Untreated coffee husks as biosorbents for the removal of heavy metals from aqueous solutions

The objective of this work was to propose an alternative use for coffee husks (CH), a coffee processing residue, as untreated sorbents for the removal of heavy metal ions from aqueous solutions. Biosorption studies were conducted in a batch system as a function of contact time, initial metal ion concentration, biosorbent concentration and pH of the solution. A contact time of 72 h assured attainment of equilibrium for Cu(II), Cd(II) and Zn(II). The sorption efficiency after equilibrium was higher for Cu(II) (89-98% adsorption), followed by Cd(II) (65-85%) and Zn(II) (48-79%). Even though equilibrium was not attained in the case of Cr(VI) ions, sorption efficiency ranged from 79 to 86%. Sorption performance improved as metal ions concentrations were lowered. The experimental sorption equilibrium data were fitted by both Langmuir and Freundlich sorption models, with Langmuir providing the best fit (R2>0.95). The biosorption kinetics was determined by fitting first and second-order kinetic models to the experimental data, being better described by the pseudo-second-order model (R2>0.99). The amount of metal ions sorbed increased with the biosorbent concentration in the case of Cu(II) and Cr(VI) and did not present significant variations for the other metal ions. The effect of the initial pH in the biosorption efficiency was verified in the pH range of 4-7, and the results showed that the highest adsorption capacity occurred at distinct pH values for each metal ion. A comparison of the maximum sorption capacity of several untreated biomaterial-based residues showed that coffee husks are suitable candidates for use as biosorbents in the removal of heavy metals from aqueous solutions.     

A comparison of low-cost biosorbents and commercial sorbents for the removal of copper from aqueous media

Three biosorbents, crab carapace, the macroalgae Fucus vesiculosus and peat were compared with two commercial materials, an activated-carbon and an ion-exchange resin for the removal of copper from aqueous media. Kinetic models of Lagergren first-order, pseudo-second order and intraparticular diffusion were used to model the data. The process for all materials is best represented by the pseudo-second order rate model. Langmuir and Freundlich isotherms were used to describe the sorption equilibrium data. Maximum uptake values were 79.4, 114.9 and 71.4 mg g(-1) for crab carapace, F. vesiculosus and ion-exchange resin, respectively. Langmuir and Freundlich isotherm models could not be fitted to the experimental data for peat and activated-carbon. Ion-exchange was calculated to contribute approximately 75%, 77% and 44% to the total biosorption by crab carapace, F. vesiculosus and peat, respectively. The removal efficiencies of crab carapace and F. vesiculosus were >95% and comparable with those achieved using ion-exchange resin. Results from this study suggest that both crab carapace and F. vesiculosus are efficient and effective biosorbent materials for the removal of copper from aqueous solutions and given that they are also low-cost, may be considered viable alternatives to activated-carbon and ion-exchange resin.     

Water-soluble magnetic-graphene nanocomposites: Use as high-performance adsorbent for removal of dye pollutants

In this study, the water-soluble magnetic-graphene nanocomposites (Fe₃O₄@GNs-SO₃H) were fabricated via a simple and efficient approach. The water-soluble magnetic-graphene nanocomposites were applied as an effective adsorbent for removal of organic dye, malachite green, from aqueous solution. It is noteworthy that the nanocomposites displayed good water-dispersibility, rapid absorption rate, high absorption capacity, and convenient magnetic separation. Furthermore, the novel adsorbent could be recovered and recycled for 15 consecutive trials without significant loss of its activity.     

