Biosorption of Cd(II) and Zn(II) by Nostoc commune: Isotherm and Kinetics Studies

In this study, Nostoc commune (cyanobacterium) was used as an inexpensive and efficient biosorbent for Cd(II) and Zn(II) removal from aqueous solutions. The effect of various physicochemical factors on Cd(II) and Zn(II) biosorption such as pH 2.0–7.0, initial metal concentration 0.0–300 mg/L and contact time 0–120 min were studied. Optimum pH for removal of Cd(II) and Zn(II) was 6.0, while the contact time was 30 min at room temperature. The nature of biosorbent and metal ion interaction was evaluated by infrared (IR) technique. IR analysis of bacterial biomass revealed the presence of amino, carboxyl, hydroxyl, and carbonyl groups, which are responsible for biosorption of Cd(II) and Zn (II). The maximum biosorption capacities for Cd(II) and Zn(II) biosorption by N. commune calculated from Langmuir biosorption isotherm were 126.32 and 115.41 mg/g, respectively. The biosorption isotherm for two biosorbents fitted well with Freundlich isotherm than Langmuir model with correlation coefficient (r² < 0.99). The biosorption kinetic data were fitted well with the pseudo‐second‐order kinetic model. Thus, this study indicated that the N. commune is an efficient biosorbent for the removal of Cd(II) and Zn(II) from aqueous solutions.     

Cd(II), Pb(II) and Zn(II) Removal from Contaminated Water by Biosorption Using Activated Sludge Biomass

Biosorption using activated sludge biomass (ASB) as a potentially sustainable technology for the treatment of wastewater containing different metal ions (Cd(II), Pb(II) and Zn(II)) was investigated. ASB metal uptake clearly competed with protons consumed by microbial biomass compared with control tests with non‐activated sludge biomass. Biosorption tests confirmed maximum exchange between metal ions and protons at pH 2.0–4.5. It was revealed by the study that the amount of metal ions released from the biomass increased with biomass sludge concentration. The result showed that maximum absorption of metal ions was observed for Cd(II) at pH 3.5, Pb(II) at pH 4.0, and pH 4.5 for Zn(II) ions. The maximum absorption capacities of ASB for Cd(II), Pb(II) and Zn(II) were determined to be 59.3, 68.5 and 86.5%, respectively. The biosorption of heavy metals was directly proportional to ASB stabilization corresponding to a reduction in heavy metals in the order of Cd < Pb < Zn. The order of increase of biosorption of metal ions in ASB was Zn(II) < Pb(II) < Cd(II), and this was opposite to that of non active sludge. The results indicate that ASB is a sustainable tools for the bioremediation of Cd(II), Pb(II) and Zn(II) ions from industrial sludge and wastewater treatment plants.     

Biosorption Kinetics and Isotherm Studies of Cd(II) by Dried Enteromorpha compressa Macroalgae Cells from Aqueous Solutions

For the first time ever, Enteromorpha compressa macroalgae (ECM), which is commonly found in Turkey, has been used as biosorbent by us. This study aims to investigate the biosorption of Cd²⁺ from aqueous solutions in a batch system by using an alga of ECM in different concentrations, pH levels, agitation rates (90–150 rpm), and contact periods. The maximum biosorption capacity of the ECM was found to be 9.50 mg/g at pH 6, Cd²⁺ initial concentration of 10 mg/L and agitation rate 150 rpm. Cadmium removal efficiency was about 95%. The experimental isotherm data were analyzed using the Langmuir and Freundlich equations. Isotherm parameters for both equations were determined and discussed. The stated biosorption mechanism is explained by the Freundlich isotherm (r² = 0.998) theory. Two simplified kinetic models including a pseudo‐first‐ and second‐order equation were selected to follow the biosorption process. Kinetic parameters; rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the biosorption of cadmium onto ECM could be described by the pseudo‐second‐order equation (r² > 0.99).     

