Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

A comparative study for the sorption of Cd(II) by K-feldspar and sepiolite as soil components, and the recovery of Cd(II) using rhamnolipid biosurfactant

This study investigated the sorption characteristics and recovery of selected heavy metal Cd(II) from K-feldspar and sepiolite, representative soil components, using rhamnolipid biosurfactant. Although the proposed technique was classified as a soil bioremediation process, it can also be applied to treatment of waste waters containing Cd(II) ions with minor modifications. The effect of initial Cd(II) concentration on sorption capacity was characterized by determining the sorption isotherms. Of the four models examined, the Freundlich model showed the best fit for the sorption of Cd(II) on K-feldspar, whereas the Langmuir-model was used successfully to characterize the sorption of Cd(II) on sepiolite. Although a high Cd(II) uptake of 7.49 mmol/kg by K-feldspar was obtained, sepiolite was a superior Cd(II) accumulater, with a maximum Cd(II) uptake of 24.66 mmol Cd(II)/kg. The presence of Cd(II) in the sepiolite or K-feldspar prior to addition of the rhamnolipid generally resulted in less rhamnolipid sorption to sepiolite or K-feldspar. The maximum Cd(II) desorption efficiency by rhamnolipid from K-feldspar was substantially higher than that of sepiolite and determined to be 96% of the sorbed Cd(II), whereas only 10.1% of the sorbed Cd(II) from sepiolite was recovered by rhamnolipid solution.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin

Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.     

Removal of Pb(II) ions from aqueous solution using activated tea waste: Adsorption on a fixed-bed column

An inexpensive and effective adsorbent was developed from waste tea leaves for the dynamic uptake of Pb(II). Characterization of the adsorbents showed a clear change between physico-chemical properties of activated tea waste and simply tea waste. The purpose of this work was to evaluate the potential of activated tea waste in continuous flow removal of Pb(II) ions from synthetic aqueous effluents. The performance of the system was evaluated to assess the effect of various process variables, viz., of bed height, hydraulic loading rate and initial feed concentration on breakthrough time and adsorption capacity. The shape of the breakthrough curves was determined for the adsorption of Pb(II) by varying different operating parameters like hydraulic loading rate (2.3–9.17 m³/h m²), bed height (0.3–0.5 m) and feed concentration (2–10 mg/l). An attempt has also been made to model the data generated from column studies using the empirical relationship based on the Bohart–Adams model. There was an acceptable degree of agreement between the data for breakthrough time calculated from the Bohart–Adams model and the present experimental study with average absolute deviation of less than 5.0%. The activated tea waste in this study showed very good promise as compared with the other adsorbents available in the literature. The adsorbent could be suitable for repeated use (for more than four cycles) without noticeable loss of capacity.     

Removal of Pb(II) from wastewater using wheat bran

The adsorption of Pb(II) ions from aqueous solutions on wheat bran (WB) has been investigated as a function of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time and pH of solution. The equilibrium process was described well by the Langmuir isotherm model with maximum sorption capacities of 69.0, 80.7 and 87.0 mgg(-1) of Pb(II) on wheat bran at 20, 40 and 60 degrees C, respectively. Thermodynamic parameters, i.e. DeltaG(0), DeltaH(0) and DeltaS(0) have also been calculated for the system and the sorption process was found to be endothermic. Good correlation coefficients were obtained for the pseudo second-order kinetic model. The metal ion could be stripped by addition of 0.5M HCl, making the adsorbent regeneration and its reutilization possible.     

Adsorption of Cu(II) ions from aqueous solutions on biochars prepared from agricultural by-products

In this study, the adsorption of Cu(II) from aqueous solutions by agricultural by-products, such as rice husks, olive pomace and orange waste, as well as compost, was evaluated. The aim was to obtain sorbent materials (biochars) through hydrothermal treatment (300?°C) and pyrolysis (300?°C and 600?°C). The effect of adsorbent dose, pH, contact time and initial Cu(II) concentration in batch-mode experiments was investigated. The optimum Cu(II) adsorption conditions was found to occur at 5-12?g/L adsorbent dose, initial pH 5-6, and reaction time 2-4?h. Furthermore, the adsorption kinetics were best described by the pseudo-second order model for all the tested materials, while the adsorption equilibrium best fitted by the linear and Freundlich isotherms. Comparing rice husks and olive pomace, the higher adsorption capacity resulted after pyrolysis at 300?°C. With respect to the orange waste and compost, the highest adsorption capacity was observed using biochars obtained after hydrothermal treatment and pyrolysis at 300?°C.     

