Coconut coir as biosorbent for Cr(VI) removal from laboratory wastewater

A high cost-effective treatment of sulphochromic waste is proposed employing a raw coconut coir as biosorbent for Cr(VI) removal. The ideal pH and sorption kinetic, sorption capacities, and sorption sites were the studied biosorbent parameters. After testing five different isotherm models with standard solutions, Redlich-Peterson and Toth best fitted the experimental data, obtaining a theoretical Cr(VI) sorption capacity (SC) of 6.3 mg g(-1). Acid-base potentiometric titration indicated around of 73% of sorption sites were from phenolic compounds, probably lignin. Differences between sorption sites in the coconut coir before and after Cr adsorption identified from Fourier transform infrared spectra suggested a modification of sorption sites after sulphochromic waste treatment, indicating that the sorption mechanism involves organic matter oxidation and chromium uptake. For sulphocromic waste treatment, the SC was improved to 26.8+/-0.2 mg g(-1), and no adsorbed Cr(VI) was reduced, remaining only Cr(III) in the final solution. The adsorbed material was calcinated to obtain Cr(2)O(3,) with a reduction of more than 60% of the original mass.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

The effectiveness of four organic matter amendments for decreasing resin-extractable Cr(VI) in Cr(VI)-contaminated soils

This paper compared the effectiveness of four organic materials for decreasing the amounts of soil extractable Cr(VI) in Cr(VI)-contaminated soils using the DOWEX M4195 resin-extraction method. Organic matters were added into Cr(VI)-spiked soils [500 mg Cr(VI)(kgsoil)(-1)] in the form of sugarcane dregs compost (SCDC), cattle-dung compost (CDC), soybean meal (SBM) and rice bran (RB), in the amounts of 0, 1%, and 2% by dry weight, respectively. The results indicated that adding only 1% organic matter to the studied soils could effectively decrease the amount of soil resin-extractable Cr(VI) after 12 days of incubation. The decrease of resin-extractable Cr(VI) by organic materials was mainly the result from the reduction of Cr(VI) to Cr(III) supported by the XANES spectroscopy. Among the four tested organic materials, SBM and RB had higher effectiveness in decreasing soil resin-extractable Cr(VI) than CDC and SCDC. This result may be due to the fact that SBM and RB have more dissolved organic carbon (DOC) and protein than CDC and SCDC. Therefore, it was concluded that the contents of DOC and protein are the main factors that determine the effectiveness of organic materials for decreasing the amounts of soil available Cr(VI) in Cr(VI)-contaminated soils.     

Potential of pomegranate husk carbon for Cr(VI) removal from wastewater: kinetic and isotherm studies

Pomegranate husk was converted into activated carbon and tested for its ability to remove hexavalent chromium from wastewater. The new activated carbon was obtained from pomegranate husk by dehydration process using concentrated sulfuric acid. The important parameters for the adsorption process such as pH, metal concentration and sorbent weight were investigated. Batch equilibrium experiments exhibited that a maximum chromium uptake was obtained at pH 1.0. The maximum adsorption capacity for pomegranate husk activated carbon was 35.2mgg(-1) as calculated by Langmuir model. The ability of activated carbon to remove chromium from synthetic sea water, natural sea water and wastewater was investigated as well. Different isotherm models were used to analyze the experimental data and the models parameters were evaluated. This study showed that the removal of toxic chromium by activated carbon developed from pomegranate husk is a promising technique.     

