Biosorption of copper(II) from aqueous solutions by pre-treated biomass of marine algae Padina sp

Biosorption of heavy metals can be an effective process for the removal and recovery of heavy metal ions from aqueous solutions. The biomass of marine algae has been reported to have high uptake capacities for a number of heavy metal ions. In this paper, the adsorption properties of a pre-treated biomass of marine algae Padina sp. for copper(II) were investigated. Equilibrium isotherms and kinetics were obtained from batch adsorption experiments. The biosorption capacities were solution pH dependent and the maximum capacity obtained was 0.80 mmol/g at a solution pH of about 5. The biosorption kinetics was found to be fast, with 90% of adsorption within 15 min and equilibrium reached at 30 min. The effects of light metal ions on copper(II) uptake were studied and the presence of light metal ions did not affect copper(II) uptake significantly. Fixed-bed breakthrough curves for copper(II) removal were also obtained. This study demonstrated that the pre-treated biomass of Padina sp. could be used as an effective biosorbent for the treatment of copper(II) containing wastewater streams.     

浮游球衣菌对Pb2+、Cu2+、Zn2+、Cd2+的吸附性能研究

研究了浮游球衣菌（Sphaerotilus natans）在不同吸附条件下对溶液中Pb^2＋、Cu^2＋、Zn^2＋、Cd^2＋的吸附规律。结果表明,Sphaerotilus natans对这4种重金属离子均有一定的吸附作用,并在20min内达到吸附平衡,pH对吸附过程影响较大,pH为5.5时Sphaerotilus natans对这4种金属离子的吸附效果最好,Sphaerotilus natans对它们的吸附选择性为Pb^2＋〉Cu^2＋〉Zn^2＋〉Cd^2＋,Pb^2＋、Cu^2＋能部分置换出已被菌体吸附的Zn^2＋、Cd^2＋。HCI和EDTA溶液可有效地将金属离子从菌体上解吸下来,解吸后的菌体可重复使用。     

The effect of operating variables on chelant-assisted remediation of contaminated dredged sediment

The paper shows the results from a number of lab-scale washing treatments using the four chelating agents EDTA, NTA, citric acid and [S,S]-EDDS aiming at the remediation of a real heavy metal-contaminated sediment. Investigation of the influence of chelant type and concentration as well as solution pH was the major focus of the work. The analysis of speciation of metals and chelating agents in solution was carried out through geochemical speciation modelling in order to identify the optimal conditions for the washing process as well as to evaluate the competition phenomena of metal-chelant complexes in solution. The major competing cations were found to be Ca above all and Mg under specific conditions. Among the investigated chelating agents, EDDS appeared to be less affected by competition by major cations while ensuring adequate heavy metal extraction efficiencies. For a 1:1 chelant/metal ratio, the following ranking was observed: EDDS>Cit>NTA>EDTA for As, EDDS>NTA congruent withEDTA>Cit for Cu, EDDS congruent withEDTA congruent withNTA>Cit for Zn, EDTA>NTA>EDDS>Cit for Pb at pH 5 and EDTA congruent withEDDS congruent withNTA>Cit for Pb at pH 8. For a 10:1 chelant/metal ratio geochemical modelling indicated that at the equilibrium the extracting solutions were dominated by the free form of the chelating agents, indicating the inability of such species to complex trace metals due the strong interactions existing between heavy metal ions and sediment constituents.     

DGT use in contaminated site characterization. The importance of heavy metal site specific behaviour

The objective of this study is to provide an insight into the techniques for measuring the lability of heavy metals in solid-phase pool of soils in order to assess the environmental risk arising from pollution. The technique of diffusive gradients in thin films (DGT) and a sequential extraction procedure were used to quantify the labile pools of Cu, Fe, Mn and Ni. These results were compared to metal concentrations in groundwater, measured directly using the in situ piezometers, and to the total concentration of metal in the soils. High concentrations of metal in the directly analysed soil solution compared to DGT measurement were attributed to the presence of colloidal metal. The use of DGT allowed only to calculate leaching parameters of the free ions and labile fractions of the metals. For this reason DGT technique needs preliminary investigation on metal speciation in soil solution before its application as a good tool in the characterization procedure of contaminated sites.     