Seaweeds for the remediation of wastewaters contaminated with zinc(II) ions

Eleven different species of marine macroalgae were screened at different pH conditions on the basis of zinc(II) biosorption potential. Among the seaweeds, a green alga, Ulva reticulata, exhibited a highest uptake of 36.1 mg/g at pH 5.5 and 100 mg/l initial zinc(II) concentration. Further experiments were conducted to evaluate the zinc(II) biosorption potential of U. reticulata. Sorption isotherm data obtained at different pH (5-6) and temperature (25-35 degrees C) conditions were fitted well with Sips model followed by Freundlich, Redlich-Peterson and Langmuir models. A maximum zinc(II) biosorption capacity of 135.5 mg/g was observed at optimum conditions of 5.5 (pH) and 30 degrees C (temperature), according to the Langmuir model. It was observed from the kinetic data that the zinc(II) biosorption process using U. reticulata follows pseudo-second-order kinetics. Various thermodynamic parameters, such as DeltaG degrees , DeltaH degrees and DeltaS degrees were calculated and they indicated that the present system was a spontaneous and an endothermic process. The influence of the co-ions (Na(+), K(+), Ca(2+) and Mg(2+)) along with zinc(II) present in the wastewater was also studied. Desorption of zinc(II) ions from the zinc(II)-loaded biomass were examined using 0.1 M CaCl(2) at different pH conditions in three sorption-desorption cycles. A fixed-bed column (2 cm i.d. and 35 cm height) was employed to evaluate the continuous biosorption performance of U. reticulata. The column experiments at different bed heights and flow rates revealed that the maximum zinc(II) uptake was obtained at the highest bed height (25 cm) and the lowest flow rate (5 ml/min). Column data were fitted well with Thomas, Yoon-Nelson and modified dose-response models. The column regeneration studies were carried out for three sorption-desorption cycles. A loss of sorption performance was observed during regeneration cycles indicated by a shortened breakthrough time and a decreased zinc(II) uptake.     

Gum kondagogu modified magnetic nano-adsorbent: An efficient protocol for removal of various toxic metal ions

Gum kondagogu (GK) modified magnetic iron oxide nanoparticles (MNP) have been prepared by co-precipitating Fe^2 + and Fe^3 + ions using ammonia solution in presence of GK biomacromolecules. The TEM analysis revealed the presence of nearly spherical size iron oxide particles with diameters in the range of 8−15 nm; while the XRD results confirmed the crystallinity of iron oxide nanoparticles. The magnetic measurements demonstrated the ferromagnetic behavior of GK − MNP with a magnetic saturation value of ~ 60 emu/g. The removal efficiencies for a variety of metal cations by the GK − MNP were determined quantitatively in the order: Cd^2 + > Cu^2 + > Pb^2 + > Ni^2 + > Zn^2 + > Hg^2 + at a pH of 5.0 ± 0.1 and at a temperature of 30.0 ± 1.0 °C. A maximum of 106.8 mg/g and a minimum of 35.07 mg/g adsorption capacities were observed for the Cd^2 + and Hg^2 + ions, respectively using the Langmuir isotherm model.     

Magnetite/reduced graphene oxide nanocomposites: One step solvothermal synthesis and use as a novel platform for removal of dye pollutants

A simple one step solvothermal strategy using non-toxic and cost-effective precursors has been developed to prepare magnetite/reduced graphene oxide (MRGO) nanocomposites for removal of dye pollutants. Taking advantage of the combined benefits of graphene and magnetic nanoparticles, these MRGO nanocomposites exhibit excellent removal efficiency (over 91% for rhodamine B and over 94% for malachite green) and rapid separation from aqueous solution by an external magnetic field. Interestingly, the performance of the MRGO composites is strongly dependent on both the loading of Fe₃O₄ and the pH value. In addition, the adsorption behavior of this new adsorbent fits well with the Freundlich isotherm and the pseudo-second-order kinetic model. In further applications, real samples—including industrial waste water and lake water—have been treated using the MRGO composites. All the results demonstrate that the MRGO composites are effective adsorbents for removal of dye pollutants and thus could provide a new platform for dye decontamination.      

Metal accumulation potential of wild plants in tannery effluent contaminated soil of Kasur, Pakistan: field trials for toxic metal cleanup using Suaeda fruticosa

The tannery effluent contaminated lands, adjacent to Depalpur Road, Kasur, Pakistan, have been rendered infertile due to long term effluent logging from the leather industry. The area has been colonized by twelve plant species among which Suaeda fruticosa, Salvadora oleoides and Calatropis procera have been found to be the most common and high biomass producing plants. S. fruticosa was subjected to further experimentation because of its high biomass and phytoextraction capabilities for metals. The pot and field experiments were carried out simultaneously. Pot experiments were conducted using the same field soil in column pots with stoppard bottoms to obtain the leachate. EDTA treatment caused a greater solubility of Cr in the soil pore water. In higher doses more amount of the heavy metal was leached. The increase in the amount of EDTA significantly caused a decrease in the biomass of plants without toxicity symptoms. A higher biomass of plants was observed in the field as compared to the pot experiment. The greatest amount of Na was accumulated by leaves of S. fruticosa followed by stem and roots. Similarly, the greatest amount of Cr was bioaccumulated by leaves of S. fruticosa, but followed by roots and then stem. S. fruticosa can be employed in rehabilitation of tannery effluent contaminated soil using small doses of EDTA.     