The effectiveness of ferrous iron and sodium dithionite for decreasing resin-extractable Cr(VI) in Cr(VI)-spiked alkaline soils

Ferrous iron, Na(2)S(2)O(4), and a mixture of Fe(II) and Na(2)S(2)O(4) (4:1 mol/mol) were tested for their effectiveness for decreasing resin-extractable Cr(VI) in alkaline Cr(VI)-spiked soils. The results indicated that adding those reductants greatly decreased the amount of resin-extractable Cr(VI) when the application rate of reductants equaled the number of equivalents of dichromate added to the Cr(VI)-spiked soils. This was mainly as a result of the Cr(VI) reduction into Cr(III), as supported by the XANES spectra. Among the tested reductants, a mixture of Fe(II) and Na(2)S(2)O(4) was the most effective to decrease resin-extractable Cr(VI). The extent to which resin-extractable Cr(VI) and soil pH were decreased was affected by the pH of the reductants. Among the tested reductants at various pH, FeSO(4) at pH below 1 was the most effective in decreasing resin-extractable Cr(VI) in alkaline soils. However, the soil pH was the most decreased as well. On the other hand, the mixtures of ferrous iron and dithionite at a wide range of pH were all efficient (>70% efficiency) in decreasing resin-extractable Cr(VI). Moreover, the extent of the decrease in soil pH was much smaller than that by FeSO(4) (pH<1) alone, and thus the possibility of the Cr(III) hazard can be avoided.     

Enhancement strategies for Cu(II), Cr(III) and Cr(VI) remediation by a variety of seaweed species

Various chemical treatments have been applied to six brown, red and green seaweed species with a view to enhancing their metal removal for Cu(II), Cr(III) and Cr(VI). Treatment with acetone resulted in the greatest enhancement for both cationic and anionic species with relatively low mass losses (15–35%), indicating its low risk to biomass operational stability. Cation binding was increased by 69%, while the total Cr removal was augmented by 15%. Cr(VI) binding was shown to be an adsorption-coupled reduction, whereby Cr(VI) was bound to the biomass surface at pH 2 and subsequently reduced to Cr(III). Acetone treatment also resulted in biomasses that were capable of converting up to 83% of Cr(VI) in solution to Cr(III). Blocking of carboxyl and amino functionalities had significant negative effects both on total Cr removal as well as percentage conversion of Cr(VI) to Cr(III). Results therefore indicated the significant role played by these moieties in metal binding to these seaweeds. Potentiometric titrations displayed agreement between the degree of esterification and the decrease in Cu(II) removal for Ulva spp. and Polysiphonia lanosa. FTIR analysis identified changes in biomass functionality and availability after chemical modification, the results of which were in agreement with metal removal studies. In conclusion, these biosorbents represent suitable candidates to replace conventional removal technologies for metal bearing wastewaters, in particular for the detoxification of hazardous Cr(VI) waste streams.     

Synthesis of Cr(VI)-imprinted poly(4-vinyl pyridine-co-hydroxyethyl methacrylate) particles: its adsorption propensity to Cr(VI)

The aim of this study is to prepare ion-imprinted polymers, which can be used for the selective removal of Cr(VI) anions from aqueous media. 4-Vinyl pyridine (4-VP) was used as functional monomer. The Cr(VI)-imprinted poly(4-vinyl pyridine-co-2-hydroxyethyl methacrylate), poly(VP-HEMA), particles were prepared by bulk polymerization. The Cr(VI)-imprinted polymer particles were grained from the bulk polymer, and the template ions (i.e., Cr(VI)) were removed using thiourea (0.5%, v/v) in 0.5M HCl. The Cr(VI)-imprinted polymer contained 21.4 μmol 4-VP/g polymers. The specific surface area of the IIP2 particles was found to be 34.5m(2)/g (size range of 75-150 μm), and the swelling ratio was about to 108%. The effect of initial concentration of Cr(VI) anions, the adsorption rate and the pH of the medium on adsorption capacity of Cr(VI)-imprinting polymer were studied. The maximum experimental adsorption capacity was 3.31 mmol Cr(VI)/g polymer. Under competitive condition, the adsorption capacity of Cr(VI)-imprinted particles for Cr(VI) is 13.8 and 11.7 folds greater than that of the Cr(III) and Ni(II) ions, respectively. The first- and second order kinetics models were estimated on the basis of comparative analysis of the corresponding rate parameters, equilibrium capacity and correlation coefficients. The Langmuir adsorption isotherm model was well described the Cr(VI)-imprinted system and the maximum adsorption capacity (Q(max)) was found to be 3.42 mmol/g. Moreover, the reusability of the poly(VP-HEMA) particles was tested for several times and no significant loss in adsorption capacity was observed.     