Metal uptake capacity of modified Saccharomyces pastorianus biomass from different types of solution

In this paper, we investigate the effect of different biomass pretreatments on metal ion uptake by various biosorbents. Heat-treated as well as caustic-treated and ground biomass of Saccharomyces pastorianus was used to remove copper, lead and cadmium from various solutions. Untreated yeast was used as the control sample. The effect of yeast modification on sorption capacity depended on the different types of heavy metal ions and whether they were in single- or multi-component solutions. The highest uptake of copper and lead from a single-metal solution was obtained from heat-treated cells. Ground biomass was the most efficient at cadmium removal. However, the sorption capacity of the modified biomass did not improve when metal ions were removed from multi-component solutions. Indeed, the results in this paper show that optimizing metal removal from single-cation solutions can lead to decreased sorption capacity in multi-component solutions. Therefore, while adjusting the procedure of biomass modification, not only the nature of the metal ion being sorbed but also the chemical composition of the metal ion solution should be taken into account.     

Removal of heavy metal ions from water by complexation-assisted ultrafiltration

Toxic heavy metals in air, soil and water are global problems that are growing threat to the environment. Therefore, the removal and separation of toxic and environmentally relevant heavy metal ions are a technological challenge with respect to industrial and environmental application. A promising process for the removal of heavy metal ions from aqueous solutions involves bonding the metals to a bonding agent (such as macromolecular species), and then separating the loaded agents from wastewater by separation processes such as membrane filtration. The choice of water-soluble macroligands remains important for developing this technology. The effects of type of complexing agent, pH value and applied pressure on retention coefficients of Zn(II) and Cd(II) complexes were investigated. At best operating conditions (pH=9.0, p=300kPa) using diethylaminoethyl cellulose, the removal of Cd(2+) and Zn(2+) was more than 95% and 99%, respectively.     

Sequestering of heavy metal ions from aqueous solutions by using a lignocellulosic material

The ability of Brown Stock Washer (BSW) unbleached kraft pulp and Chemi-Thermo-Mechanical Pulp (CTMP) to sequester heavy metals was studied. The BSW pulp is chemically produced while the CTM one is produced by mechanical treatment aided by some chemicals. The two pulps were rendered in their protonated form and then equilibrated with two aqueous solutions of metals. One was ocean water and the other was a laboratory prepared solution of metal ions. Both pulps were able to remove metal ions from the solution in a one-stage procedure. The overall metal removal efficiency of CTMP was in general greater than that of the BSW pulp for the low concentration metals.     

改性γ-聚谷氨酸络合重金属离子性能

研究了不同控制条件(温度、Pb2+浓度、pH)对交联改性γ-聚合谷氨酸(γ-PGA)吸附重金属离子所形成的絮凝颗粒性质的影响,对于治理水中重金属污染的相关研究有一定参考价值。实验表明,C-L-γ-PGA絮凝吸附Pb2+的最佳温度段在30℃附近。随着交联度的增加,不同的Pb2+浓度影响絮凝颗粒的大小,当处于较低浓度时,静电引力成为影响絮凝颗粒粒径最主要的因素,当Pb2+浓度增加到一定程度时,重金属的吸附量成为絮凝颗粒的粒径的决定因素。溶液pH达到7附近时,能够形成粒径最大的絮凝颗粒,并出现了最大的Pb2+去除率。C-L-γ-PGA对其他重金属离子也有类似的吸附絮凝作用,且絮凝吸附强弱顺序为Cu2+>Cr3+>Pb2+>Hg2+。吸附絮凝颗粒的粒径反映了重金属被吸附之后分离的难易程度,因此研究不同条件对絮凝颗粒粒径的影响对重金属离子的吸附和去除有重要意义。     