Dynamic,Mechanistic, and Thermodynamic Modeling of Zn(II) Ion Biosorption onto Zinc Sequestering Bacterium VMSDCM

The surface of the bacterial cells before the biosorption of Zn(II) ion has been found rough, heterogeneous, and non‐crystalline together with tremendous protrusions and negatively charged functional groups. The bacterium was characterized as rod shaped with Gram‐negative type of cell wall structure. In reaction dynamics, pseudo‐second‐order kinetics with higher linear correlation coefficient (R²) ranging between 0.97 and 0.99, lower sum of square errors (SSE) (0.035–0.081) and chi (χ²) (0.0013–0.009) provided a better explanation of sorption of Zn(II) ion on bacterium surface as compared to pseudo‐first‐order model. The removal of Zn(II) was governed by both film and intra‐particle diffusion at onset and later stage of sorption of metal ion on the surface of bacterial cells. The R² (0.92–0.94) for intra‐particle diffusion model was quite higher with lower values of SSE (9.56–16.33) and chi (χ²) (11.26–19.65) against the Bangham's model. The positive value of ΔH (16.628 × 10^?6 kJ/mol) and ΔS (5320.90 kJ/mol/K) showed that the biosorption of Zn(II) ion across liquid phase on bacterial surface was endothermic with increased randomness at solid–liquid interface. The negative values of ΔG demarcated the whole process as spontaneous in nature. In the present work, the distribution coefficient was found to be > 0.5 at various temperature ranges. At the attainment of equilibrium, the residual concentration of Zn(II) ion in liquid phase was around 0.6 mg/L, which was much below the limit described by United States Environmental Protection Agency (USEPA), i.e. 5 mg/L.     

A Study: Removal of Cu(II), Cd(II), and Pb(II) Ions from Real Industrial Water and Contaminated Water Using Activated Sludge Biomass

This study aims to remove of Cu²⁺, Cd²⁺, and Pb²⁺ ions from solution and to investigate the adsorption isotherms, adsorption kinetics, and ion‐exchange affinities of these metals using waste activated sludge (AS) biomass. The adsorptions of the metals on biomass were optimal at an acidic pH value of 6.0 based on its monolayer capacities. Maximum monolayer capacities of AS biomass (q_max) were calculated as 0.478, 0.358, and 0.280 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺, respectively, and the adsorption equilibrium time was found as 60 min for each metal. The adsorbed amount of metal rose with increasing of initial metal ion concentration. The equilibrium adsorption capacity of AS for initial 0.25 mmol L^?1 metal concentration was determined as 0.200, 0.167, and 0.155 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively. These relevant values were determined as 0.420, 0.305, and 0.282 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively, when initial metal concentration was 0.50 mmol L^?1. In the multi‐metal sorption system, the adsorption capacity of AS biomass was observed in the order of Cu²⁺ > Cd²⁺ > Pb²⁺. In the presence of 100 mmol L^?1 H⁺ ion, the order of ion‐exchange affinity with H⁺ was found as Cu²⁺ > Cd²⁺ > Pb²⁺. The adsorption kinetics were also found to be well described by the pseudo‐second‐order and intraparticle diffusion models. Two different rate constants were obtained as k_i1 and k_i2 and k_i1 (first stage) was found to be higher than k_i2 (second stage).     

Preparation and evaluation of polyaluminum chloride sulfate (PACS) as a coagulant to remove natural organic matter from water

A series of polyaluminum chloride sulfate (PACS) coagulants, which have different SO₄^2–/Al³⁺ and OH/Al (γ) mole ratio, has been successfully developed using AlCl₃·6H₂O, Al₂(SO₄)₃·18H₂O and Na₂CO₃ as raw materials. The coagulation performance of PACS for removing natural organic matter (NOM) from surface water was evaluated, and the effect of SO₄^2–/Al³⁺ mole ratio and γ value in coagulants PACS on DOC and UV₂₅₄ removal was determined. Furthermore, the influence of pH and dosage of the selected PACS with a SO₄^2–/Al³⁺ ratio of 0.0664 and a γ value of 2.0, which achieved the best coagulation performance for the removal of DOC and UV₂₅₄ of all PACS coagulants, on the removal of DOC and UV₂₅₄ and residual aluminum concentration in treated water was investigated. The results were compared with the ones of polyaluminum chloride (PAC) with γ value of 2.0. The experimental data show that the performance of PACS as a coagulant was highly dependent on SO₄^2–/Al³⁺ mole ratio and γ value. Both for the selected PACS and for PAC, the best DOC and UV₂₅₄ removal results were obtained in the range of pH from 5.0 to 8.2 and at the coagulation dose of 5.0 mg/L as Al. Under the optimum coagulation conditions, the selected PACS gave higher DOC and UV₂₅₄ removal efficiencies, and lower residual aluminum concentrations in the treated water than PAC. The maximum removal of DOC and UV₂₅₄ for PACS was approximately 88.0% and 93.0%, respectively. At the optimum coagulant dose and pH 6.5, the concentration of residual aluminum in treated water by both selected PACS and PAC can comply with the regulated limits. The major mechanisms of NOM removal by PACS and PAC coagulation involve complexation‐charge‐neutralization‐precipitation.     