Mathematical models applied to the Cr(III) and Cr(VI) breakthrough curves

Trivalent and hexavalent chromium continuous biosorption was studied using residual brewer Saccharomyces cerevisiae immobilized in volcanic rock. The columns used in the process had a diameter of 4.5 cm and a length of 140 cm, working at an inlet flow rate of 15 mL/min. Breakthrough curves were used to study the yeast biosorption behavior in the process. The saturation time (ts) was 21 and 45 h for Cr(III) and Cr(VI), respectively, and a breakthrough time (tb) of 4 h for Cr(III) and 5 h for Cr(VI). The uptake capacity of the biosorbent for Cr(III) and Cr(VI) were 48 and 60 mg/g, respectively. Two non-diffusional mathematical models with parameters t0 and sigma were used to adjust the experimental data obtained. Microsoft Excel tools were used for the mathematical solution of the two parameters used.     

Treatment of electroplating wastewater containing Cu2+, Zn2+ and Cr(VI) by electrocoagulation

The performance of electrocoagulation, with aluminium sacrificial anode, in the treatment of metal ions (Cu2+, Zn2+ and Cr(VI)) containing wastewater, has been investigated. Several working parameters, such as pH, current density and metal ion concentrations were studied in an attempt to achieve a higher removal capacity. Results obtained with synthetic wastewater revealed that the most effective removal capacities of studied metals could be achieved when the pH was kept between 4 and 8. In addition, the increase of current density, in the range 0.8-4.8 A dm(-2), enhanced the treatment rate without affecting the charge loading, required to reduce metal ion concentrations under the admissible legal levels. The removal rates of copper and zinc were found to be five times quicker than chromium because of a difference in the removal mechanisms. The process was successfully applied to the treatment of an electroplating wastewater where an effective reduction of (Cu2+, Zn2+ and Cr(VI)) concentrations under legal limits was obtained, just after 20 min. The electrode and electricity consumptions were found to be 1 g l(-1) and 32 A h l(-1), respectively. The method was found to be highly efficient and relatively fast compared to conventional existing techniques.     

Bioremediation of Cr(VI) in contaminated soils

Ex situ treatment of hexavalent chromium (Cr(VI)) contaminated soil using a bioreactor-biosorption system was evaluated as a novel remediation alternative. Leaching of Cr(VI) from the contaminated soil using various eluents showed that desorption was strongly affected by the solution pH. The leaching process was accelerated at alkaline conditions (pH 9). Though, desorption potential of ethylene diamine tetra acetic acid (EDTA) was the maximum among various eluents tried, molasses (5 g/L) could also elute 72% of Cr(VI). Cr(VI) reduction studies were carried out under aerobic and facultative anaerobic conditions using the bacterial isolates from contaminated soil. Cr(VI) reduction was moderately higher in aerobic conditions than in facultative anaerobic conditions. The effect of various electron donors on Cr(VI) reduction was also investigated. Among five electron donors screened, peptone (10 g/L) showed maximum Cr(VI) reduction followed by molasses (10 g/L). The time required for complete Cr(VI) reduction was increased with increase in the initial Cr(VI) concentration. However, specific Cr(VI) reduction was increased with increase in initial Cr(VI) concentration. Sulfates and nitrates did not compete with Cr(VI) for accepting the electrons. A bioreactor was developed for the detoxification of Cr(VI). Above 80% of Cr(VI) reduction was achieved in the bioreactor with an initial Cr(VI) concentration of 50 mg/L at an HRT of 8 h. An adsorption column was developed using Ganoderm lucidum (a wood rooting fungus) as the adsorbent for the removal of trivalent chromium (Cr(III)) and excess electron donor from the effluent of the bioreactor. The specific Cr(III) adsorption capacity of G. lucidum in the column was 576 mg/g. The new biosystem seems to be a promising alternative for the ex situ bioremediation of Cr(VI) contaminated soils.     