The removal of heavy metals in urban runoff by sorption on mulch

A series of adsorption experiments was conducted in order to assess the ability of three mulches to remove several of the heavy metal ions typically encountered in urban runoff. Three types of mulch, cypress bark (C), hardwood bark (H), and pine bark nugget (P), were selected as potential sorbents to capture heavy metals in urban runoff. The hardwood bark (H) mulch had the best physicochemical properties for adsorption of heavy metal ions. In addition, because of its fast removal rate and acceptably high capacity for all the heavy metal ions, it was concluded that the H mulch is the best of the three adsorbents for treatment of urban runoff containing trace amounts of heavy metals. In order to investigate the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. The sorption of these metals on H mulch conformed to the linear form of the Langmuir adsorption equation. At pH 5 and 6, the Langmuir constants (S(m)) for each metal were found to be 0.324 and 0.359 mmol/g (Cu); 0.306 and 0.350 mmol/g (Pb); and 0.185 and 0.187 mmol/g (Zn) at 25 degrees C.     

Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid

Arsenic and heavy metal mobilization from mine tailings is an issue of concern as it might pose potential groundwater or ecological risks. Increasing attention recently has been focused on the effects of natural organic matter on the mobility behavior of the toxicants in the environment. Column experiments were carried out in this research study to evaluate the feasibility of using humic acid (HA) to mobilize arsenic and heavy metals (i.e., Cu, Pb and Zn) from an oxidized Pb-Zn mine tailings sample collected from Bathurst, New Brunswick, Canada. Capillary electrophoresis analyses indicated that arsenate [As(V)] was the only extractable arsenic species in the mine tailings and the addition of HA at pH 11 did not incur the oxidation-reduction or methylation reactions of arsenic. A 0.1% HA solution with an initial pH adjusted to 11 was selected as the flushing solution, while distilled water (initial pH adjusted to 11) was used as the control to account for the mobilization of arsenic and the heavy metals by physical mixing and the effect of pH. It was found that the HA could significantly enhance the mobilization of arsenic and heavy metals simultaneously from the mine tailings. After a 70-pore-volume-flushing, the mobilization of arsenic, copper, lead and zinc reached 97, 35, 838 and 224 mg kg(-1), respectively. The mobilization of arsenic and the heavy metals was found to be positively correlated with the mobilization of Fe in the presence of the HA. Moreover, the mobilization of arsenic was also correlated well with that of the heavy metals. The mobilization of co-existing metals to some extent might enhance arsenic mobilization in the presence of the HA by helping incorporate it into soluble aqueous organic complexes through metal-bridging mechanisms. Use of HA in arsenic and heavy metal remediation may be developed as an environmentally benign and possible effective remedial option to reduce and avoid further contamination.     

Preparation of macromolecular heavy metal coagulant and treatment of wastewater containing copper.

Many treatment technologies for wastewater containing heavy metals have been developed in recent years, but these technologies have some disadvantages, such as poor removing efficiency and complex operation. For this reason, a macromolecular heavy metal coagulant polyethyleneimine-sodium xanthogenate (PEX) was prepared by grafting a xanthogenate group to polyethyleneimine. It was determined that PEX has the function of removing both turbidity and copper ions. It was also determined that copper ions and turbidity have a cooperative removal effect with each other in the process of treating wastewater containing both turbidity and copper ions by PEX. The investigation showed that PEX is an amphoteric polyelectrolyte. At lower pH values, the amino groups of the macromolecule are electrically positive; therefore, turbidity is removed because of electroneutralization coagulation; at higher pH values, both amino groups and xanthogenic radical groups contribute to the removal of heavy metals, as a result of chelation. Compared with traditional chemical precipitation by calcium oxide and coagulation by an ordinary inorganic coagulant, PEX showed obvious advantages, for example, removing both turbidity and copper ions, higher removal efficiency, lower suitable pH value, and higher floc settlement velocity.     

