Cadmium removal in a biosorption column

New biosorbent material derived from a ubiquitous brown marine alga Ascophyllum nodosum has been examined in packed-bed flow-through sorption columns. It effectively removed 10 mg/L of cadmium down to 1.5 ppb levels in the effluent, representing 99.985% removal. The experimental methodology used was based on the early Bohart and Adams sorption model, resulting in quantitative determination of the characteristic process parameters which can be used for performance comparison and process design. An average metal loading of the biosorbent (N(0)) determined was 30 mg Cd/g, corresponding closely to that observed for the batch equilibrium metal concentration of 10 mg Cd/L. The critical bed depth (D(min)) for the potable water effluent quality standard (0.005 mgg Cd/L) varied with the column feed flow rate (2.4 to 9.6 L/h . cm(2)) from 20 to 50 cm. The sorption column mass transfer and dispersion coefficients were determined, which are also required for solving the sorption model equations. (c) 1994 John Wiley & Sons, Inc.     

Statistical modelling and optimization of substrate composition for bacterial growth and cadmium removal using response surface methodology

In this study, substrate composition was optimized for the growth of Achromobacter xyloxidans and biosorption of Cd(II) from aqueous solution. Response surface methodology (RSM) was used to investigate the function of three independent operating variables, namely, peptone (2.5-10 g/L), beef extract (2.5-5.0 g/L) and incubation time (24-96 h), on dependent variables, i.e. sorption of Cd(II) ions, protein content and biomass growth of A. xyloxidans. The maximum Cd(II) removal efficiency of 69.2%, protein content 1.9 mg/L and growth 0.354 optical density was found at optimal conditions of peptone 10 g/L, incubation time 60 h and beef extract 2.5 g/L. The significance of independent variables and interactions between variables were tested by means of the analysis of variance (ANOVA) with 95% confidence limits and values of “Prob > F” less than 0.0500 indicate that model terms are significant. Fourier transfer infrared (FTIR) analysis was used to investigate sorption mechanism and involved functional groups in Cd(II) binding.     

Adsorption of paraquat using methacrylic acid-modified rice husk

This work investigates the adsorption of paraquat from aqueous medium using a methacrylic acid (MAA)-modified rice husk. The carboxyl groups were chemically bound to the surface of the rice husk by graft copolymerization using Fenton's reagent as a redox initiator. The graft copolymerization was examined to determine the H(2)O(2) concentration and the amount of MAA monomer used. FT-IR spectra confirmed the presence of carbonyl groups on the structural units of the rice husk derivative. The MAA-modified rice husks were hydrolyzed to sodium salt and used to adsorb paraquat. The adsorption was rapid in the first few minutes and quickly reached equilibrium. Equilibrium adsorption data are more consistent with the Langmuir isotherm equation than with the Freundlich equation. The maximum adsorption capacity of modified rice husks was 317.7mg/g-adsorbent. This value clearly exceeds the 60mg/g of Fuller's earth and the 90mg/g of activated carbon, which are the most commonly used binding agents for paraquat.     

Composites with alginate beads: A novel design of nano-adsorbents impregnation for large-scale continuous flow wastewater treatment pilots

The sorption capacity of cadmium (Cd (II)) on three new generated nanocomposite beads sodium alginate (SA) based; SA-Clay (SA-C) beads, SA-Phosphate (SA-P) beads, and SA- Activated Charcoal (SA-Ch) beads was investigated in a batch scale, then a continuous flow reactor.The highest adsorption capacity (137 mg/g) was obtained for SA-Ch using 1000 mg/L of initial Cd (II). The isotherm results showed that the adsorption equilibrium is compatible with the Langmuir isotherm and the sorption capacity of SA-Nano-adsorbent beads is very high. The models used for representing kinetic data was given that the removal of Cd (II) be well-fitted by second-order reaction kinetics. For the fixed bed column treatment, the maximum breakthrough times were 30, 38, and 48  h respectively for the SA-C, SA-P, and SA-Ch.According to the obtained results, it was concluded that SA-Nano-adsorbent bead is an excellent designed material as a nanocomposite for cadmium elimination from wastewater in a continuous treatment process.     