Removal of phosphorus from aqueous solutions using chemically modified sawdust of Aleppo pine (<Emphasis Type=Italic>Pinus halepensis Miller</Emphasis>): kinetics and isotherm studies

In the present study, chemically modified Aleppo pine (Pinus halepensis Miller) sawdust was used for the removal of phosphate from water. Biosorbent preparation process included size fractionation, extraction for surface activation, acid prehydrolysis, and treatment with urea. Sorption of phosphate ions onto biosorbent was studied using the batch technique. The effect of different parameters such as contact time, adsorbate concentration, and temperature was investigated. The adsorption kinetics data were best described by the pseudo-second-order rate equation, and equilibrium was achieved after 40 and 80 min for modified and unmodified sawdust, respectively. The Langmuir and Freundlich equations for describing adsorption equilibrium were applied to data. The constants and correlation coefficients of these isotherm models were calculated and compared. The adsorption isotherms obey the Freundlich equation. The thermodynamic parameters like free energy, enthalpy, and entropy changes for the adsorption of phosphate ions have been evaluated, and it has been found that the reaction was spontaneous and endothermic in nature. The low value of activated energy of adsorption, 3.088–3.540 kJ mol⁻¹, indicates that the phosphate ions are easily adsorbed on the sawdust. Results suggest that the prepared chemically modified Aleppo pine sawdust has potential in remediation of contaminated waters by phosphate.     

石墨炉测定土壤中镉的升温程序优化研究

采用硝酸钯作为基体改进剂,进行了微波消解-石墨炉原子吸收光谱法测定土壤中镉的方法研究。通过研究灰化温度、原子化温度对镉元素吸光度的影响,优化了石墨炉加热程序。研究表明:选择盐酸-硝酸-氢氟酸体系以及程序升温微波消解方式,能够对土壤样品进行较好的消解。针对测试体系及仪器,灰化温度设定为650℃、原子化温度设定为1 850℃,能够获得较好的吸光度测试结果。测试条件下,镉元素方法检出限为0.11ng/mL、精密度为2.12%。采用微波消解-石墨炉原子吸收光谱法测定土壤中镉的方法具有准确、快捷、灵敏度高的优点。     

Screening of factors influencing Cu(II) extraction by soybean oil-based organic solvents using fractional factorial design

This study aimed to identify the significant factors that give large effects on the efficiency of Cu(II) extraction from aqueous solutions by soybean oil-based organic solvents using fractional factorial design. Six factors (mixing time (t), di-2-ethylhexylphosphoric acid concentration ([D2EHPA]), organic to aqueous phase ratio (O:A), sodium sulfate concentration ([Na(2)SO(4)]), equilibrium pH (pH(eq)) and tributylphosphate concentration ([TBP])) affecting the percentage extraction (%E) of Cu(II) were investigated. A 2(6-1) fractional factorial design was applied and the results were analyzed statistically. The results show that only [D2EHPA], pH(eq) and their second-order interaction ([D2EHPA] × pH(eq)) influenced the %E significantly. Regression models for %E were developed and the adequacy of the reduced model was examined. The results of this study indicate that fractional factorial design is a useful tool for screening a large number of variables and reducing the number of experiments.     

Fly ash for the treatment of Zn(II) rich effluents

Summary The ability of fly ash to remove Zn(II) from water by adsorption has been tested at different concentrations, temperatures and pH of the solution. It was found that low adsorbate concentration, small particle size of adsorbent and higher temperature favoured the removal of Zn(II) from aqueous solution. The Langmuir isotherm was used to represent the equilibrium data at different temperatures. The apparent heat of adsorption has been found to be 17.325 Kcal mol^–1, which indicates the process to be endothermic. The uptake of Zn(II) is diffusion controlled and the mass transfer coefficient is 3.56 × 10^–5 cm s ^–1.The maximum removal was noted at pH 7.5. Dr V.N. Singh is Professor and Head of the Department of Applied Chemistry, Dr A.K. and Prof. D.P. Singh are members of the Department of Mining Engineering; all are situated in the Institute of Technology at Banaras Hindu University.     

Development of a highly sensitive extractive spectrophotometric method for the determination of nickel(II) from environmental matrices using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone

Nickel(II) reacts with N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone (ECCT) and forms a yellow colored complex, which was extracted into n-butanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-ECCT complex was measured at different intervals of time at 400nm, to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72h. The system obeyed Beer's law in the concentration range of 1.2-5.6mugml(-1) of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.114x10(4)Lmol(-1)cm(-1) and 5.29x10(-3)mugcm(-2) at 400nm, respectively. Hence, a detailed study of the extraction of nickel(II) with ECCT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.     

