Biosorption of hexavalent chromium and malachite green from aqueous effluents,using Cladophora sp.

Biosorption potential of green macroalgae Cladophora sp., (GAC) for the removal of hexavalent chromium (Cr(VI)) and malachite green (MG) from aqueous medium was investigated. Optimal conditions for biosorption experiments were determined as a function of initial pH, GAC dosage, temperature and initial concentration of Cr(VI) and MG. The biosorption equilibrium data were fitted with the isotherm models of Langmuir, Freundlich, Kiselev, Frumkin and Jovanovic, while the experimental data were analysed using the kinetic models such as pseudo-first-order, pseudo-second-order, Ritchie's and intraparticle diffusion. The Langmuir maximum biosorption capacity was calculated as 100.00?mg/g (Cr(VI)) and 142.85?mg/g (MG). The biosorption kinetic data showed better agreement with the pseudo-second-order kinetic model. The thermodynamic parameters indicated spontaneous and endothermic nature of the biosorption process for Cr(VI) removal, whereas exothermic in the case of MG removal. Furthermore, the biosorption efficiencies of the GAC reusability were found significant up to five cycles and tested using 0.1, 0.5 and 1.0?M HCl, respectively. The results of the present study indicated that GAC is a suitable biosorbent for the sequestration of Cr(VI) and MG from aqueous solutions.     

Equilibrium,kinetics and thermodynamics of hexavalent chromium biosorption on pristine and zinc chloride activated Senna siamea seed pods

Hexavalent chromium contamination in water is an issue of huge concern due to its use at a high scale, toxicity and non-biodegradability. Biosorption is a cost effective and unconventional strategy for the elimination of Cr(VI). Here, a novel biosorbent Senna siamea seed pod biomass and its chemically activated form have been investigated for the elimination of hexavalent chromium from aqueous solution. The biosorbent was characterized by using BET, FTIR, FESEM-EDX and TGA techniques. Parameters controlling the biosorption process were optimized as pH 2.0, temperature 30°C, initial Cr(VI) concentration 500?mg/L, biosorbent dose 0.5?g/L. Optimized contact time was 210 and 180 min for pristine biomass and activated carbon, respectively. Langmuir isotherm correlated well with experimental data revealing that the biosorption occurred in monolayer pattern. Maximum biosorption capacity calculated by Langmuir biosorption isotherm was 119.18 and 139.86?mg/g for S. siamea pristine biomass and activated carbon, respectively. Pseudo-second order kinetic model correlated well with experimental data. Thermodynamic studies suggested that the biosorption process occurs in a non-spontaneous, stable and endothermic manner. These interesting findings on Cr(VI) biosorption by S. siamea seed pod biomass and S. siamea zinc chloride activated carbon vouches for its potential application as an unconventional biosorbent.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

Biosorption of Cr(VI) from wastewater using Sorghastrum Nutans L. Nash

Sorghastrum Nutans L. Nash is used as an adsorbent for the removal of Cr(VI) from wastewater. Adsorption coupled reduction i.e. indirect reduction is the mechanism of Cr(VI) removal by the biomaterial. The adsorbent surface became highly positively charged at lower pH, adsorption rate of Cr(VI) is faster and reduction reaction also accelerates at lower pH since the binding of negatively charged Cr(VI) ion species to the cationic groups is enhanced and protons take part in this reaction. The adsorbent is characterised by using XRD, FTIR, SEM and EDAX analysis. OH bending, CN stretching/bending and NH stretching play a major role in Chromium adsorption. Experimental values follow pseudo-second order reaction and Langmuir adsorption isotherm. Surface diffusion is the rate controlling mechanism for the process. The maximum percentage of Cr(VI) removal obtained is 75.5% with 7?g/L dosage at pH 1.3 and adsorbate concentration was 100?mg/L. From the normal probability, residual, contour, 3D surface, main effect and interaction plot along with t-test, ANOVA, and F-test, it is observed that pH has the most significant effect on the percentage removal followed by adsorbent dosage and time. The adsorbate concentration has the least effects and interaction effects are found to be significant.     