不同黑稻品种黑米和谷壳的花青素产量及其抗氧化性比较

该研究以5个黑稻品种籽粒为材料,通过单因素实验探究树脂吸附法中各因素对黑米花青素纯化效果的影响,优化花青素纯化工艺,比较分析对不同黑稻品种黑米和谷壳的花青素纯化后的产量;采用1,1-二苯基-2-三硝基苯肼(DPPH)法比较其抗氧化活性,并采用PCR方法检测花青素生物合成代谢途径中关键结构基因,以明确不同黑稻品种中黑米和谷壳花青素产量及其抗氧化特性,为黑稻花青素开发利用提供技术支撑。结果表明:(1)黑稻花青素提取液的最佳纯化条件为:静态吸附平衡时间4 h,解吸时间1.5 h,吸附液pH为2.5,温度30℃,70%乙醇洗脱。(2)黑稻黑米中花青素产量最高的品种是‘辐黑香糯’(213μg/g),谷壳中花青素产量最高的品种是‘固城黑糯’(226μg/g),且‘固城黑糯’黑米和谷壳的总花青素产量最高(432μg/g)。(3)黑米花青素的DPPH清除率为65.1%,黑色谷壳花青素的DPPH清除率为73.7%,每克黑米和黑色谷壳的花青素冻干粉对DPPH自由基清除能力分别相当于3.694和4.208 mmol维生素E,谷壳花青素抗氧化能力比黑米花青素高13.9%。(4)对5个黑稻品种的花青素合成途径的5个关键基因检测发现,仅‘矮血糯’中无黄酮-3′-氢化酶基因(OsF3′H),而且其谷壳中的花青素产量(125μg/g)也显著低于其余4个品种,表明OsF3′H基因可能与黑稻谷壳的花青素含量有关。     

Removal of cadmium(II) ion from aqueous system by dry biomass, immobilized live and heat-inactivated Oscillatoria sp. H1 isolated from freshwater (Mogan Lake)

Oscillatoria sp. H1 (Cyanobacteria, microalgae) isolated from Mogan Lake was used for the removal of cadmium ions from aqueous solutions as its dry biomass, alive and heat-inactivated immobilized form on Ca-alginate. Particularly, the effect of physicochemical parameters like pH, initial concentration and contact time were investigated. The sorption of Cd(II) ions on the sorbent used was examined for the cadmium concentrations within the range of 25-250 mg/L. The biosorption of Cd(II) increased as the initial concentration of Cd(II) ions increased in the medium up to 100 mg/L. Maximum biosorption capacities for plain alginate beads, dry biomass, immobilized live Oscillatoria sp. H1 and immobilized heat-inactivated Oscillatoria sp. H1 were 21.2, 30.1, 32.2 and 27.5 mg/g, respectively. Biosorption equilibrium was established in about 1 h for the biosorption processes. The biosorption was well described by Langmuir and Freundlich adsorption isotherms. Maximum adsorption was observed at pH 6.0. The alginate-algae beads could be regenerated using 50 mL of 0.1 mol/L HCl solution with about 85% recovery.     

Adsorption studies on rice husk: removal and recovery of Cd(II) from wastewater

Adsorption behaviour of Ni(II), Zn(II), Cd(II) and Cr(VI) on untreated and phosphate-treated rice husk (PRH) showed that adsorption of Ni(II) and Cd(II) was greater when PRH was used as an adsorbent. Sorption of Cd(II) was dependent on contact time, concentration, temperature, adsorbent doses and pH of the solution. The Langmuir constants and thermodynamic parameters have been calculated at different temperatures. It was found that recovery of Cd(II) from synthetic wastewater by column operation was better than a batch process.     