Application of Brazilian pine-fruit shell as a biosorbent to removal of reactive red 194 textile dye from aqueous solution kinetics and equilibrium study

The Brazilian pine-fruit shell (Araucaria angustifolia) is a food residue, that was used as biosorbent for the removal of non-hydrolyzed reactive red 194 (NRR) and hydrolyzed reactive red 194 (HRR) forms from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with chromium (Cr-PW), with acid (A-PW), and with acid followed by chromium (Cr-A-PW) were also tested as alternative biosorbents for the removal of NRR and HRR from aqueous effluents. It was observed that the treatment of the Brazilian pine-fruit shell with chromium (Cr-PW and Cr-A-PW) leaded to a remarkable increase in the specific surface area and average porous volume of these biosorbents when compared to unmodified Brazilian pine-fruit shell (PW). The effects of shaking time, biosorbent dosage and pH on biosorption capacity were studied. In acidic pH region (pH 2.0) the biosorption of NRR and HRR were favorable. The contact time required to obtain the equilibrium was 24h at 25 degrees C. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. For NRR reactive dye the equilibrium data were best fitted to the Sips isotherm model using PW and A-PW as biosorbents, and Redlich-Peterson isotherm model using Cr-PW and Cr-A-PW as biosorbents. For HRR reactive dye the equilibrium data were best fitted to the Sips isotherm model using PW, A-PW and Cr-A-PW and the Redlich-Peterson isotherm model for Cr-PW as biosorbent.     

Evaluation of magnetic nanoparticles performance as photocatalyst for the catalytic treatment of direct red 28 dye in synthetic and real water effluents

Integrated water resources management practice is gaining popularity as an alternative water source due to the limited supply of freshwater. The present study was carried out on the photocatalytic degradation of Direct red 28 (DR-28) dye using magnetic nanoparticles (MNPs; Fe₃O₄) as a photocatalyst. The study was conducted on the photocatalytic degradation of DR-28 dye in synthetic dye effluent water, to understand the effects of different photoreaction parameters on the degradation kinetics. The influence of different parameters such as time, amount of photocatalyst, concentration of H₂O₂ and pH was investigated. At the optimum dosage of MNPs (0.6?g/L) with 4?mmol/L of H₂O₂, significant photocatalytic degradation of DR-28 dye (93.2%) was observed. The kinetic study revealed that the photocatalytic degradation followed pseudo-first-order kinetics. The degradation performance of Fe₃O₄ nanoparticles as a photocatalyst for DR-28 dye was compared with titanium dioxide (TiO₂) and it was found that the performance of Fe₃O₄ as a photocatalyst is superior to TiO₂ photocatalyst. The real dye effluent was also degraded at optimum conditions and promising results were achieved.     

Novel biofiltration methods for the treatment of heavy metals from industrial wastewater

Most heavy metals are well-known toxic and carcinogenic agents and when discharged into the wastewater represent a serious threat to the human population and the fauna and flora of the receiving water bodies. In the present review paper, the sources have discussed the industrial source of heavy metals contamination in water, their toxic effects on the fauna and flora and the regulatory threshold limits of these heavy metals. The various parameters of the biofiltration processes, their mechanism for heavy metals removal along with the kinetics of biofilters and its modeling aspects have been discussed. The comparison of various physico-chemical treatment and the advantages of biofiltration over other conventional processes for treatment of heavy metals contaminated wastewater have also been discussed. The applications of genetic engineering in the modification of the microorganisms for increasing the efficiency of the biofiltration process for heavy metals removal have been critically analyzed. The results show that the efficiency of the process can be increased three to six folds with the application of recombinant microbial treatment.     

Use of rice husks as potential filler in styrene butadiene rubber/linear low density polyethylene blends in the presence of maleic anhydride

In the present study, rice husks filled styrene butadiene rubber (SBR)/linear low density polyethylene (LLDPE) 50/50 blends with a compatibilizer, maleic anhydride (MAH) were prepared using a brabender plasti-corder. Virgin SBR/LLDPE blend was also prepared. The physico-mechanical as well as dielectric properties were investigated. Increasing MAH concentrations in SBR/LLDPE blends resulted in an increase in the tensile strength, elongation at break and hardness. After a certain concentration (2.5 phr), a reduction in these properties was found. On the other hand an increase in the dielectric properties as well as in the mass swell in both toluene and oil with MAH was noticed. After certain concentration of rice husk filler (25 phr) an abrupt increase in permittivity ε′ and dielectric loss ε″ was obtained. These results are supported by the mechanical properties measurements. The scanning electron microscopy (SEM) indicates that the presence of MAH increases the interfacial interaction between SBR/LLDPE blends on one hand and also rice husk filler and the blend on the other hand.     

