Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.     

Polyelectrolyte enhanced ultrafiltration (PEUF) for the removal of Cd(II): effects of organic ligands and solution pH

This study focused on the effects of pH and organic ligands, namely ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and citric acids, on the removal and recovery of Cd(II) in polyelectrolyte enhanced ultrafiltration (PEUF). Polyethylenimine (PEI), which can bind with both positively charged metal ions by coordination bonding and negatively charged ligand-metal complexes by charge attraction, was employed as a chelating polymer. The removal and recovery of Cd species was greatly dependent on the chemistry of organic ligands according to solution pH, particularly being related to the distribution of Cd-ligand complexes at different pH levels. In the presence of EDTA, the dominant Cd species are negatively charged Cd(EDTA)(2-) and CdH(EDTA)(-) over the range of pH levels investigated, interacting with PEI via electrostatic attraction and being less pH dependent. On the other hand, the pH effects of both NTA and citric acid systems are similar to that for the system without organic ligands. This was associated with the fact that free Cd ions were predominant at the acidic pH range in both NTA and citric acid systems.     

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.     

Industrial wastewater pre-treatment for heavy metal reduction by employing a sorbent-assisted ultrafiltration system

This work examined the adoption of a sorbent-assisted ultrafiltration (UF) system for the reduction of Pb(II), Cu(II), Zn(II) and Ni(II) from industrial wastewater. In such a system metals were removed via several processes which included precipitation through the formation of hydroxides, formation of precipitates/complexes among the metal ions and the wastewater compounds, adsorption of metals onto minerals (bentonite, zeolite, vermiculite) and retention of insoluble metal species by the UF membranes. At pH = 6 the metal removal sequence obtained by the UF system was Pb(II) > Cu(II) > Zn(II) > Ni(II) in mg g⁻¹ with significant amount of lead and copper being removed due to chemical precipitation and formation of precipitates/complexes with wastewater compounds. At this pH, zinc and nickel adsorption onto minerals was significant, particularly when bentonite and vermiculite were employed as adsorbents. Metal adsorption onto zeolite and bentonite followed the sequence Zn(II) > Ni(II) > Cu(II) > Pb(II), while for vermiculite the sequence was Ni(II) > Zn(II) > Cu(II) > Pb(II) in mg g⁻¹. The low amount of Pb(II) and Cu(II) adsorbed by minerals was attributed to the low available lead and copper concentration. At pH = 9 the adoption of UF could effectively reduce heavy metals to very low levels. The same was observed at pH = 8, provided that minerals were added. The prevailing metal removal process was the formation of precipitates/complexes with wastewater compounds.     

Removal of mercury (II) from aqueous solution by activated carbon obtained from furfural

The adsorption of Hg(II) from aqueous solution at 293 K by activated carbon obtained from furfural is studied. The carbon is prepared by polymerization of furfural following carbonization and activation of the obtained polymer material with water vapor at 800 degrees C. Adsorption studies of Hg(II) are carried out varying some conditions: treatment time, metal ion concentration, adsorbent amount and pH. It is determined that Hg(II) adsorption follows both Langmuir and Freundlich isotherms. The adsorption capacity of the carbon is 174 mg/g. It is determined that Hg(II) uptake increases with increasing pH. Desorption studies are performed with hot water. The percent recovery of Hg(II) is 6%.     

Use of natural clinoptilolite to improve water quality: sorption and selectivity studies of lead(II), copper(II), zinc(II), and nickel(II).

Natural clinoptilolite can be used as an ion exchanger for removal of heavy metals and treatment of environmental pollution because of its desirable characteristics of high ion exchange selectivity and resistance to different media. In this work, the potential of natural clinoptilolite from G?rdes mines (West Anatolia, Turkey) for the uptake of lead(II), nickel(II), copper(II), and zinc(II), from their single and mixed ion solutions, was evaluated using the batch method. The mineralogical and chemical properties of the sorption material were carried out by X-ray diffraction, X-ray fluoremetry, scanning electron microscopy, and wet analysis. Contact time, initial solution pH, solid-to-liquid ratio, and initial metal cation concentration were determined as single ion sorption parameters. The silicon/aluminum ratio and the theoretical and equivalent exchange capacities, both in single and mixed solutions, were established. Corresponding adsorption constants and distribution coefficients have been found.     