Modelling Cr(VI) removal by a combined carbon-activated sludge system

The combined carbon-activated sludge process has been proposed as an alternative to protect the biomass against toxic substances in wastewaters; however, the information about the effect of powdered-activated carbon (PAC) addition in activated sludge reactors for the treatment of wastewaters containing Cr(VI) is limited. The objectives of the present study were: (a) to evaluate the removal of hexavalent chromium by (i) activated sludge microorganisms in aerobic batch reactors, (ii) powdered-activated carbon, and (iii) the combined action of powdered-activated carbon and biomass; (b) to propose mathematical models that interpret the experimental results. Different Cr(VI) removal systems were tested: (S1) biomass (activated sludge), (S2) PAC, and (S3) the combined activated carbon-biomass system. A Monod-based mathematical model was used to describe the kinetics of Cr(VI) removal in the system S1. A first-order kinetics with respect to Cr(VI) and PAC respectively, was proposed to model the removal of Cr(VI) in the system S2. Cr(VI) removal in the combined carbon-biomass system (S3) was faster than both Cr(VI) removal using PAC or activated sludge individually. Results showed that the removal of Cr(VI) using the activated carbon-biomass system (S3) was adequately described by combining the kinetic equations proposed for the systems S1 and S2.     

Selective Determination of Cr(VI) by a Self-Assembled Monolayer-Based Electrode

We have developed a selective electrode for chromium(VI), based on a self-assembled monolayer of 4-(mercapto-n-alkyl)pyridinium on gold surfaces, which exhibits unique speciation capabilities. Cr(VI) levels as low as 1 parts per trillion can be detected using a 4-(mercaptoethyl)pyridinium monolayer. The different parameters that govern the analytical performance of these electrodes have been studied in detail and optimized. In addition, the organization of the monolayers has been examined by a variety of surface techniques such as XPS, FT-IR, and electrochemistry. Our results show that structuring and understanding the solid-liquid interface at the molecular level are essential for designing probes with superior analytical characteristics.     

Azadirachta indica (Neem) leaf powder as a biosorbent for removal of Cd(II) from aqueous medium

A biosorbent, Neem leaf powder (NLP), was prepared from the mature leaves of the Azadirachta indica (Neem) tree by initial cleaning, drying, grinding, washing to remove pigments and redrying. The powder was characterized with respect to specific surface area (21.45 m2g(-1)), surface topography and surface functional groups and the material was used as an adsorbent in a batch process to remove Cd(II) from aqueous medium under conditions of different concentrations, NLP loadings, pH, agitation time and temperature. Adsorption increased from 8.8% at pH 4.0 to 70.0% at pH 7.0 and 93.6% at pH 9.5, the higher values in alkaline medium being due to removal by precipitation. The adsorption was very fast initially and maximum adsorption was observed within 300 min of agitation. The kinetics of the interactions was tested with pseudo first order Lagergren equation (mean k(1)=1.2x10(-2)min(-1)), simple second order kinetics (mean k2=1.34x10(-3) gmg(-1)min(-1)), Elovich equation, liquid film diffusion model (mean k=1.39x10(-2)min(-1)) and intra-particle diffusion mechanism. The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 158mgg(-1) for the NLP and Freundlich adsorption capacity of 18.7 Lg(-1). A 2.0 g of NLP could remove 86% of Cd(II) at 293 K from a solution containing 158.8 mg Cd(II) per litre. The mean values of the thermodynamic parameters, DeltaH, DeltaS and DeltaG, at 293 K were -73.7 kJmol(-1), -0.24 Jmol(-1)K(-1) and -3.63 kJmol(-1), respectively, showing the adsorption process to be thermodynamically favourable. The results have established good potentiality for the Neem leaf powder to be used as a biosorbent for Cd(II).     