Grass waste: A novel sorbent for the removal of basic dye from aqueous solution

The aim of the present work was to investigate the feasibility of grass waste (GW) for methylene blue (MB) adsorption. The adsorption of MB on GW material was studied as a function of GW dose (0.05–1.20 g), solution pH 3–10, contact time and initial concentration (70–380 mg/L). The influence of these parameters on the adsorption capacity was studied using the batch process. The experimental data were analyzed by the Langmuir and Freundlich isotherms. The adsorption isotherm was found to follow the Langmuir model. The monolayer adsorption capacity was found to be 457.640 mg/g. The kinetic data were fitted to the pseudo-first-order and pseudo-second-order models, and were found to follow closely the pseudo-second-order kinetic model. The results revealed that GW adsorbent is potentially low-cost adsorbent for adsorption of MB.     

Batch kinetics and isotherms for biosorption of copper(II) ions onto pre-treated powdered waste sludge (PWS)

Waste sludge samples from different plants were tested for Cu(II) ion biosorption capacities with and without pre-treatment. Waste sludge from a paint industry wastewater treatment plant was found to perform better than the others after pre-treatment with 1% H(2)O(2). Powdered waste sludge (PWS) from the paint industry wastewater treatment plant was used for recovery of Cu(II) ions from aqueous solution by biosorption after pre-treatment with 1% H(2)O(2). Batch kinetics and isotherms of biosorption of Cu(II) ions were investigated at variable initial Cu(II) concentrations between 50 and 400 mg l(-1) with a PWS particle size of 64 microm. The pseudo-first and -second order kinetic models were used to correlate the experimental data. The kinetic constants were determined for both models and the second order kinetic model was found to be more suitable. The Langmuir, Freundlich and the generalized isotherm models were used to correlate the equilibrium biosorption data and the isotherm constants were determined. The Langmuir isotherm was found to fit the experimental data better than the other isotherms tested. The maximum biosorption capacity (116 mg g(-1)) of the pre-treated powdered waste sludge for Cu(II) ions was found to be superior as compared to the other biosorbents reported in literature.     

Evaluation of quicklime mixing for the remediation of petroleum contaminated soils

Quicklime mixing is an established solidification/stabilization technique to improve mechanical properties and immobilise contaminants in soils. This study examined the effects of quicklime mixing on the concentrations and leachability of petroleum hydrocarbon compounds, in two natural soils and on a number of artificial sand/kaolinite mixtures. Several independent variables, such as clay content, moisture content and quicklime content were considered in the study. After mixing the soils with the quicklime, pH, temperature, moisture content, Atterberg limits and concentrations of petroleum hydrocarbon compounds were determined on soil and leachate samples extracted from the treated soils. Significant decreases in concentrations of petroleum hydrocarbon compounds were measured in soils and leachates upon quicklime mixing, which may be explained by a number of mechanisms such as volatilization, degradation and encapsulation of the hydrocarbon compounds promoted by the quicklime mixing. The increase in temperature due to the exothermic hydration reaction of quicklime when in contact with porewater helps to volatilize the light compounds but may not be entirely responsible for their concentration decreases and for the decrease of heavy aliphatics and aromatics concentrations.     

Evaluation of starch based cryogels as potential biomaterials for controlled release of antibiotic drugs

In the present study starch has been blended with poly(vinyl alcohol) to design macroporous architectures following a repeated freeze-thaw method. These macroporous cryogels were loaded with an antibiotic drug, ciprofloxacin hydrochloride (Cfx), and evaluated for its in vitro delivery in a completely controlled manner thus exploring possibilities to use it as a biomaterial in burn or wound healing applications. The key advantage of the present system is that cryogels formed do not contain any chemical crosslinking agent which is often harmful to organic compounds. These Cfx loaded cryogels were characterized by infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) techniques. The controlled release of Cfx drug from cryogels was investigated under varying experimental conditions such as percent loading of the antibiotic drug, chemical architecture of the cryogels and pH, temperature, and nature of the release media. The prepared cryogels show promise to provide a possible pathway for controlling delivery of antibiotic drug thus minimizing the known side effects and improving efficacy also.     

