Thermodynamic and breakthrough column studies for the selective sorption of chromium from industrial effluent on activated eucalyptus bark

Studies were carried out on adsorption of Cr(VI) on an adsorbent made from eucalyptus bark. Results revealed that sorption of chromium on activated eucalyptus bark (AEB) was endothermic in nature. Thermodynamic parameters such as the entropy change, enthalpy change and Gibb's free energy change were found out to be 100.97 J mol(-1)K(-1), 33 kJ mol(-1) and -0.737 kJ mol(-1), respectively. Industrial chrome effluent of different chromium concentration at different pH was used as feedstock for the fixed bed adsorption studies. When effluent was fed to the column at low pH of 2, the breakthrough volume increased significantly compared to effluent at higher pH of 4.85. The surface properties of sorbent were characterized by the Scanning electron microscopy, X-ray diffraction technique and Infrared techniques. It was concluded that AEB sorbent column could be used effectively for removal of chromium from industrial effluents by reducing the pH of chrome effluent to two and at optimal column conditions.     

Removal of hexavalent chromium using distillery sludge

Batch mode experiments were conducted to study the removal of hexavalent chromium from aqueous and industrial effluent using distillery sludge. Effects of pH, contact time, initial concentration and adsorbent dosage on the adsorption of Cr(VI) were studied. The data obeyed Langmuir and Freundlich adsorption isotherms. The Langmuir adsorption capacity was found to be 5.7 mg/g. Freundlich constants K(f) and n were 2.05 [mg/g(L/mg)(n)] and 3.9, respectively. Desorption studies indicated the removal of 82% of the hexavalent chromium. The efficiency of adsorbent towards the removal of chromium was also tested using chromium-plating wastewater.     

Removal of chromium(VI) from water and wastewater using surfactant modified coconut coir pith as a biosorbent

Coconut coir pith, an agricultural solid waste was used as biosorbent for the removal of chromium(VI) after modification with a cationic surfactant, hexadecyltrimethylammonium bromide. Optimum pH for Cr(VI) adsorption was found to be 2.0. Reduction of Cr(VI) to Cr(III) occurred to a slight extent during the removal. Langmuir, Freundlich and Dubinin Radushkevich (D-R) isotherms were used to model the adsorption equilibrium data and the system followed all the three isotherms. The adsorption capacity of the biosorbent was found to be 76.3 mg g(-1), which is higher or comparable to the adsorption capacity of various adsorbents reported in literature. Kinetic studies showed that the adsorption obeyed second order and Elovich model. Thermodynamic parameters such as delta G0, delta H0 and delta S0 were evaluated, indicating that the overall adsorption process was endothermic and spontaneous. Effects of foreign anions were also examined. The adsorbent was also tested for the removal of Cr(VI) from electroplating effluent.     

Effect of organic Cr(III) complexes on chromium speciation

Abstract

Chromium speciation in the presence of organic chromium(III) complexes was investigated using solid-phase extraction. The adsorptions of Cr(VI) and Cr(III) on alumina and pumice powder were studied. Maximum sorption of Cr(VI) was obtained by alumina (90.22%), while Cr(III) was highly adsorbed onto pumice powder (86.65%). This result shows that pumice may be a new and promising adsorbent for Cr(III). The experimental equilibrium data for Cr(VI) adsorption onto alumina and Cr(III) sorption onto pumice were analysed using Langmuir and Freundlich isotherms. The separation and adsorption of Cr(VI), Cr(III) and five organic chromium(III) complexes onto pumice and alumina at different pH values were evaluated. Ethylenediaminetetraacetate (EDTA), oxalate, citrate, glycine, alanine and 8-hydroxyqinoline were used as ligands. Sorption of alanine and ethylenediaminetetraacetate complexes was higher onto alumina than pumice at pH>3. The enhancement of adsorption of chromium(III) complexes onto pumice was achieved by surface modification of pumice using a surfactant, namely hexadecyltrimethylammoniumbromür (HDTMA). The presence of surfactant enhanced the adsorption of Cr(III) citrate, oxalate, glycine and 8-hydroxyquinoline complexes onto pumice. However, the adsorption of EDTA and alanine complexes decreased, with ratio of 13.40% and 4.00% respectively. Here we demonstrate that chromium speciation methods depending on adsorption onto various adsorbents including alumina may lead erroneous results. Analytical measurements were performed by flame AAS, data were obtained by standard addition method.     