Sorption of Zn(II) in aqueous solutions by scoria

We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water.     

Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

Preparation and characterization of surfactant-modified hydroxyapatite/zeolite composite and its adsorption behavior toward humic acid and copper(II)

A novel composite material, i.e., surfactant-modified hydroxyapatite/zeolite composite, was used as an adsorbent to remove humic acid (HA) and copper(II) from aqueous solution. Hydroxyapatite/zeolite composite (HZC) and surfactant-modified HZC (SMHZC) were prepared and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscope. The adsorption of HA and copper(II) on SMHZC was investigated. For comparison purposes, HA adsorption onto HZC was also investigated. SMHZC exhibited much higher HA adsorption capacity than HZC. The HA adsorption capacity for SMHZC decreased slightly with increasing pH from 3 to 8 but decreased significantly with increasing pH from 8 to 12. The copper(II) adsorption capacity for SMHZC increased with increasing pH from 3 to 6.5. The adsorption kinetic data of HA and copper(II) on SMHZC obeyed a pseudo-second-order kinetic model. The adsorption of HA and copper(II) on SMHZC took place in three different stages: fast external surface adsorption, gradual adsorption controlled by both film and intra-particle diffusions, and final equilibrium stage. The equilibrium adsorption data of HA on SMHZC better fitted to the Langmuir isotherm model than the Freundlich isotherm model. The equilibrium adsorption data of copper(II) on SMHZC could be described by the Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. The presence of copper(II) in solution enhanced HA adsorption onto SMHZC. The presence of HA in solution enhanced copper(II) adsorption onto SMHZC. The mechanisms for the adsorption of HA on SMHZC at pH 7 may include electrostatic attraction, organic partitioning, hydrogen bonding, and Lewis acid–base interaction. The mechanisms for the adsorption of copper(II) on SMHZC at pH 6 may include surface complexation, ion exchange, and dissolution–precipitation. The obtained results indicate that SMHZC can be used as an effective adsorbent to simultaneously remove HA and copper(II) from water.     

The recovery of copper from a copper mine effluent in a hybrid flotation/microfiltration cell

A new hybrid process for cleaning wastewater, combining flotation and membrane microfiltration, was investigated. The hybrid process combined the advantages of both flotation and membrane separation: the flotation cell removed a large proportion of suspended solid particles, while the membrane module produced clean water permeate effluent. The hybrid cell performance has been studied in depth and reviewed in the current paper. The proof of concept for the hybrid solid/liquid separation process was investigated using an aqueous suspension of fine and ultra fine particles (synthetic adsorbents, ion exchangers). The feasibility of this combined process was investigated in the recovery of metal cations (copper) from a Bulgarian copper mine effluent.     

Pre-concentration and separation of heavy metal ions by chemically modified waste paper gel

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II)  Fe(III) > Pb(II) > Ni(II)  Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.     

Removal of aqueous nickel (II) using laterite as a low-cost adsorbent.

The present paper describes the laboratory study of laterite as a low-cost adsorbent for removal of aqueous nickel (II). At pH 7 and a temperature of 30 degrees C, a sorbent dose of 15 mg/L resulted in approximately 90% removal of nickel (II) from its initial concentration of 10 mg/L. A maximum removal of 98% of the adsorbate was observed with an adsorbent particle size of 210 micro with the above conditions. Batch kinetics results were described by fitting in a Langmuir isotherm. Helffrich's half-time equation (Helffrich, 1962) has been applied to evaluate the adsorption process. It appears that film diffusion would be the rate-limiting step. The effect of pH on the sorption process was carried out to a value of 8.0. The removal rate of nickel was found to be the function of pH of the reaction mixture. The rate of nickel uptake by laterite with the decrease in pH value has been explained on the basis of aqueous-complex formation and the subsequent acid-base dissociation at the solid-solution interface.     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

聚合物强化超滤处理含铜废水

聚合物强化超滤工艺（PEUF）是一种将高分子聚合物和超滤技术结合的新型、高效的重金属废水治理方法。以壳聚糖（CTS）为聚合物去除水中的铜离子。考察了吸附络合和超滤过程中影响铜去除率的多种因素。结果表明,溶液pH值为6.0、CTS浓度为0.15 g/L和反应时间为60 min时,通过超滤系统后效果最佳。装载比一定时,铜初始浓度的变化对铜的去除率没有明显影响。CTS对铜的吸附过程符合Langmuir吸附等温方程。还研究了超滤膜的污染情况和膜清洗方法,结果表明,酸清洗效果较好,可使膜通量恢复达87%左右。     