Adsorption of Pb and Cd on the natural surface coatings (NSCs) in the presence of organochlorine pesticides: a preliminary investigation

Adsorption of Pb and Cd in the presence and absence of organochlorine pesticides (OCPs) on natural surface coatings (NSCs), which were collected in the Nanhu Lake in Changchun, China, was measured in order to investigate the effect of the OCPs on the adsorption of heavy metals on the NSCs. Adsorption of Pb/Cd was carried out under controlled laboratory conditions (mineral salt solution with defined species, ionic strength 0.05 mol/l, 25 degrees C and pH 6.0) with initial Pb and Cd concentrations ranging from 0.2 to 2.5 mol/l. The classical Langmuir adsorption isotherm was applied to estimate the equilibrium coefficients of the adsorption of Pb and Cd on the NSCs. Adsorption interference between Pb/Cd and the OCPs on the NSCs indicated that the adsorption of Pb/Cd on the NSCs was influenced by the OCPs, and competitive adsorption between Pb and the OCPs was observed while adsorption of Cd was enhanced by addition of the OCPs. Adsorption data fit the Langmuir isotherm well for the NSCs treated with the OCPs at different equilibrium concentrations. The results showed that the amount of adsorbed Pb decreased by more than 40% while the amount of adsorbed Cd increased by over 60% with an increase in the initial concentrations of the OCPs ranging from 0 to 5.0 microg/l and that adsorption of Pb/Cd on the NSCs was strongly affected by the OCPs. This preliminary study highlights the importance of the OCPs on the NSCs in controlling the transport, fate, biogeochemistry, bioavailability and toxicity of trace metals in aquatic environments.     

Assessment of the small modular reactor (SMR) marketing using modified network dynamics-based system dynamics (SD) method

Following the export success of the South Korean small modular reactor (SMR), it has been investigated for the marketing strategy of nuclear power plants (NPPs). The information feedback oriented method for the social-business matters, system dynamics (SD), is applied to the assessment of the marketing strategy in which the forecasting skills are performed. Each element has the Boolean value as 0 or 1 in which the values are selected by the random number generation. If the generated values are higher than the designed value decided by the operator, it is 1. Otherwise, it is 0. The networking based dynamical modeling is discussed. The modification of the linear networking is changed by the SD algorithm where the feedback and multiple connections are added to the original network dynamics theory. This new method has shown the complexity of the marketing strategy, especially for the NPPs.     

Water quality modelling of the river Yamuna (India) using QUAL2E-UNCAS

This paper describes the utility of QUAL2E as a modelling package in the evaluation of a water quality improvement programme. In this study, QUAL2E was applied to determine the pollution loads in the river Yamuna during its course through the national capital territory of Delhi, India. The study aimed at examining the influence of different scenarios on river water quality. Four different pollution scenarios were analysed besides the 'business as usual' situation. The study revealed that it was necessary to treat the discharge from drains to the river Yamuna and diversion of a substantial load to the Agra canal for further treatment was also essential. It was also established through this study that maintaining a flow rate of more than 10 m(3)/s in the river could also help preserve the river's water quality. To clearly display the model outcomes and demarcate polluted zones in the river stretch, model results were interfaced with a Geographical Information System (GIS) to produce cartographic outputs. In addition, uncertainty analysis in the form of first-order error analysis and Monte Carlo analysis was performed, to realise the effect of each model parameter on DO and BOD predictions. The uncertainty analysis gave satisfactory results on simulated data.     

Assessment of the Enabling Rural Innovation (ERI) approach: Case studies from Malawi and Uganda

This paper presents lessons from applying an innovative action research approach for linking smallholder farmers to markets, in eastern and southern Africa. The Enabling Rural Innovation (ERI) approach aims to strengthen social organization and entrepreneurial capacity in rural communities. It focuses on fostering community‐based capacity for the inclusion of rural women and the poor in analyzing and accessing market opportunities. Using case studies from Malawi and Uganda the paper assesses the outcomes of ERI on rural communities with a focus on human capital, gender issues and investment in natural resource management. Results show that households are benefiting significantly from linkages to markets in terms of increasing household incomes, and accumulating assets. Skills in analyzing markets and in negotiating with traders have increased among smallholder farmers. The integration of gender in the approach has led to changes in gender decision making patterns at household and community level towards a more shared decision‐making process. The results however show a difference in skills between men and women, with women showing lower levels of skills acquisition. Farmer participatory research has increased investments in improved technologies such as fertilizer applications for soil fertility management.     

Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.     

Use of an activated carbon from antibiotic waste for the removal of Hg(II) from aqueous solution

Porous carbon has been prepared from waste antibiotic material by a chemical activation method using K(2)CO(3) as an activating reagent. Carbon was studied systematically by the adsorption of nitrogen and iodine. It was found that the process parameters such as activation temperature and activation time are crucial for preparing high-quality activated carbon. The proper choice of the preparation conditions allows to produce microporous activated carbon with a micropore volume up to 0.492 cm(3)/g and a BET surface area of 1260 m(2)/g. Adsorption of mercury(II) from an aqueous solution on antibiotic carbon was investigated under the varying conditions of agitation time, metal ion concentration and pH. The adsorption capacity of the carbon is 129 mg/g.