Column study on the adsorption of Cr(III) and Cr(VI) using Pumice, Yarikkaya brown coal, Chelex-100 and Lewatit MP 62

In the present study, adsorption of Cr(III) and Cr(VI) on Pumice (Pmc), Yarikkaya (YK) brown coal, Chelex-100, and Lewatit MP 62 is examined at room temperature and at initial chromium concentration of 1.0 x 10(-3) mol/L. Column method was carried out as a function of pH, concentration of Cr(III) and Cr(VI) ions, volume of samples and flow rate. The experimental data were evaluated by Freundlich and Langmuir isotherm models. The dynamic breakthrough capacities of the adsorbents for Cr(III) and Cr(VI) were calculated. The maximum chromium sorption occurred at 5 mL/min flow rate and 25 mL volume for all adsorbents. The results showed that the two readily available adsorbents namely Pmc and YK, were suitable for removing chromium from aqueous solution.     

Hexavalent chromium removal from aqueous solutions by a novel powder prepared from Colocasia esculenta leaves

In this study, batch removal of hexavalent chromium from aqueous solutions by powdered Colocasia esculenta leaves was investigated. Batch experiments were conducted to study the effects of adsorption of Cr(VI) at different pH values, initial concentrations, agitation speeds, temperatures, and contact times. The biosorbent was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectrometer analysis. The biosorptive capacity of the adsorbent was dependent on the pH of the chromium solution in which maximum removal was observed at pH 2. The adsorption equilibrium data were evaluated for various adsorption isotherm models, kinetic models, and thermodynamics. The equilibrium data fitted well with Freundlich and Halsey models. The adsorption capacity calculated was 47.62 mg/g at pH 2. The adsorption kinetic data were best described by pseudo-second-order kinetic model. Thus, Colocasia esculenta leaves can be considered as one of the efficient and cheap biosorbents for hexavalent chromium removal from aqueous solutions.     

Bioaccumulation and biosorption of chromium by Aspergillus niger MTCC 2594

Chromium toxicity is of prime concern due to chrome tanning processes in the leather sector. Chrome tanning results in the discharge of toxic levels of chromium causing pollution hazards. Chromium levels of Cr(III) and Cr(VI) were high above permissible limits in chrome samples after chrome tanning. The potential of Aspergillus niger MTCC 2594 to accumulate chromium as well as its biosorption capacity is investigated in this study. Bioaccumulation of Cr(III) and Cr(VI) in the spent chrome liquor has resulted in a 75-78% reduction of the initial Cr content in 24-36 h. A. niger biomass is found to be very effective in the biosorption of Cr(III) and Cr(VI) in spent chrome liquor. Maximum adsorption of 83% for biosorption of Cr(III) at 48 h and 79% of Cr(VI) at 36 h in spent chrome liquor is observed. The biosorption characteristics fit well with Langmuir and Freundlich isotherms and the adsorption parameters are evaluated. The biosorption of Cr also follows Lagergren kinetics. A. niger biomass is effectively used for the biosorption of chromium with 79-83% Cr removal in 36-48 h.     

Hexavalent chromium reduction by bacterial consortia and pure strains from an alkaline industrial effluent

Aims: To characterize the bacterial consortia and isolates selected for their role in hexavalent chromium removal by adsorption and reduction. Methods and Results: Bacterial consortia from industrial wastes revealed significant Cr(VI) removal after 15 days when incubated in medium M9 at pH 6·5 and 8·0. The results suggested chromium reduction. The bacterial consortia diversity (T‐RFLP based on 16S rRNA gene) indicated a highest number of operational taxonomic units in an alkaline carbonate medium mimicking in situ conditions. However, incubations under such conditions revealed low Cr(VI) removal. Genomic libraries were obtained for the consortia exhibiting optimal Cr(VI) removal (M9 medium at pH 6·5 and 8·0). They revealed the dominance of 16S rRNA gene sequences related to the genera Pseudomonas/Stenotrophomonas or Enterobacter/Halomonas, respectively. Isolates related to Pseudomonas fluorescens and Enterobacter aerogenes were efficient in Cr(VI) reduction and adsorption to the biomass. Conclusions: Cr(VI) reduction was better at neutral pH rather than under in situ conditions (alkaline pH with carbonate). Isolated strains exhibited significant capacity for Cr(VI) reduction and adsorption. Significance and Impact of Study: Bacterial communities from chromium‐contaminated industrial wastes as well as isolates were able to remove Cr(VI). The results suggest a good potential for bioremediation of industrial wastes when optimal conditions are applied.     