Biosorption of copper(II) by Pseudomonas aeruginosa

The mechanism of accumulation of copper(II) by Pseudomonas aeruginosa was investigated. Uptake consisted of a rapid process (likely to be extracellular binding) followed by a slow phase (possibly cellular uptake). The sorption capacity of the microbe was found to be 50 mg/g, and sorption followed the Langmuir isotherm. The presence of mild mineral acids (0.1 N HCl) led to destructive desorption of 95% of sorbed metal, whereas citrate buffer (pH 4) desorbed 80% of the accumulated metal ions non-destructively. Spectroscopic and microscopic studies indicated the accumulation of metal inside the cell, though the maximum uptake was by the cell wall.     

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.     

Compressed air-assisted solvent extraction (CASX) for metal removal

A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.     

Biomass-derived materials in the remediation of heavy-metal contaminated water: removal of Cadmium(II) and copper(II) from aqueous solutions

Manganese-coated activated carbon (MCAC) and activated carbon were used in batch experiments for the removal of cadmium(II) and copper(II). Results showed that uptake of Cd(II) and Cu(II) was unaffected by increases in pH (3.0 to 8.5) or concentration (1 to 20 mg/L). Increased ionic strength (from 0.001 to 1 M NaNO3), however, significantly affected the uptake of Cd(II); adsorption of Cu(II) was not affected. Freundlich adsorption isotherm results indicated that MCAC possessed higher sorption capacity than activated carbon. Second-order rate constants were found to be 0.0386 for activated carbon and 0.0633 g/mg x min for MCAC for Cd(II) and 0.0774 for AC and 0.1223 g/mg x min for MCAC for Cu(II). Column experiments showed that maximum sorption capacity of MCAC was 39.48 mg/g for Cu(II) and 12.21 mg/g for Cd(II).     

Biosorption of nickel(II) from aqueous solution by Aspergillus niger: Response surface methodology and isotherm study

In the present study, the effects of biosorbent Aspergillus niger dosage, initial solution pH and initial Ni(II) concentration on the uptake of Ni(II) by NaOH pretreated biomass of A. niger from aqueous solution were investigated. Batch experiments were carried out in order to model and optimize the biosorption process. The influence of three parameters on the uptake of Ni(II) was described using a response surface methodology (RSM) as well as Langmuir and Freundlich isotherm models. Optimum Ni(II) uptake of 4.82 mg Ni(II) g⁻¹ biomass (70.30%) was achieved at pH 6.25, biomass dosage of 2.98 g L⁻¹ and initial Ni(II) concentration of 30.00 mg L⁻¹ Ni(II). Langmuir and Freundlich were able to describe the biosorption isotherm fairly well. However, prediction of Ni(II) biosorption using Langmuir and Freundlich isotherms was relatively poor in comparison with RSM approaches. The biosorption mechanism was also investigated by using Fourier transfer infrared (FT-IR) analysis of untreated, NaOH pretreated, and Ni(II) loaded A. niger biomass.     

高效聚合氯化铝对超滤膜污染影响的中试研究

针对某水厂以超滤为核心的短流程水处理工艺,在通过聚氯乙烯(PVC)超滤膜之前选择不同投加量(5、10、15和20 mg/L)的高效聚合氯化铝(HPAC)对长江下游原水进行混凝处理。通过跨膜压差(TMP)增长趋势、CODMn的去除率以及混凝后的水质,可知HPAC的最优投加量为15 mg/L。在此投加量下,运用体积排阻色谱法分析原水、膜前水、膜后水中各相对分子质量有机物的变化,可以发现混凝去除有机物的效果要优于超滤截留的。继而将HPAC与另外4种常用混凝剂:硫酸铝(分析纯)、氯化铁(化学纯)、聚合氯化铝(PAC)、聚合硫酸铁进行对比,结果表明,在它们各自最优投加量下,HPAC能够更有效地减缓超滤膜TMP的增长率,从而降低膜污染。因此,认为HPAC是与PVC超滤合金膜契合效果最佳的混凝剂。