Sequential eluent injection technique as a new approach for the on-line enrichment and speciation of Cr(III) and Cr(VI) species on a single column with FAAS detection

This paper introduces a sequential eluent injection (SEI) technique combined with an on-line preconcentration/separation system for a fast and sensitive FAAS determination of trace amounts of Cr(III) and Cr(VI) species. The method is based on the simultaneous retention of Cr(III) and Cr(VI) on a single mini-column packed with a chloromethylated polystyrene functionalized with N,N-bis(naphthylideneimino)diethylenetriamine (PS-NAPdien) at pH 6.7. The retained chromium species was eluted by sequential injection of HCl for desorption of Cr(III), and NH₃ and NH₄NO₃ buffer solutions for desorption of Cr(VI). All the chemical and flow injection variables were optimized for the quantitative preconcentration and speciation of Cr(III) and Cr(VI). Under the optimum conditions, the calibration graph obtained is linear over the concentration range of 2.0-60.0 μg L⁻¹ for Cr(III), and 8.0-180.0 μg L⁻¹ for Cr(VI). The preconcentration factors for Cr(III) and Cr(VI) were 70 and 30, respectively. The 3σ detection limits were 0.6 μg L⁻¹ and 2.5 μg L⁻¹ for Cr(III) and Cr(VI), respectively. The relative standard deviations were 2.55% and 0.8%, respectively, for 6 replicate determinations of Cr(III) and Cr(VI) at the 40.0 μg L⁻¹ level. The proposed method was applied for determination of Cr(III) and Cr(VI) in different water samples with satisfactory results.     

Synthesis of ordered large-pore mesoporous carbon for Cr(VI) adsorption

Highly ordered mesoporous carbon with large accessible pores (OMC-P) was prepared by using laboratory-made poly(ethylene oxide)-b-polystyrene diblock copolymer as template via the evaporation-induced self-assembly method. The OMC-P was first used as adsorbent for removal of Cr(VI) ion from aqueous solution. Adsorption behavior was studied as a function of time, concentration of adsorbate, temperature, and pH. The kinetics of adsorption of Cr(VI) ion onto OMC-P is well fit to the pseudo-second order model. The Cr(VI) ion adsorption is favored at lower temperatures and at initial acid pH values in the equilibrium. The Freundlich and the Langmuir isotherm fit the equilibrium data satisfactorily. The influence of porosity on equilibrium adsorption capacity was investigated on three types of carbon materials, namely, OMC-P, ordered mesoporous carbon templated from amphiphilic triblock copolymer F127 (OMC-F) and commercial activated carbon (AC). The prepared OMC-P exhibits much higher adsorption performance than the other two carbons.     

Layered double hydroxides intercalated with EDTA as effective sorbents for U(VI) recovery from wastewater

The performance of the synthetic hydrotalcite-like sorbents, initial {[Zn₄Al₂(OH)₁₂]CO₃·nH₂O} and heat-treated (Zn₄Al₂O₇) forms and the form intercalated with EDTA and prepared in a nitrogen atmosphere from [Zn₄Al₂(OH)₁₂]Cl₂·nH₂O, was evaluated and compared. Increased concentrations of hydrocarbonate and carbonate ions do not noticeably affect the degree of U(VI) recovery from wastewaters with pH 8, which is due to tight binding of U(VI) with EDTA anions in the interlayer space of layered double hydroxides. [Zn₄Al₂(OH)₁₂]EDTA·nH₂O is one of the most effective and cheapest synthetic sorbents for recovering from aqueous media not only cationic but also anionic U(VI) species, which is particularly important. Therefore, the sorbent can be recommended for practical use.     