Lime enhanced chromium removal in advanced integrated wastewater pond system

The removal of trivalent chromium from a combined tannery effluent in horizontal settling tanks and subsequent Advanced Integrated Wastewater Pond System (AIWPS) reactors was investigated. The raw combined effluent from Modjo tannery had pH in the range of 11.2-12. At this pH, a trivalent chromium removal of 46-72% was obtained in the horizontal settling tanks after a one-day detention time. Trivalent chromium precipitated as chromium hydroxide, Cr(OH)3. 58-95% Cr(III) was removed in the advanced facultative pond (AFP) where the water column pH of 7.2-8.4 was close to pH 8, which is the optimum precipitation pH for trivalent chromium. Chromium removals in the secondary facultative pond (SFP) and maturation pond (MP) were 30-50% and 6-16%, respectively. With Cr(III) concentration of 0.2-0.8 mg/l in the final treated effluent, the AIWPS preceded by horizontal settling tanks produced effluent that could easily meet most of the current Cr(III) discharge limits to receive water bodies.     

Modeling, simulation, and experimental validation for continuous Cr(VI) removal from aqueous solutions using sawdust as an adsorbent

Continuous adsorption experiments were performed in a fixed-bed adsorption column to evaluate the performance of low-cost adsorbent (sawdust) developed for the removal of Cr(VI) from aqueous solutions. The effects of influencing parameters such as flow rate, mass of adsorbent, initial Cr(VI) concentration were studied and the corresponding breakthrough curves were obtained. The fixed-bed adsorption process parameters such as breakthrough time, total percentage removal of Cr(VI), adsorption exhaustion rate and fraction of unused bed-length were obtained. A mathematical model for fixed-bed adsorption column was proposed by incorporating the effect of velocity variation along the bed-length in the existing model. Pore and solid diffusion models were used to describe the intra-particle mechanism for Cr(VI) adsorption. The proposed mathematical model was validated with the literature data and the experimental data obtained in the present study and the model was found to be good for explaining the behavior of breakthrough curves.     

Advanced kinetic model of the Cr(VI) removal by biomaterials at various pHs and temperatures

Recently, a new and simple kinetic model was derived from a basic concept of the redox reaction between Cr(VI) and biomaterials, and successfully described the removal behavior of Cr(VI) under various Cr(VI) and biomaterial concentrations. However, this model did not consider the effects of pH and temperature on the Cr(VI) removal by biomaterials. In this study, a new efficient biomaterial, pine needle, capable of removing Cr(VI) was used as a model one to study the Cr(VI) removal by biomaterials. Analysis of chromium species in aqueous and solid phases revealed that the removal mechanism of Cr(VI) by pine needle was its reduction into Cr(III). The removal rate of Cr(VI) increased with a decrease in pH or with an increase of temperature. Finally, an advanced kinetic model in the form of -d[Cr(VI)]/dt = Ae(Ea/RT)[H+]n[Cr(VI)][OCs] was derived, and successfully predicted the time-dependent Cr(VI) concentration at various pHs (2-4) and temperatures (10-55 degrees C).     

Preliminary studies on continuous chromium(VI) biological removal from wastewater by anaerobic-aerobic activated sludge process

The long-term continuous chromium(VI) removal from synthetic wastewater affected by influent hexavalent chromium (Cr(VI)) and glucose concentrations were studied with an anaerobic-aerobic activated sludge process. It was observed that before activated sludge was acclimated, the chromium in the effluent increased immediately as the influent chromium increased. However, both Cr(VI) and total chromium (TCr) in the effluent significantly decreased after acclimation. In the acclimated activated sludge, the chromium removal efficiency was 100% Cr(VI) and 98.56% TCr at influent Cr(VI) levels of 20 mg/day, 100% Cr(VI) and 98.92% TCr at influent Cr(VI) levels of 40 mg/day, and 98.64% Cr(VI) and 97.16% TCr at influent Cr(VI) levels of 60 mg/day. The corresponding effluent Cr(VI) and TCr concentrations were 0 and 0.012 mg/l, 0 and 0.018 mg/l, and 0.034 mg/l and 0.071 mg/l, respectively. When the influent glucose increased from 1125 to 1500 mg/l at influent Cr(VI) dosage of 60 mg/day, the Cr(VI) and TCr removal efficiency with the acclimated activated sludge improved from 98.64% and 97.16% to 100% and 98.48%, respectively, and the chromium concentration in the effluent decreased from 0.034 mg/l of Cr(VI) and 0.071 mg/l of TCr to 0 (Cr(VI)) and 0.038 mg/l (TCr). The effluent COD and turbidity was around 40 mg/l and 0, respectively, after the activated sludge was acclimated. Further studies showed that after the activated sludge was acclimated, its specific dehydrogenases activity (SDA) and protein contents increased. The SDA and protein increased respectively 15% and 10% when influent Cr(VI) increased from 20 to 60 mg/day.     