Kinetic studies on the adsorption of Cd2+, Cu2+ and Zn2+ ions from aqueous solutions by cassava (Manihot sculenta Cranz) tuber bark waste

The kinetics of Cd2+, Cu2+ and Zn2+ adsorption onto pure and thioglycolic acid treated cassava tuber bark wastes (CTBW) were investigated using a batch sorption technique at 30 degrees C. Kinetic data suggested that the adsorption process was exothermic, the rate limiting sorption step was physisorption and adsorption rates could be best described by a pseudo-second order model. Rate coefficients were determined to range between 1.39x10(-2)min(-1) and 5.94x10(-2)min(-1), 1.46x10(-3)min(-1) and 5.76x10(-3)min(-1) and 0.69x10(-3)min(-1) and 5.8x10(-3)min(-1) for Cd2+, Cu2+ and Zn2+, respectively. The results from these studies indicated that the sorption process is fast and stable. The adsorption equilibria were evaluated using the Langmuir equation and the monolayer sorption capacity was found to range between 5.88-26.3mg/g, 33.3-90.9 mg/g and 22.2-83.3mg/g for Cd2+, Cu2+ and Zn2+, respectively. Negative values of DeltaG(ads)(0) indicated that the adsorption process was spontaneous and exothermic in nature.     

Copper flotation waste from KGHM as potential sorbent for heavy metal removal from aqueous solutions

Sorption affinity of copper flotation waste from KGHM toward Cd(II), Cr(III), Cu(II), and Pb(II) ions was investigated in this work. Batch sorption studies, using single-element synthetic aqueous solutions at various pH (2–12), contact time (10–300 min), initial concentration (100–5000 mg dm^?3; 1–100 mg dm^?3 for Cd(II)) and adsorbent dose (25–200 g dm^?3), were performed. Bonding strength of adsorbed metals was tested from the degree of desorption. The maximum metal removal was observed at pH 5–8, ≥120 min reaction time, and 25 g dm^?3 adsorbent dose. Maximum sorption capacities of studied material were 41.6, 58.8, and 83.8 mg g^?1 for Cr(III), Cu(II), and Pb(II), respectively, for 5000 mg dm^?3 initial concentration, and 0.86 mg g^?1 for Cd(II) for initial concentration of 50 mg dm^?3. Sorption isotherms were very well fitted to Langmuir (Cd, Cr, Pb) and Freundlich (Cu) models. Sorption kinetics was nearly ideally fitted to pseudo-second-order kinetic model. Desorption studies showed that most of Cr(III) (98.5%) and Pb(II) (67.3%) ions remained bound to the surface, indicating that the chemisorption dominated as a controlling process. On the other hand, mostly desorbed were Cd(II) (98.5%) and Cu(II) (90.3%) ions, which indicated that processes like physisorption or precipitation were prevailing.     

Sorption of Cd(II) and Pb(II) by exopolymeric substances (EPS) extracted from activated sludges and pure bacterial strains: Modeling of the metal/ligand ratio effect and role of the mineral fraction

The present study deals with the sorption of Cd(II) and Pb(II) by exopolymeric substances (EPS) extracted from activated sludges or pure bacterial strains. The percentage of sorbed metal increases with the concentration of the EPS–water solution. Pb(II) always presents a higher affinity than Cd(II) for EPS. For the EPS extracted from pure bacterial strains, only one global binding constant from a simple equilibrium sorption model, may be used to assess the effect of microbial products such as EPS on Cd(II) and Pb(II) speciation or mobility in the environment. However, for EPS extracted from activated sludges, the wide variation of the global binding constants determined for Cd(II) and Pb(II) do not permit such a simple approach. The differences in sorption to metals between the two types of EPS (bacterial, activated sludges) could be explained by the differences in EPS composition: organic macromolecules, as well as the nature of the mineral fraction.     

Biosorption of cadmium(II), lead (II) and copper(II) with the filamentous fungus Phanerochaete chrysosporium

The biosorption from artificial wastewaters of heavy metals (Cd(II), Pb(II) and Cu(II)) onto the dry fungal biomass of Phanerochaete chryosporium was studied in the concentration range of 5-500 mg l(-1). The maximum absorption of different heavy metal ions on the fungal biomass was obtained at pH 6.0 and the biosorption equilibrium was established after about 6 h. The experimental biosorption data for Cd(II), Pb(II) and Cu(II) ions were in good agreement with those calculated by the Langmuir model.     