Removal of toxic chromium(VI) from aqueous solution by activated carbon using Casuarina equisetifolia

Highly activated carbon from the seed husk of Casuarina Casuarinas equisetifolia, a worldwide famous plant, have been prepared and tested for the removal of toxic Cr(VI) from its aqueous solution. The adsorbent was investigated for influences of initial chromium concentration (75, 100, 125, and 150 mg l^-1), pH, contact time, and quantity of carbon on removal of Cr(VI) from aqueous solution at room temperature (25±2 °C). The adsorption kinetic of Cr(VI) was studied, and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R²≥0.99). The Langmuir and Freundlich models fit the isotherm data well. Furthermore, the Gibbs free energy was obtained for each system and was found to be-5.29 kJ mol^-1 for removal of Cr(IV). The negative value of Δ G° indicates the feasibility and spontaneous nature of adsorption. The results indicate that acidic pH (1.05) supported the adsorption of Cr(IV) on activated carbon. The maximum adsorption capacity of Cr(VI) on activated carbon was about 172.4 mg g^-1 at pH 1.05.     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Cr (VI) and Fe (III) removal using Cajanus cajan husk

Husk of tur dal (Cajanus cajan) was investigated as a new biosorbent for the removal of Fe (III) and Cr (VI) ions from aqueous solutions. Parameters like agitation time, adsorbent dosage and pH were studied at different initial Fe (III) and Cr (VI) concentrations. The biosorptive capacity of the Tur dal husk was dependent on the pH of the chromium and iron solution, with pH 2 and 2.5 respectively being optimal. The adsorption data fit well with Langmuir and Freundlich isotherm models. The practical limiting adsorption capacity (qmax) calculated from the Langmuir isotherm was 96.05 mg of Cr(VI)/ g of the biosorbent at an initial pH of 2.0 and 66.65 mg/g at pH 2.5. The infrared spectra of the biomass revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Cr (VI) and Fe (III) ions. Characterisation of tur dal husk has revealed that it is an excellent material for treating wastewaters containing low concentration of metal ions.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

A review for chromium removal by carbon nanotubes

Water pollution is still a serious problem for the entire world. Adsorption technology is a promising process which is based on the fabrication of novel, cheap, non-dangerous and highly sorptive materials for application in wastewater purification processes. Nanomaterials are functional groups which find use in many important fields such as medicine, food processing and agriculture. This review collects information from published works about the use of carbon nanotubes as efficient and promising adsorbents in chromium removal from (real or synthesised) wastewater. For this purpose, isotherm (Langmuir, Freundlich, etc.), kinetic (pseudo-first-, second-order, etc.), thermodynamic (free-energy Gibbs, enthalpy, entropy) and desorption–regeneration studies were discussed in detail. Moreover, significant factors such as pH, agitation time, temperature, adsorbent dosage and initial dye concentration are also reported extensively. The maximum monolayer adsorption capacities of Cr(III) and Cr(VI) ions were 0.39–238.09 and 1.26–370.3?mg/g, respectively. The absolute values of ΔG⁰ and ΔH⁰ ranged 0.237–48.62 and 0.16–58.43?kJ/mol, respectively.     

Chromium (VI) biosorption by immobilized Aspergillus niger in continuous flow system with special reference to FTIR analysis

Aspergillus niger was treated with acid and immobilized in calcium alginate matrix. The dynamic removal of Cr (VI) ion was studied using continuously fed column packed with immobilized biosorbent beads. Column experiments were carried out to study the effect of various bed heights (20, 30, 40 cm) under different flow rates (5, 7.5, 10 ml min(-1)) on efficiency of biosorption. The maximum time (1020 minutes; 17 hr) before breakthrough point was observed in case of 40 cm bed height with flow rate of 5ml min(-1). FTIR analysis of acid treated immobilized A. niger was used fora qualitative and preliminary analysis of chemical functional groups present on its cell wall which provided the information on nature of cell wall and Cr (VI) interaction during the process of biosorption. The IR spectra of biosorbent recorded before and after chromium biosorption had shown some changes in the band patterns, which were finally analyzed and was found that chemical interaction such as ion-exchange between carboxyl (-COOH), hydroxyl (-OH) and amine (-NH2) group of biosorbent and Chromium ion were mainlyinvolved in biosorption of Cr (VI) onto A. niger cell wall surface. The biosorbed metal was eluted from biosorbent by using 0.1 M H2SO4 as eluant. Immobilized biosorbent could be reused for five consecutive biosorption and desorption cycles without apparent loss of efficiency after its reconditioning. Considering all above factors together this paper discusses the efficient chromium biosorption process carried out by immobilized A. niger biosorbent.     

Mass-transfer processes of chromium(VI) adsorption onto guava seeds

The chromium(VI) biosorption onto guava seeds, as an alternative method for Cr⁶⁺ removal from aqueous solutions, was investigated. The parameters affecting kinetics and equilibrium of Cr⁶⁺ adsorption onto guava seeds were studied. An external mass-transfer diffusion coefficient k and intra-particle diffusion coefficient k_i were determined to measure the rate-limiting step of adsorption. A single external mass-transfer diffusion model and intra-particle diffusion models were used. The effects of initial pH, sorbent mass, and initial Cr⁶⁺ concentrations on mass-transfer coefficients were investigated. The external mass-transfer coefficient has an average value of 7.2×10^-3 cm s^-1, while the intra-particle mass-transfer diffusion coefficient was 0.34 mg g^-1 min^-0.5. This indicates that external diffusion to the guava seeds surface and intra-particle diffusion are both involved in the sorption process. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models with an average correlation coefficient R²=0.98. The maximum removal of Cr⁶⁺ was obtained at pH 1 (about 100% for adsorbent dose of 15 g l^-1 and 25 mg l^-1 initial concentration of Cr⁶⁺). The results indicated that the guava seeds exhibit acceptable sorption capacity.     