Synthesis and Characterization of Poly(2‐hydroxyethylmethacrylate‐hydroxyapatite) a Novel Composite for the Removal of Lead(II) from Aqueous Solutions

In the present study, a novel adsorbent, poly (2‐hydroxyethylmethacrylate‐hydroxyapatite) [P(HEMA‐Hap)], was prepared and characterized. The synthesis was achieved by means of free‐radical polymerization and a number of structural characterization methods, including FT‐IR, XRD, TGA, SEM, BET‐porosity, and swelling tests. Pb²⁺ adsorption was performed using a series of pH, time, and temperature ranges. The reusability of the composite was also tested. The results obtained indicated that the novel adsorbent is able to bind Pb²⁺ ions with strong chemical affinity. The adsorption results were fitted to the classic Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) sorption models. Thermodynamic parameters obtained demonstrated that the sorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), as expected. The process was also consistent with the pseudo‐second‐order model, and chemical adsorption was determined to be the rate‐controlling step. It was also shown that the composite could be used for five consecutive adsorption processes.     

Biosorption of Cd(II), Ni(II) and Pb(II) from Aqueous Solution by Dried Biomass of Aspergillus niger: Application of Response Surface Methodology to the Optimization of Process Parameters

In this study, the biosorption of Cd(II), Ni(II) and Pb(II) on Aspergillus niger in a batch system was investigated, and optimal condition determined by means of central composite design (CCD) under response surface methodology (RSM). Biomass inactivated by heat and pretreated by alkali solution was used in the determination of optimal conditions. The effect of initial solution pH, biomass dose and initial ion concentration on the removal efficiency of metal ions by A. niger was optimized using a design of experiment (DOE) method. Experimental results indicated that the optimal conditions for biosorption were 5.22 g/L, 89.93 mg/L and 6.01 for biomass dose, initial ion concentration and solution pH, respectively. Enhancement of metal biosorption capacity of the dried biomass by pretreatment with sodium hydroxide was observed. Maximal removal efficiencies for Cd(II), Ni(III) and Pb(II) ions of 98, 80 and 99% were achieved, respectively. The biosorption capacity of A. niger biomass obtained for Cd(II), Ni(II) and Pb(II) ions was 2.2, 1.6 and 4.7 mg/g, respectively. According to these observations the fungal biomass of A. niger is a suitable biosorbent for the removal of heavy metals from aqueous solutions. Multiple response optimization was applied to the experimental data to discover the optimal conditions for a set of responses, simultaneously, by using a desirability function.     

Impact of an inter‐basin water transfer and reservoir operation on a karst open streamflow hydrological regime: an example from the Dinaric karst (Croatia)

This paper describes the hydrological changes caused by inter‐basin water transfer and the reservoir development on the hydrological regimes of two rivers. The Sabljaki Reservoir in the Zagorska Mre?nica River and the Bukovik Reservoir in the upper Dobra River began operation in 1959. Both are part of the hydroelectric power plant (HEPP) Gojak, whose installed capacity is 50 m³/s. Their water volumes at the spillway altitudes of 320·10 and 320·15 m a. s. l. are 3·3 × 10⁶ and 0·24 × 10⁶ m³ respectively. Both the Dobra and Mre?nica Rivers are losing, sinking and underground karst rivers. A 9376‐m‐long tunnel provides water from the Sabljaki Reservoir to the HEPP Gojak, which was constructed in the Lower Dobra River. The Sabljaki Reservoir is located in the Pla?ki karst polje, while the Bukovik Reservoir is located in the neighbouring Ogulin karst polje. The consequences of the inter‐basin water transfer are strong and have caused abrupt changes in the hydrological regimes of the downstream sections of both rivers. At the same time, the construction and development of both the reservoirs have also caused hydrological changes to the upstream section of the Upper Dobra River. Copyright © 2010 John Wiley & Sons, Ltd.