Biosorption of Cr3+, Cd2+ and Cu2+ ions by blue-green algae Spirulina sp.: kinetics, equilibrium and the mechanism of the process

The process of biosorption of heavy metal ions (Cr3+, Cd2+, Cu2+) by blue-green algae Spirulina sp. is discussed in this paper. Spirulina sp. was found to be a very efficient biosorbent. The aim of the present study was to investigate quantitatively the potential binding sites present at the surface of Spirulina sp., using both potentiometric titrations and adsorption isotherms. The kinetic experiments showed that the process equilibrium was reached quickly, in less than 5-10 min. It was found that the equilibrium dependence between biosorption capacity and bulk metal ion concentration could be described with Langmuir equation. This suggests that the mechanism of biosorption is rather chemisorption than physical adsorption and was further confirmed by the low surface area associated with physical adsorption and by the presence of cations that appeared in the solution after biosorption. The maximum contribution of physical adsorption in the overall biosorption process was evaluated as 3.7%. It was proposed that functional groups on the cell surface contributed to the binding of metal ions by a biosorbent via equilibrium reaction. Three functional groups capable of cation exchange were identified on the cell surface. The biomass was described as weakly acidic ion exchanger. Since deprotonation of each functional group depends on pH, the process of biosorption is strongly pH-dependent. This was confirmed in the biosorption experiments carried out at different pH. The contribution of functional groups in the biosorption process was confirmed by chemical modification of the groups. Chemically blocked groups did not show neither biosorption nor ion-exchange capabilities. It has been shown that growth conditions can affect the metal adsorption properties of microalgae. The paper also discusses desorption characteristics of the biosorbent. The criteria for desorption were high elution efficiency and preservation of biosorptive properties. Desorbent that possessed these characteristics was nitric acid.     

三乙二醇二甲基丙烯酸酯为交联剂制备的高吸水树脂对重金属的吸附

以前期工作中合成的树脂PAANa-TE为吸附剂进行重金属吸附测试,考察吸附剂用量、丙烯酸中和度、吸附时间、溶液pH、初始浓度和吸附温度对树脂吸附重金属离子Cu2+、Pb2+、Cr3+和Co2+性能的影响,用原子吸收分光光度计测定了树脂吸附Cu2+、Pb2+、Cr3+和Co2+后的残留浓度,树脂对4种金属离子的吸附容量分别为21.59、2.39、5.66和4.98 mmol/g,吸附容量大小为Cu2+Cr3+Co2+Pb2+,吸附速率顺序为Cr3+Pb2+Cu2+Co2+。结果表明,该树脂对高浓度重金属离子有较快速,高效率的吸附,吸附过程在100 min左右吸附容量达到最大,并用不同浓度的酸对吸附重金属离子的树脂进行脱附处理,脱附量很小,据此可考虑进一步对金属离子进行回收处理。且脱附率较低,因此,可对工业化和城市化进程所产生的各种化学形态的重金属水体污染物造成的生态环境和质量问题起到重要的改善作用。     

Loofa sponge immobilized fungal biosorbent: a robust system for cadmium and other dissolved metal removal from aqueous solution

The potential of loofa sponge discs to immobilize fungal biomass of Phanerochaete chrysosporium (a known biosorbent) was investigated as a low cost biosorbent for the removal of Cd(II) ions from aqueous solution. A comparison of the biosorption of Cd(II) by immobilized and free fungal biomass from 10 to 500 mg l(-1) aqueous solutions showed an increase in uptake of over 19% when the biomass is immobilized (maximum biosorption capacity of 89 and 74 mg Cd(II) g(-1) biomass for immobilized and free biomass respectively at a solution pH of 6). Equilibrium was established within 1h and biosorption was well defined by the Langmuir isotherm model. The immobilized biomass could be regenerated using 50 mM HCl, with up to 99% metal recovery and reused in ten biosorption-desorption cycles without significant loss of capacity. This study suggests that such an immobilized biosorbent system has the potential to be used in the industrial removal/recovery of cadmium and other pollutant metal ions from aqueous solution.     