1,3,5-triazine-triethylenetetramine polymer: an efficient adsorbent for removal of Cr(VI) ions from aqueous solution

The synthesis of 1,3,5-triazine-triethylenetetramine (TATETA), its characterization by infrared spectroscopy and elemental analysis, and its application for removal of Cr(VI) ions from aqueous solution is reported. The effects of pH, contact time, initial concentration of Cr(VI), sorbent dose, and temperature on adsorption were investigated and optimized by batch adsorption experiments. Adsorption was highest at acidic conditions with an equilibration time of 25 min. The adsorption followed a Langmuir model, with an adsorption capacity of 303 mg g^?1, was second order in its kinetics, and exothermic and thus spontaneous.     

Role of NADH-dependent chromium reductases,exopolysaccharides and antioxidants by Paenibacillus thiaminolyticus PS 5 against damage induced by reactive oxygen species

ABSTRACT

Cr (VI) being used in various activities of industries and its improper treatment lead to contamination of environment. Among different methods, biological is the most efficient method to control pollution from soils affected with metals. Present study was designed to assess the role of Paenibacillus thiaminolyticus PS5 for adsorption, Cr (VI) reduction and mechanism of reduction. Sorption of chromium (VI) by strain PS5 was obtained by batch equilibrium method. Cr (VI) reduction in both free and immobilised cells were evaluated by 1,5-Diphenyl Carbazide method. The formation of biofilm by Paenibacillus thiaminolyticus PS5 was observed for colour change as well as quantified spectrophotometrically. Analysis kits were used to measure the amount of eDNA, superoxide and malondialdehyde (MDA). Metal resistant strain PS5 was characterised as P. thiaminolyticus using 16S rRNA gene sequence. Maximum biosorption of Cr (VI) by strain PS5 was found at pH 6–8 and 100–400 µgCr/mL within 24 hours of incubation. Complete reduction of Cr (VI) by strain PS5 was achieved at pH 6–8 and100–300 µg/mL Cr (VI). Paenibacillus thiaminolyticus PS5 immmobilisation on sodium alginate and polyvinyl alcohol facilitated complete reduction of Cr (VI) within 18 hours due to the formation of more biofilm under metal stress conditions. Strain PS5 reduced almost all Cr (VI) into Cr (III) in supernatant, most of which was immobilised by cell debris. Experiments confirmed the reduction of Cr (VI) by cytosolic cell-free extracts which is a mechanism of detoxification. The release of exopolysaccharides and antioxidants by strain PS5 played a protective role against cell damage by Cr (VI) as Cr (VI) could not release the significant amount of eDNA, superoxide and MDA. The present study proved strain PS5 to be a super bioinoculant which has great capacity for adsorption, biotransformation and can activate cytosolic reductases, exopolysaccharides and antioxidants against oxidative damage.     

Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium,kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔG^o (−0.8– −4.58 kJ·mol⁻¹), ΔH^o (15.6–44.4 kJ·mol⁻¹), and ΔS^o (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr(III) concentration. The analysis of the values of biosorption activation energy (E_a = −7 kJ·mol⁻¹) and the intra-particle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Selective targeted adsorption and inactivation of antibiotic-resistant bacteria by Cr-loaded mixed metal oxides

• LDHs and MMOs was synthesized by ultrasound-assisted one-step co-precipitation. • MMOs performs the best for Cr(VI) and E. coli_NDM-1 simultaneous removal. • Possible antibacterial pathways of Cr-MMOs were proposed. Herein we provide a novel high-efficiency nanocomposite for bacterial capture based on mixed metal oxides (MMOs) with deleterious chromium properties. With both the layer structure of layered double hydroxides (LDHs) and the magnetic properties of Fe, MMOs enrich the location of ionic forms on the surface, providing a good carrier for adsorption of the heavy metal Cr(VI). The capacity for adsorption of Cr(VI) by MMOs can be as high as 98.80 mg/g. The prepared Cr(VI)-MMOs achieved extremely expeditious location of gram-negative antibiotic-resistant E. coli_NDM-1 by identifying lipid bilayers. Cr-MMOs with a Cr loading of 19.70 mg/g had the best bactericidal effect, and the concentration of E. coli_NDM-1 was decreased from ~10⁸ to ~10³ CFU/mL after 30 min of reaction. The binding of nitrogen and phosphorus hydrophilic groups to chromate generated realistic models for density functional theory (DFT) calculations. The specific selectivity of MMOs toward bacterial cells was improved by taking Cr(VI) as a transferable medium, thereby enhancing the antibacterial activity of Cr-MMOs. Under the combined action of chemical and physical reactions, Cr(VI)-MMOs achieved high capacity for inactivation of bacteria. Moreover, the metallic elements ratio in Cr-MMOs remained stable in their initial valence states after inactivation. This guaranteed high removal efficiency for both heavy metals and bacteria, allowing recycling of the adsorbent in practical applications.     

