-neutral pH 6. The maximal adsorption capacity was 6.23, 10.87, 9.52 and 4.46 mg/g for Cd, Cu, Pb and Zn, respectively. The adsorption process proceeded via a fast initial metal uptake during the first 6 h, followed by slow uptake and equilibrium after 24 h. Data fitted well the pseudo second-order kinetic model. Equilibrium experiments showed that the adsorbent has a high affinity for Cu and Pb followed by Cd and Zn. Furthermore, the rock is a stable sorbent that can be reused in multiple sorption–desorption–regeneration cycles. Therefore, the Gisenyi volcanic rock was found to be a promising adsorbent for heavy metal removal from industrial wastewater contaminated with heavy metals.     

Preparation of specific monoclonal antibodies (MAbs) against heavy metals: MAbs that recognize chelated cadmium ions

Monoclonal antibodies (MAbs) were produced against chelated Cd (2+). Since Cd (2+) ions are too small to elicit an immune response, the metal was coupled to protein carrier (keyhole limpet hemocyanin, KLH) using a bifunctional chelator 1-(4-isothiocyanobenzyl)ethylenediamine N, N, N', N'-tetraacetic acid (ITCBE). Several mice were immunized with this Cd (2+)-ITCBE-KLH immunoconjugate. Spleen cells of two immunized mice were fused with myeloma cells, and the resulting hybridomas were screened using protein conjugates with covalently bound metal-free ITCBE (ethylenediamine tetraacetic acid) or Cd (2+)-ITCBE. Four hybridoma cell lines that produced MAbs with high selectivity and sensitivity (Aa4, Aa6, Ac4, and Ba2) were expanded for further study. Cross-reactivities with other metals were below 1% except for Hg (2+), which showed a slight cross-reactivity in competitive ELISA. These antibodies were used to construct competitive ELISAs for ionic cadmium; the IC 50 of the four antibodies (Aa4, Aa6, Ac4, and Ba2) were 10.59, 4.19, 29.45, and 6.63 microg/L, respectively. The detection range and the lowest detection limit for cadmium, using the Aa6 antibody, were 2.19-86.38 microg/L and 0.313 microg/L, respectively. Spike-recovery studies in tap and stream water showed that the most sensitive antibody can be used for cadmium detection in drinking water.     

Chemical Characteristics of Precipitation at an Atlantic Station

Weekly or half-monthly bulk rainwater samples were collected over 3 yr (1993–1995) at Porspoder, an Atlantic station near Brest, France. They were analyzed for 0.08 M HNO3-leachable trace metals Cd, Cu, Fe, Mn, Ni, Pb and Zn by direct electrothermal atomic absorption spectrometry. Major ions and nitrogen species (NO3- and NH4+) in precipitation were determined by ion chromatography. In coastal precitation, a high correlation was observed for major ions having a seawater origin (Na+, CL- and Mg2+. Zn, Cd, Cu, Ni and Pb were well correlated indicating their anthropogenic origin. In the case of nitrogen species and nssSO42- a high correlation with Zn was observed, taken as an anthropogenic pollution tracer. Major ions and nitrogen species were determined according to wind sector direction showing clearly the impact of the pollution at this station attributed to continental air masses. A relative constancy of pH values in all wind directions was observed. Due to an important oceanic influence, trace metal concentrations and annual deposition densities were significantly lower at Porspoder than at North Sea coastal stations. In the case of nitrogen species, the relatively higher concentration levels probably indicated a significant local agricultural contribution.     

Reaction kinetics of the adsorption and desorption of nickel, zinc and cadmium by goethite. I. Adsorption and diffusion of metals

The reactions of Ni, Zn and Cd with goethite were studied over a range of initial metal concentrations (10⁻⁶ to 10⁻⁴M), pH values (4 to 8), reaction times (2h to 42d) and temperatures (5 to 35°C). The adsorption of metals increased with pH, reaction time and temperature. Adsorption of Ni increased relative to Zn and Cd with increasing time and temperature. The initially rapid adsorption of metals within a few hours was followed by a much slower reaction linearly related to time^1/2, interpreted as diffusion–controlled penetration of goethite. The pH–dependent relative diffusion rates (Ni > Zn > Cd) were influenced by both affinity for goethite surfaces and by ionic radius. Diffusion coefficients of the three metals ranged from about 10⁻¹⁹to 10⁻²⁰cm²s⁻¹. The corresponding activation energies of diffusion were also calculated (Ni 35, Cd 55, Zn 90 kJ mol⁻¹). Our view about the reactions of heavy metals with goethite involves (i) adsorption of metals on external surfaces, (ii) solid–state diffusion of metals from external to internal binding sites, and (iii) metal binding and fixation at positions inside the goethite particles. The general parameters of these processes are related to the hydrolytic properties (p K values) and the ionic radii of the metals. The results show that goethite may be an efficient sink for trace metals.