Removal of Ni(II) and Cu(II) ions using native and acid treated Ni-hyperaccumulator plant Alyssum discolor from Turkish serpentine soil

Alyssum discolor biomass was collected from serpentine soil and was used for removal of metal ions. The plant species grown on serpentine soils are known to be rich with metals ions and thus have more capability for accumulating heavy metals. Native and acid-treated biomass of A. discolor (A. discolor) were utilized for the removal of Ni(II) and Cu(II) ions from aqueous solutions. The effects of contact time, initial concentration, and pH on the biosorption of Ni(II) and Cu(II) ions were investigated. Biosorption equilibrium was established in about 60 min. The surface properties of the biomass preparations were varied with pH, and the maximum amounts of Ni(II) and Cu(II) ions on both A. discolor biomass preparations were adsorbed at pH 5.0. The maximum biosorption capacities of the native, and acid-treated biomass preparations for Ni(II) were 13.1 and 34.7 mg g⁻¹ and for Cu(II) 6.15 and 17.8 mg g⁻¹ dry biomass, respectively. The biosorption of Ni(II) and Cu(II) ions from single and binary component systems can be successfully described by Langmuir and Freundlich isotherms. When the heavy metal ions were in competition, the amounts of biosorbed metal ions on the acid treated plant biomass were found to be 0.542 mmol g⁻¹ for Ni(II) and 0.162 mmol g⁻¹ for Cu(II), the A. discolor biomass was significantly selective for Ni(II) ions. The information gained from these studies was expected to indicate whether the native, and acid-treated forms can have the potential to be used for the removal and recovery of Ni(II) ions from wastewaters.     

Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

Application of flotation for the separation of metal-loaded zeolites

Several industrial wastewater streams may contain heavy metal ions, which must be effectively removed, before the discharge or reuse of treated waters could take place. Different bonding materials, presenting selectivity and fast reaction kinetics for the removal of metals, have been examined for this purpose. The objective of the present paper was to investigate the application of dispersed-air flotation for the separation of metal-loaded sorbents. Two similar zeolite samples were applied as effective bonding agents for the removal of zinc, a toxic metal commonly found in many industrial wastewaters. This combined process, termed sorptive flotation, involves the preliminary scavenging of metal ions, by using the appropriate sorbent particles (usually present as ultrafine particulates), followed by flotation for the effective separation of them. The obtained results were very promising, as both metal and sorbent were effectively removed/separated from the dispersion.     

Role of magnetite and humic acid in radionuclide migration in the environment

Sorption of ¹³⁷Cs, ⁹⁰Sr, ¹⁵⁴Eu and ¹⁴¹Ce by magnetite has been studied at varying pH (4 to 11) in the presence and absence of humic acid. The sorption studies have also been carried out at varying ionic strength (0.01 to 0.2 M NaClO₄) and humic acid concentration (2 to 20 mg/L). Percentage sorption of ¹³⁷Cs and ⁹⁰Sr was found to be pH dependent, with the sorption increasing with increasing pH of the suspension. At any pH, the percentage sorption of ⁹⁰Sr was higher than that of ¹³⁷Cs. The results have been explained in terms of the electrostatic interaction between the positively charged metal ions and the surface charge of the magnetite which becomes increasingly negative with increasing pH. On the other hand, ¹⁵⁴Eu and ¹⁴¹Ce were found to be strongly sorbed by the magnetite at all pH values, with the sorption being independent of pH. The strong sorption of trivalent and tetravalent metal ions suggests the role of complexation reactions during sorption, apart from the electrostatic interactions. However, in the case of ¹⁴¹Ce surface precipitation of Ce(III) formed by reduction of Ce(IV) in the presence of magnetite cannot be ruled out. Presence of humic acid (2 mg/L) was found to have negligible effect on sorption of all metal ions.     

Sorption equilibria of metal ions on bone char

The ability of bone char to adsorb three metal ions, namely, copper(II), zinc(II) and cadmium(II) ions from wastewater has been studied. Three single-component equilibrium systems and three binary equilibrium systems have been measured experimentally. The three single-component equilibrium data were analyzed using the Langmuir and the Sips equilibrium isotherm equations. The Sips isotherm gave a better fit of the experimental data than the Langmuir isotherm based on the sum of squares errors (SSE) analysis. The Cu-Zn, Cu-Cd and Cd-Zn binary equilibrium experimental data were examined by incorporating the Langmuir and the Sips isotherm equations into the ideal adsorbed solution theory (IAST). The solution methods and the predicted results for the three binary systems at different metal ion compositions have been evaluated. In addition, the application of the IAST to the model prediction for the fixed bed system is presented.