Efficient removal of hexavalent chromium by a tolerant Streptomyces sp. affected by the toxic effect of metal exposure

AIMS: To isolate and analyse chromium-resistant micro-organisms suitable for bioremediation. METHODS AND RESULTS: Strain CG252, with a minimal inhibitory concentration of 500 microg ml(-1), was isolated from contaminated soils and identified as a Streptomyces sp. by 16S rDNA sequence analysis. Assays carried out at various Cr(VI) concentrations indicated that chromium removal was more efficient at lower concentrations and that this activity resulted in accumulation of Cr(III). Atomic adsorption analysis indicated that the chromium removed was not associated with cell mass and activity assays showed that the capacity to reduce Cr(VI) was most probably due to a soluble cytosolic enzyme. Cells grown as biofilms showed enhanced removal of Cr(VI) with respect to planktonic cells, while analysis of growth and colony morphology indicated that Cr(VI) had a toxic effect on this strain. CONCLUSIONS: Streptomyces sp. CG252 tolerated heavy metals and elevated levels of chromium, despite its negative effect on growth and development, and was efficient at removing Cr(VI) by promoting reduction to Cr(III). SIGNIFICANCE AND IMPACT OF THE STUDY: Strain CG252's capacity to tolerate heavy metals and to reduce Cr(VI) to the less toxic Cr(III), especially when forming biofilms, makes it a promising candidate for detoxification of sites containing this heavy metal.     

Hexavalent chromium removal by viable, granular anaerobic biomass

Hexavalent chromium in industrial wastewater is a major concern due to its extreme toxicity. This study investigates the removal of Cr(VI) using viable anaerobic granular biomass as a biosorbent. The effect of Cr(VI) concentration on biogas content and COD removal using batch studies indicated that the phase II (methanogenic-rich) culture was more sensitive than the phase I (acidogenic-rich) culture. Toxicity indices for both cultures using COD removal were developed based on linear-log interpolation. The median inhibition Cr(VI) concentration (IC(50)), for phase II cultures was found to be 263mg/L, while that for phase I cultures was 309mg/L. A sorption study was conducted on viable and non-viable (dried) phase I-rich biomass: both followed the Langmuir model. In addition, the biosorption capacity for metabolically inhibited biomass was 25% less indicating some level of cellular uptake associated with Cr(VI) removal. This study demonstrated the potential for a two-phase anaerobic treatment system for a Cr(VI)-contaminated effluent.     

The removal of chromium(VI) from aqueous solutions by Fagus orientalis L

The removal of chromium(VI) from aqueous solution under different conditions using an adsorbent was investigated. This adsorbent is Beech (Fagus orientalis L.) sawdust studied by using batch techniques. Batch studies indicated that the percent adsorption decreased with increasing initial concentration of chromium(VI). A contact time of 80 min was found to be optimum. Maximum chromium(VI) removal was observed near a pH of 1.0. Adsorption conformed to the Freundlich and Langmuir isotherms.     