Comparison of the Heavy Metal Biosorption Capacity of Active,Heat‐Inactivated and NaOH‐Treated Phanerochaete chrysosporium Biosorbents

Three different kinds of Phanerochaete chrysosporium (NaOH‐treated, heat‐inactivated and active) biosorbent were used for the removal of Cd(II) and Hg(II) ions from aquatic systems. The biosorption of Cd(II) and Hg(II) ions on three different forms of Phanerochaete chrysosporium was studied in aqueous solutions in the concentration range of 50–700 mg/L. Maximum biosorption capacities of NaOH‐treated, heat‐inactivated and active Phanerochaete chrysosporium biomass were found to be 148.37 mg/g, 78.68 mg/g and 68.56 mg/g for Cd(II) as well as 224.67 mg/g, 122.37 mg/g and 88.26 mg/g for Hg(II), respectively. For Cd(II) and Hg(II) ions, the order of affinity of the biosorbents was arranged as NaOH‐treated > heat‐inactivated > active. The order of the amount of metal ions adsorbed was established as Hg(II) > Cd(II) on a weight basis, and as Cd(II) > Hg(II) on a molar basis. Biosorption equilibriums were established in about 60 min. The effect of the pH was also investigated, and maximum rates of biosorption of metal ions on the three different forms of Phanerochaete chrysosporium were observed at pH 6.0. The reusability experiments and synthetic wastewater studies were carried out with the most effective form, i.e., the NaOH‐treated Phanerochaete chrysosporium biomass. It was observed that the biosorbent could be regenerated using 10 mM HCl solution, with a recovery of up to 98%, and it could be reused in five biosorption‐desorption cycles without any considerable loss in biosorption capacity. The alkali‐treated Phanerochaete chrysosporium removed 73% of Cd(II) and 81% of Hg(II) ions from synthetic wastewater.     

Synthesized β-cyclodextrin modified graphene oxide (β-CD-GO) composite for adsorption of cadmium and their toxicity profile in cervical cancer (HeLa) cell lines

In the current study, a composite material was constructed using β-cyclodextrin/graphene oxide (β-CD-GO) and was then applied for the purpose of eliminating cadmium (Cd) from aqueous solution. The synthesized β-CD-GO composite material was then subjected to characterization using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The batch study was conducted for the purpose of removing Cd(II). The results of the study revealed that the β-CD-GO composite material demonstrated a high adsorption capacity of 196 mg/g of Cd(II) at pH 7.0. Further, the adsorption of Cd(II) on the β-CD-GO followed pseudo second-order kinetics and equilibrium adsorption data, which fitted well to the Langmuir isotherm model. The evaluation of the toxicity of the synthesized β-CD-GO composite material was done by the examination of the cervical cancer (HeLa) cell lines. Increasing concentration of β-CD-GO composite material (50 μg to 200 μg) leads to a decline in the percentage of cell viability as from 74 % to 25 %. This study has suggested that the β-CD-GO could play an efficient and beneficial source of the adsorbent for the purpose of eliminating Cd(II) from aqueous solution.     

Impact of Cell Wall Structure on the Behavior of Bacterial Cells as Sorbents of Cadmium and Lead

