Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

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.     

Biosorption of lead by maize (Zea mays) stalk sponge

This study investigated the removal of Pb(II) from aqueous solutions by a maize (Zea mays) stalk sponge. Equilibrium and kinetic models for Pb(II) sorption were developed by considering the effect of the contact time and concentration at the optimum pH of 6 ± 0.2. The Freundlich model was found to describe the sorption energetics of Pb(II) by Z. mays stalk sponge, and a maximum Pb(II) loading capacity of 80 mg g^?1 was determined. The kinetic parameters were obtained by fitting data from experiments measuring the effect of contact time on adsorption capacity into pseudo-first and second-order equations. The kinetics of Pb(II) sorption onto Z. mays biosorbent were well defined using linearity coefficients (R²) by the pseudo-second-order equation (0.9998). The results obtained showed that Zea may stalk sponge was a useful biomaterial for Pb(II) sorption and that pH has an important effect on metal biosorption capacity.     

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 copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Removal of chromium(VI) from electroplating industry wastewater using bagasse fly ash—a sugar industry waste material

A waste product generated in the sugar industry in India has been converted into a cheap potential adsorbent. This has been characterised and utilized for the removal of chromium (VI) from synthetic and actual wastewater. The sorption efficiency decreases with increase in pH. Adsorption of Cr (VI) on bagasse fly ash follows the Freundlich and Langmuir isotherms and these have been used to obtain the thermodynamic parameters of the process. The sorption capacity of this adsorbent for chromium removal is found to be comparable to other low cost adsorbents.     

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.     

Sorption and desorption of Cd, Cu and Pb using biomass from an eutrophized habitat in monometallic and bimetallic systems

This work examines the sorption capacity of a natural biomass collected from an irrigation pond. The biomass mainly consisted of a mixture of chlorophyte algae with caducipholic plants. Biosorption experiments were performed in monometallic and bimetallic solutions containing different metals commonly found in industrial effluents (Cd, Cu and Pb). The biosorption process was slightly slower in the binary system comparing with monometallic system which was related to competition phenomena between metal cations in solution. The biosorbent behaviour was quantified by the sorption isotherms fitting the experimental data to mathematical models. In monometallic systems, the Langmuir model showed a better fit with the following sorption order: Cu ~ Pb > Cd; and biomass-metal affinity order: Pb > Cd ~ Cu. In bimetallic systems, the binary-type Langmuir model was used and the sorption order obtained was: Pb ~ Cu > Cd. In addition, the effectiveness of the biomass was investigated in several sorption-desorption cycles using HCl and NaHCO(3). The recovery of metal was higher with HCl than with NaHCO(3), though the sorption uptake of the biomass was sensitively affected by the former desorption agent in subsequent sorption cycles.     

Removal of mercury from aqueous solutions using activated carbon prepared from agricultural by-product/waste

Removal of mercury from aqueous solutions using activated carbon prepared from Ceiba pentandra hulls, Phaseolus aureus hulls and Cicer arietinum waste was investigated. The influence of various parameters such as effect of pH, contact time, initial metal ion concentration and adsorbent dose for the removal of mercury was studied using a batch process. The experiments demonstrated that the adsorption process corresponds to the pseudo-second-order-kinetic models and the equilibrium adsorption data fit the Freundlich isotherm model well. The prepared adsorbents ACCPH, ACPAH and ACCAW had removal capacities of 25.88 mg/g, 23.66 mg/g and 22.88 mg/g, respectively, at an initial Hg(II) concentration of 40 mg/L. The order of Hg(II) removal capacities of these three adsorbents was ACCPH > ACPAH > ACCAW. The adsorption behavior of the activated carbon is explained on the basis of its chemical nature. The feasibility of regeneration of spent activated carbon adsorbents for recovery of Hg(II) and reuse of the adsorbent was determined using HCl 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.     

Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Platinum (IV) recovery from chloride solution by functionalized acrylic copolymers

Two acrylic adsorbents with different morphological structures and bearing amidoethylenamine and thiol groups were obtained and used for platinum sorption from chloride solution by the batch method. Physico-chemical parameters that influence adsorption such as initial Pt(IV) concentration, stirring time, pH, and adsorbent amount were investigated. The thermodynamic parameters of Pt(IV) sorption on the synthesized adsorbent were also evaluated based on Langmuir and Freundlich isotherms. Thermodynamic parameters estimated from Langmuir constants indicated that the adsorption is spontaneous, exothermic and there is a disordered state at the molecular level. The models used to analyze the sorption rate led to the conclusion that the most important step in the sorption of Pt(IV) could be both particle diffusion and chemical reaction of [PtCl₆]⁻ with amine functional groups. Thus, both the ion exchange and complex formation mechanisms can occur via nitrogen atoms in the recovery of Pt(IV) on the studied adsorbent.     

Sorption of dissolved lead from shooting range soils using hydroxyapatite amendments synthesized from industrial byproducts as affected by varying pH conditions

For immobilization technologies to be successful, the use of readily available and cost advantageous amendment is important when the remediation targets vast amounts of contaminated soils. The objectives of this study were to investigate whether the byproduct-synthesized hydroxyapatite can be used as an immobilizing amendment for dissolved Pb from a shooting range soil, and to model the kinetic data collected from dissolution experiments. A soil–solution kinetic experiment was conducted under fixed pH conditions as a function of time. A Pb-contaminated soil was reacted with various hydroxyapatite amendments to determine the dissolution rate and mineral products of soil Pb. Three types of amendments used were pure hydroxyapatite (HA), and poorly crystalline hydroxyapatites synthesized from gypsum waste (CHA), and synthesized from incinerated poultry litter (PHA). The dissolved Pb concentration decreased with the addition of amendments at pH 3–7. Both CHA and PHA were more effective than HA for attenuating Pb dissolution at pH 6 and above. According to the thermodynamic calculation at pH 6, the dissolved Pb concentration for CHA and PHA treatments was predicted to be 66% and 50% lower than that of HA treatment, respectively. A better Pb immobilization effect demonstrated by CHA and PHA resulted in their greater solubility at higher pH, which may promote the formation of chloropyromorphite precipitates. Dissolution kinetics of soil Pb was adequately explained by pseudo-first order and pseudo-second order equations in acid pH ranges. According to the ion exchange model, an adequate agreement between the experimental data and regression curves was shown in the initial 40 min of the reaction process, but the accuracy of model predictability decreased thereafter. According to kinetic models and dissolution phenomena, CHA and PHA amendments had better Pb sorption capacity with rapid kinetics than pure hydroxyapatite at weak acid to neutral pH.     

Attenuation of divalent toxic metal ions using natural sericitic pyrophyllite

The present study investigated the effectiveness of an inexpensive and ecofriendly alumino silicate clay mineral, sericitic pyrophyllite, as an adsorbent for the possible application in the removal of some divalent toxic metal cations such as Pb(2+), Cu(2+)and Zn(2+) from aqueous systems. Batch scale equilibrium adsorption studies were carried out for a wide range of initial concentration from 24.1 to 2410mumolL(-1) for lead, 78.65 to 7865mumolL(-1) for copper and 76.45 to 7645mumolL(-1) for zinc solutions. The removal of Pb(2+) was almost complete at low concentration (maximum lead removal capacity, LRC, 32mg of lead/g of pyrophyllite) with 10gL(-1) of adsorbent in a 30min equilibration time. The effects of temperature on adsorption of heavy metal ions were studied. The applicability of the Langmuir, Freundlich and Dubinin-Radushkevich adsorption models in each case of lead, copper and zinc adsorption was examined separately at different temperatures. The adsorption process was found to be endothermic and the Freundlich adsorption model was found to represent the data at different temperatures more suitably.     

Uncertainty and sensitivity analysis of spatial predictions of heavy metals in wheat

Heavy metals seriously threaten the health of human beings when they enter the food chain. Therefore, policymakers require precise predictions of heavy metal concentrations in agricultural crops. In this paper we quantify the uncertainty of regression predictions of Cd and Pb in wheat (Triticum aestivum L.) and the contributions to the uncertainties in these predictions associated with inputs to the regression model. For each node of the 500- x 500-m grid covering the arable soils in The Netherlands, a latin hypercube sample size of 1000 is constructed from the uncertainty distributions of the explanatory variables (pH, soil organic matter [SOM], and heavy metal concentration in soil), the regression coefficients, and the random term of the regression model. This sample is used as input for the regression model to obtain 1000 values from the uncertainty distributions of the log(Cd) and log(Pb) concentration in wheat. There were no nodes where the recent EU quality standards for Cd and Pb (0.2 mg kg(-1) fresh wt.) in wheat were almost certain to be exceeded. For most nodes with clay soils, the quality standard for Cd in wheat almost certainly will not be exceeded; for Pb this is much less certain. The uncertainty in the Cd concentration in soil contributes most to the uncertainty in the predicted Cd concentrations in wheat (36% on the average), followed by the random term of the regression model (23%). For Pb the contribution of the random term is by far the largest (52%).     