Effect of Rhamnolipids on Chromium-Contaminated Kaolinite

Hexavalent chromium Cr(VI) is a common environmental pollutant that is treated by its reduction to the trivalent form Cr(III). The latter can be re-oxidized to the toxic form, Cr(VI), under specific conditions. A study was conducted on the removal of Cr(III) to eliminate the hazard imposed by its presence in soil as there has been some evidence that organic compounds can decrease its sorption. The effect of addition of negatively-charged biosurfactants (rhamnolipids) on chromium contaminated kaolinite was studied. Results showed that the rhamnolipids have the capability of extracting 25% portion of the stable form of chromium, Cr(III), from the kaolinite, under optimal conditions. The removal of hexavalent chromium was also enhanced compared to water by a factor of 2 using a solution of rhamnolipids. Results from the sequential extraction procedure showed that rhamnolipids remove Cr(III) mainly from the carbonate and oxide/hydroxide portions of the kaolinite. The rhamnolipids had also the capability of reducing close to 100% of the extracted Cr(VI) to Cr(III) over a period of 24 days. This study indicated that rhamnolipids could be beneficial for the removal or long–term conversion of chromium Cr(VI) to Cr(III).     

Removal of chromium on Polyalthia longifolia leaves biomass

Adsorption is an environmental friendly process for removal and/or recovery of heavy metals from wastewater. In recent years, it has been substantiated as a popular technique to treat industrial waste effluents, with significant advantages. In this work, batchwise removal of chromium (III) ions from water by Polyalthia longifolia leaves was studied as a function of adsorbent dose, pH, contact time, and agitation speed. Surface characteristics of the leaves were evaluated by recording IR spectra. The Langmuir, Freundlich, and Temkin adsorption isotherms were employed to explain the sorption process. It was found that one gram of leaves can remove 1.87 mg of trivalent chromium when working at pH 3.0. It has been concluded that Polyalthia longifolia leaves can be used as cost-effective and benign adsorbents for removal of Cr(III) ions from wastewater.     

Adsorption of chromium(III) on lignin

In order to assess the possibility of using lignin to remove Cr(III) from waters, the adsorption of Cr(III) on lignin isolated from black liquor, a waste product of the paper industry, was investigated. The influences of pH, lignin dosage, contact time, ionic strength, Cr(III) concentration and other metals were investigated. The Cr(III) adsorption was strongly dependent on pH and adsorbent dosage, but independent of ionic strength and other metal ions. The adsorption kinetic data can be described well with pseudo-second-order model and the equilibrium data can be well fitted using Langmuir two-surface model with a maximum adsorption capacity of 17.97 mg/g. Cr(III) adsorption on lignin was mainly through the ion-exchange mechanism and formed inner-sphere complexes with lignin. Successful application in removing Cr(III) was achieved by using a real wastewater sample. This study indicates that lignin has the potential to become an effective and economical adsorbent for the removal of Cr(III) from wastewaters.     

The Suitability of Jatropha Seed Press Cake as a Biosorbent for Removal of Hexavalent Chromium from Aqueous Solutions

Jatropha seed press cake (JPC), a biodeisel waste, was investigated for its use as biosorbent for Cr(VI) removal from wastewater. The acid-pretreated biomass exhibited 1.9-fold higher biosorption efficiency for Cr(VI). The Cr(VI) biosorption efficiency was found to increase with decrease in pH of aqueous medium. The adsorption capacity of biosorbent for Cr(VI) increased with increasing concentration of Cr(VI). The biosorption of Cr(VI) by acid-treated JPC followed a pseudo-second-order kinetics. The results of equilibrium studies showed that the biosorption process fitted the Langmuir isotherm model, with a maximum adsorption capacity of 22.727 mg of Cr(VI)/g of biosorbent at 30°C. The activation energy was found to be 27.114 kJ/mol, suggesting that the adsorption process was mainly a physical process. The important thermodynamic parameters of adsorption (ΔG, ΔH, andΔS) were determined, which indicated that the Cr(VI) sorption by JPC is a spontaneous and endothermic process.     

Chromium (VI) uptake by grape stalks wastes encapsulated in calcium alginate beads: equilibrium and kinetics studies

Abstract

The removal of hexavalent chromium from aqueous solution using grape stalks wastes encapsulated in calcium alginate (GS–CA) beads was investigated. Cr(VI) sorption kinetics were evaluated as a function of chromium initial concentration and grape stalks (GS) content in the calcium alginate (CA) beads. The process follows pseudo second-order kinetics. Transport properties of hexavalent chromium on GS–CA beads was characterised by calculating chromium diffusion coefficient using the Linear Absorption Model (LAM). Langmuir isotherms, at pH 3.0 were used to describe sorption equilibrium data as a function of GS percentage in the CAbeads. Maximum uptake obtained was 86.42 mmol of Cr(VI) per L of wet sorbent volume. Results indicated that both kinetic and equilibrium models describe adequately the adsorption process.