Batch metal sorption studies were conducted to compare the behavior of Gram-positive Bacillus subtilis and Gram-negative Escherichia coli as sorbents of Cd 2+ and Pb 2+ . A pH range from 3.0 to 6.5 was investigated at total metal concentrations of 1 2 10 -4.0 and 3.2 2 10 -5 M. Concentration apparent equilibrium sorption constants (K s n M ) and sorption capacity (S max n ) values were determined for the bacteria by fitting experimental data to one- ( n = 1) and two-site ( n = 2) Langmuir sorption isotherms. The sorption data for each of the bacteria were described well by a one-site model (r 2 > 0.9), Cd 2+ exhibited somewhat lower sorption affinities (log K s M =- 1.5 for B. subtilis , and -0.7 for E. coli ) than Pb 2+ (log K s M =-0.6 for B. subtilis and -0.8 for E. coli ). Corresponding S max values for Cd 2+ and Pb 2+ on B. subtilis were 0.36 mmole/g and 0.27 mmole/g, respectively. For E. coli Cd 2+ and Pb 2+ S max values were lower at 0.10 mmole/g and 0.21 mmole/g. A two-site sorption model yielded an improved fit for only the E. coli data with several orders of magnitude difference evident between high (Cd 2+ log K s1 M = 0.9; Pb 2+ log K s1 M = 1.5) and low (Cd 2+ log K s2 M =- 1.1; Pb 2+ log K s2 M = -1.6) affinity sorption sites. In addition, allowing for the presence of low affinity sorption (i.e., S max2 ) sites further increased the total E. coli metal sorption capacity closer to that of B. subtilis . As expected, the sorption of Cd 2+ and Pb 2+ by the bacteria exhibited a strong dependence on pH with sorption edges in the range of pH 4.2 to 5.6. The results of this study show that, despite differences in cell wall structure and composition, B. subtilis and E. coli exhibit remarkably similar sorption behavior toward Cd 2+ and Pb 2+ , respectively. These similarities can be attributed to the specific chemical reactivity of acidic functional groups (e.g., carboxyl, phosphoryl) that occur in the cell walls of both bacteria.     

Chromium Removal from Aqueous System and Industrial Wastewater by Agricultural Wastes

This study involved the development of formaldehyde-treated, deseeded sunflower head waste–based biosorbent (FSH) for the biosorption of Cr(VI) from aqueous solution and industrial wastewater. Batch-mode experiments were conducted to determine the kinetics, sorption isotherms, effect of pH, initial Cr(VI) concentration, biosorbent dose, and contact time. The results demonstrated that FSH can sequester Cr(VI) from the aqueous solution. The maximum sorption occurred at pH = 2.0, biosorbent dose = 4.0 g/L, concentration of 100 mg/L at 25°C at 180 rpm after 2 h contact time. The FSH had an adsorption capacity of 7.85 mg/g for Cr(VI) removal at pH 2.0. The rate of adsorption was rapid, and equilibrium was attained within 2 h. The equilibrium sorption data fitted the Langmuir isotherm model, which was further confirmed by the chi-square test.     

Batch and column studies of biosorption of heavy metals by Caulerpa lentillifera

The biosorption of Cu(II), Cd(II), and Pb(II) by a dried green macroalga Caulerpa lentillifera was investigated. The sorption kinetic data could be fitted to the pseudo second order kinetic model. The governing transport mechanisms in the sorption process were both external mass transfer and intra-particle diffusion. Isotherm data followed the Sips isotherm model with the exponent of approximately unity suggesting that these biosorption could be described reasonably well with the Langmuir isotherm. The maximum sorption capacities of the various metal components on C. lentillifera biomass could be prioritized in order from high to low as: Pb(II)>Cu(II)>Cd(II). The sorption energies obtained from the Dubinin-Radushkevich model for all sorption systems were in the range of 4-6 kJ mol(-1) indicating that a physical electrostatic force was potentially involved in the sorption process. Thomas model could well describe the breakthrough data from column experiments. Ca(II), Mg(II), and Mn(II) were the major ions released from the algal biomass during the sorption which revealed that ion exchange was one of the main sorption mechanisms.     