Use of hen feathers as potential adsorbent for the removal of a hazardous dye, Brilliant Blue FCF, from wastewater

Waste material, hen feather, a biosorbent, was successfully utilized in removing a water-soluble hazardous triphenylmethane dye, Brilliant Blue FCF from wastewater. The paper incorporates effect of pH, temperature, amount of adsorbent, contact time, concentration of adsorbate, etc. The adsorption data validates Langmuir and Freundlich adsorption isotherms and on the basis of these isotherms thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy were calculated. Kinetics of the ongoing adsorption was also monitored and specific rate constants for the involved process were calculated at different temperatures. Kinetic measurements suggest a first order adsorption kinetics and adsorption was found to be applicable via film diffusion process in the entire concentration range.     

Small hazardous waste generators in developing countries: use of stabilization/solidification process as an economic tool for metal wastewater treatment and appropriate sludge disposal

The aim of this study was to propose a profitable destination for an industrial sludge that can cover the wastewater treatment costs of small waste generators. Optimized stabilization/solidification technology was used to treat hazardous waste from an electroplating industry that is currently released untreated to the environment. The stabilized/solidified (S/S) waste product was used as a raw material to build concrete blocks, to be sold as pavement blocks or used in roadbeds and/or parking lots. The quality of the blocks containing a mixture of cement, lime, clay and waste was evaluated by means of leaching and solubility tests according to the current Brazilian waste regulations. Results showed very low metal leachability and solubility of the block constituents, indicating a low environmental impact. Concerning economic benefits from the S/S process and reuse of the resultant product, the cost of untreated heavy metal-containing sludge disposal to landfill is usually on the order of US$ 150-200 per tonne of waste, while 1tonne of concrete roadbed blocks (with 25% of S/S waste constitution) has a value of around US$ 100. The results of this work showed that the cement, clay and lime-based process of stabilization/solidification of hazardous waste sludge is sufficiently effective and economically viable to stimulate the treatment of wastewater from small industrial waste generators.     

Evaluation of bioremediation methods for the treatment of soil contaminated with explosives in Louisiana Army Ammunition Plant, Minden, Louisiana

Two bioremediation methods, namely, soil slurry reactor and land farming technique were evaluated for the treatment of soil contaminated with explosives in Louisiana Army Ammunition Plant, Minden, Louisiana. The soil had a high concentration of 2,4,6-trinitrotoluene (TNT) of 10,000 mg/kg of soil and medium level contamination of RDX 1900 mg/kg and HMX 900 mg/kg of soil. The results indicated that soil slurry reactor under co-metabolic condition with molasses as co-substrate removed TNT more efficiently than land farming method. TNT removal efficiency was 99% in soil slurry reactor compared to 82% in land farming after 182 days. HMX and RDX were also removed from the soil in both methods, but the removal efficiency was low. The radiolabeled study showed that soil microbes mineralize TNT. The mass-balance of TNT indicated 23.5% of TNT was mineralized to CO(2), 22.6% was converted to biomass, and 52.3% was converted to various TNT intermediates in the soil slurry reactor. Both methods maintained high bacterial population fairly well. The results of this bench-scale study are promising with regard to transferring the technology to full-scale application at this site.     

The use of protonated Sargassum muticum as biosorbent for cadmium removal in a fixed-bed column

The protonated Sargassum muticum seaweed was studied as a possible biosorbent for cadmium removal in a fixed-bed column. The experiments were conducted in order to determine the effect of flow rate (0.42, 5, 10 and 20 mL min(-1)) and bed height (0.6 and 15.3 cm for the lowest flow rate or 7.4, 13 and 16.6 cm for the others) on breakthrough curves behaviour. The determined breakthrough and exhaustion times increased with the diminution in flow rate and with the increase in bed height. The maximum cadmium uptake capacity, obtained from the area below adsorbed cadmium concentration versus time curves, was found to remain practically constant with bed depth and flow rate. The bed depth service time (BDST) model was applied to analyse experimental data, determining the characteristic process parameters. The optimal lowest sorbent usage rate was evaluated at 2 min contact time and the minimum bed height values necessary to prevent the effluent solution concentration from exceeding 0.02 mg L(-1) at zero time were 5.3, 6.9 and 7.5 cm for flow rates of 5, 10 and 20 mL min(-1), respectively. Several empirical models proposed in the literature (Bohart-Adams, Yan, Belter and Chu models) were investigated in order to obtain the best fit of column data, describing in a simple manner the breakthrough curves. A correlation between model parameters and the variables implied in the process was attempted.