The application of tree bark as bio-indicator for the assessment of Cr(VI) in air pollution

The impact of a chromium smelter on pollution was evaluated by determining Cr(VI) in topsoil, grass and tree bark by electrothermal atomic absorption spectrometry (ETAAS). It was found that bark reflected the levels of air pollution better than soil and grass due to its high accumulative ability of Cr(VI). The tree bark was contaminated with Cr(VI) by a factor of 9 than in soil. It is therefore suggested that the bark be used as an indicator of air pollution for long-term exposure. The concentration of Cr(VI) in the bark was always a fraction of the total concentration of Cr and ranges between 1.6 and 3%. The method used in the preparation of samples was validated by the analysis of certified reference materials.     

Application of Doehlert matrix to the study of electrochemical oxidation of Cr(III) to Cr(VI) in order to recover chromium from wastewater tanning baths

The aim of this study was to optimize simultaneously the chemical and faradic yields of electrochemical oxidation of chromium(III) to chromium(VI) over a titanium-platinum anode in order to recover trivalent chromium from aqueous and tanning baths effluent. A Doehlert design was used to optimize the significant experimental variables: concentration of chloride ions [Cl(-)] (mol L(-1)); temperature of reactional media T (degrees C); pH of reactional media; intensity of electrolysis current I (A); time of electrolysis t(h). The quadratic models of second degree relate chemical (R(C)) and faradic (R(F)) yields to the different variables affecting the electrochemical reaction were determined by the NEMROD software program. Having to study simultaneously two responses, the Pareto graphic analysis of effects was used. The results obtained in this study have shown that the current intensity and the electrolysis time were the main influent parameters on the removal ratio of chemical oxygen demand (COD), total organic carbon (TOC) and electrochemical oxidation of trivalent chromium.     

Cr(VI) reduction in aqueous solutions by siderite

Hexavalent chromium is a common and toxic pollutant in soils and wastewaters. Reduction of the mobile Cr(VI) to less mobile and less toxic Cr(III) is a solution for decontamination of industrial effluents. In this study, the reduction of hexavalent chromium in aqueous solutions by siderite was investigated. The influences of amount of acid, contact time, siderite dosage, initial Cr(VI) concentration, temperature and particle size of siderite have been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The amount of acid is the most effective parameter affecting the Cr(VI) reduction since carbonaceous gangue minerals consume acid by side reactions. The highest Cr(VI) reduction efficiency (100%) occurred in the 50 mg/l Cr(VI) solution containing two times acid with respect to stoichiometric amount of Cr(VI) and at the conditions of siderite dosage 20 g/l, contact time 120 min and temperature 25 degrees C. Reduction efficiency increased with increase in temperature and decrease in particle size. The reduction capacity of siderite was found to be 17 mg-Cr(VI)/g.     

Cr(VI) and Cr(III) speciation on Bacillus sphaericus loaded diaion SP-850 resin

A speciation procedure for chromium(III) and chromium(VI) in the environmental samples has been established in the presented work. The procedure presented based on quantitative biosorption of chromium(III) on Bacillus sphaericus loaded Diaion SP-850 at pH 5. The Cr(VI) recoveries at pH 5 were below 5% on the biosorbent. After reduction of Cr(VI) by concentrated H(2)SO(4) and ethanol, the system was applied to the total chromium. Cr(VI) was calculated as the difference between the total chromium content and the Cr(III) content. Optimal analytical conditions including pH, amounts of biosorbent, etc. for Cr(III) recoveries were investigated. The influences of the some alkaline and earth alkaline ions and some transition metals on the recoveries were also investigated. The capacity of biosorbent for chromium(III) was 6.95 mgg(-1). The detection limit (3 sigma) of the reagent blank for chromium(III) was 0.50 microgL(-1). The procedure was successfully applied to the speciation of chromium(III) and chromium(VI) in natural water samples (R.S.D. lower than 5%, recoveries greater than 95%).