Adsorption of transition metals in aqueous solutions by fluted pumpkin (Telfairia occidentalis Hook f) waste

The adsorption of some divalent transition metal (Hg, Rh, Pt, and Pd) ions in aqueous solution onto fluted pumpkin waste biomass has been investigated. The data were discussed in terms of ionic radii, surface area, and the hard-soft acid-base (HSAB) concept. The monolayer sorption capacities as obtained by the Langmuir adsorption isotherm model were determined to be ca. 9.89 mg/g, 9.81 mg/g, 10.59 mg/g, and 6.84 mg/g for for Hg(II), Rh(II), Pt(II), and Pd(II), respectively. The results are relevant for the optimal design of a wastewater treatment plant and for prediction of model parameters of sorbate-sorbent interactions.     

The effects of biochars produced in different pyrolsis temperatures from agricultural wastes on cadmium uptake of tobacco plant

Abiotic stresses caused by cadmium (Cd) contamination in soil retard plant growth and decline the quality of food. Amendment of biochar was reported effective in reduction of mobility, plant uptake and toxicity of Cd in plants. The aim of this study was to investigate the effect of biochar applications produced from corn cob and rice husk at three different pyrolysis temperatures (400, 500 and 600 °C) on Cd uptake of tobacco plants. The results showed that the shoot Cd concentration and content of tobacco plants significantly increased with the application of Cd in increasing doses. The results showed that increasing Cd dosescaused significant increase (P < 0.01) in shoot Cd concentration and content of the tobacco plant at three different pyrolysis temperatures of both corn cob and rice husk biochars. The concentration of Cd was 0.48 mg kg^?1 in Cd0 dose of corn cob biochar produced at 500 °C and increased to 61.6 mg kg^?1 at Cd5, while Cd concentration increased to 72.3 mg kg^?1 with rice husk biochar. Despite the increase in Cd concentrations and content, shoot Cd concentrations and contents were significantly (P < 0.01) reduced with the treatments of corn cob and rice husk biochars produced at different pyrolysis temperatures. The Cd concentration at Cd5 dose in the absence of biochar addition was 90.5 mg kg^?1, while Cd concentration at Cd5 dose in 400, 500 and 600 °C treatments of corn cob biochar was reduced to 66.5, 61.6 and 67.3 mg kg^?1 respectively, and to 77.0, 72.3 and 70.2 mg kg^?1 in rice husk biochar. The results also revealed that corn cob biochar treatments were more effective in reducing Cd uptake of tobacco plants compared to rice husk biochar. Higher specific surface area of corncob biochar compared to rice husk biochar caused to the difference between two biochar sources on Cd uptake of tobacco plants.     

Alginate coated loofa sponge discs for the removal of cadmium from aqueous solutions

A biosorbent was prepared by coating the fibrous network of loofa sponge (Luffa cylindrica) with a thin film of calcium alginate. Alginate-coated loofa sponge removed Cd(II) rapidly, reaching equilibrium loading of 124 mg g(-1) in 30 min. Seventy % of equilibrium uptake was achieved in 10 min. In contrast, it took 240 min for alginate beads to reach a loading equilibrium of 88 mg g(-1) under identical conditions. The biosorption behaviour followed the Langmuir adsorption isotherm and the ACLS biosorbent was shown to be highly effective in removing Cd(II) from a 10 mg l(-1) solution in a continuous flow fixed-bed column bioreactor.     

Entrapment of white-rot fungus Trametes versicolor in Ca-alginate beads: preparation and biosorption kinetic analysis for cadmium removal from an aqueous solution

The biosorption of cadmium ions onto entrapped Trametes versicolor mycelia has been studied in a batch system. The maximum experimental biosorption capacities for entrapped live and dead fungal mycelia of T. versicolor were found as 102.3 +/- 3.2 mg Cd(II) g(-1) and 120.6 +/- 3.8 mg Cd(II) g(-1), respectively. Biosorption equilibrium was established in about 1 h and biosorption was well described by the Langmuir and Freundlich biosorption isotherms. The change in the biosorption capacity with time was found to fit the pseudo-second-order equation. Since the biosorption capacities were relatively high for both entrapped live and dead forms, those fungal forms could be considered as suitable biosorbents for the removal of cadmium in wastewater-treatment systems. The biosorbents were reused in three consecutive adsorption/desorption cycles without a significant loss in the biosorption capacity.