Binding of heavy metal contaminants onto chitosans--an evaluation for remediation of metal contaminated soil and water

The binding efficiency of chitosan samples for Ag(+), Cd(2+), Cu(2+), Pb(2+) and Zn(2+) has been evaluated in order to consider their application to remediate metal contaminated soil and water. The sorption behaviour of metal ions was assessed using a batch technique at different contact time and initial metal concentration with different background electrolytes. The kinetics followed a pseudo-second-order model, while the equilibrium data correlated well with the Freundlich and Langmuir isotherm models. For example, the maximum sorption capacity (Q) for chitosan was estimated as 1.93 mmol/g for Ag(+), 1.61 mmol/g for Cu(2+), 0.94 mmol/g for Zn(2+), 0.72 mmol/g for Cd(2+) and 0.64 mmol/g for Pb(2+). Covalent interaction between metal ions and functional groups (amino and hydroxyl) of the chitosans was the main binding mechanism. Ion exchange is not an important process. Chitosan and cross-linked chitosans were able to bind metal ions in the presence of K(+), Cl(-) and NO(3)(-). The nature of Cl(-) and NO(3)(-) ions did not affect Zn(2+) binding by the chitosans. Even at 11x dilution, the chitosans were able to retain metal ions on their surfaces.     

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.     

Contamination time effect on lead and cadmium fractionation in a tropical coastal clay

The capability of a tropical coastal clay to immobilize lead (Pb) and cadmium (Cd) was investigated in laboratory batch sorption tests conducted under acidic, neutral, and slightly alkaline conditions. The contact time was extended to 65 d. The distribution of Pb and Cd among various sorbed phases was examined using a sequential extraction technique. The sorbed phases were fractionated into the exchangeable, carbonate, reducible, organic, and residual fractions. There were only small changes in the total Pb and Cd sorption beyond a 1-d sorption period. The metal fractionation results show that the amount of Pb and Cd in various fractions changed with sorption time, and the changes were pH-dependent. These changes could be attributed to mineral dissolution and transformation or redistribution of the sorbed phases. Transformation of the sorbed phases resulted in increasing Pb and Cd retention in the more persistent fractions with time, at the expense of reductions in the loosely bound fractions. Nevertheless, Pb and Cd fractionation in the solid phase appeared to reach equilibrium within the 65-d sorption period. These Pb and Cd fractionation results reflect the effect of contamination time on the heavy metal lability and bioavailability in the subsurface environment.     

An Assessment of U(VI) removal from groundwater using biochar produced from hydrothermal carbonization

The ever-increasing growth of biorefineries is expected to produce huge amounts of lignocellulosic biochar as a byproduct. The hydrothermal carbonization (HTC) process to produce biochar from lignocellulosic biomass is getting more attention due to its inherent advantage of using wet biomass. In the present study, biochar was produced from switchgrass at 300 °C in subcritical water and characterized using X-ray diffraction, fourier transform infra-red spectroscopy, scanning electron micrcoscopy, and thermogravimetric analysis. The physiochemical properties indicated that biochar could serve as an excellent adsorbent to remove uranium from groundwater. A batch adsorption experiment at the natural pH (~3.9) of biochar indicated an H-type isotherm. The adsorption data was fitted using a Langmuir isotherm model and the sorption capacity was estimated to be ca. 2.12 mg of U g(-1) of biochar. The adsorption process was highly dependent on the pH of the system. An increase towards circumneutral pH resulted in the maximum adsorption of ca. 4 mg U g(-1) of biochar. The adsorption mechanism of U(VI) onto biochar was strongly related to its pH-dependent aqueous speciation. The results of the column study indicate that biochar could be used as an effective adsorbent for U(VI), as a reactive barrier medium. Overall, the biochar produced via HTC is environmentally benign, carbon neutral, and efficient in removing U(VI) from groundwater.