Heavy metals uptake from aqueous solutions using marine algae (Colpomenia sinuosa): kinetics and isotherms

The adsorption of copper, zinc, cobalt, lead and cadmium ions onto Colpomenia sinuosa was studied as a function of contact time, initial metal ion concentration and initial pH. In addition, desorption studies were performed. Characterisation of this adsorbent was also confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analysis. Batch adsorption experimental data were analysed using Langmuir, Freundlich and Dubinin–Raduschkevich (D–R) adsorption isotherms. The results indicated that the biosorption equilibrium was well described by both the Freudlich and D–R isotherms. Moreover, sorption kinetics was performed and it was observed that equilibrium was reached in<60 min, which could be described by the pseudo-second-order kinetic model for all heavy metals. The sorption of heavy metals onto the biomass was largely dependent on the initial solution pH. The elution efficiency for heavy metal ions desorption from C. sinuosa was determined for 0.1 M HCl, 1.0 M HCl and 1.0 M HNO₃. Desorption efficiency and also adsorption capacity were highest for Pb(II). The results indicate that C. sinuosa has great potential for the removal of heavy metals in an ecofriendly process.     

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

Removal of Novacron Golden Yellow dye from aqueous solutions by low-cost agricultural waste: Batch and fixed bed study

The present work describes the removal of Novacron Golden Yellow (NGY) dye from aqueous solutions using peanut hulls. The experiments were performed with native, pretreated and immobilised forms of peanut hulls. The effect of various operational parameters (pH, biosorbent dose, initial dye concentration and temperature etc.) was explored during batch study. NGY showed maximum removal at low pH and low biosorbent dose. High initial dye concentration facilitated the biosorption process. Maximum dye removal with native, pretreated and immobilised biomass was found to be 35.7, 36.4 and 15.02 mg/g respectively. The experimental data were subjected to different kinetic and equilibrium models. The kinetic data confirmed the fitness of pseudo-second-order rate law for NGY biosorption. The equilibrium modelling was carried out by Freundlich, Langmuir and Temkin models. The isothermal data of NGY removal were best described by Freundlich adsorption isotherm. Negative values of Free energy change (Δ G⁰) for NGY with native and pretreated biomass depicted the spontaneous nature of biosorption process. In column mode, the effects of bed height, flow rate and initial dye concentrations were optimised. Maximum NGY biosorption (7.28 mg/g) was observed with high bed height, low flow rate and high initial concentration in continuous mode. Bohart–Adams model best fitted to the data obtained from column studies. The results indicated that the peanut hulls could be used effectively for the removal of dyes containing wastewater.     

不同价态铬在不同水分条件下的生物有效性及其对水稻的毒性

氧化还原过程在铬的形态转化中起了重要作用,而铬形态的转化能够影响其生物有效性及毒性。通过温室土培试验研究了六价铬(Cr(Ⅵ))与三价铬(Cr(Ⅲ))在淹水与不淹水条件下在土壤溶液中的动态变化及水稻对其吸收的变化。结果表明,土壤中添加Cr(Ⅲ)时,土壤溶液中检测不出Cr;而随着土壤中添加Cr(Ⅵ)浓度的增加,土壤溶液中Cr(Ⅵ)的浓度增加,但是溶液中检测不出Cr(Ⅲ);淹水处理总体上降低了土壤溶液中Cr(Ⅵ)的浓度。而土壤添加Cr(Ⅲ)、Cr(Ⅵ)和水分处理对土壤溶液p H没有显著影响,p H在7.08.0之间变动。土壤添加Cr(Ⅵ)处理的水稻中,只有90 mg·kg-1Cr(Ⅵ)淹水处理的水稻成活,而其余处理水稻没有成活。土壤中添加Cr(Ⅲ)处理,水稻幼苗生物量随Cr(Ⅲ)浓度的增加而显著降低;除了200mg·kg-1Cr(Ⅲ)处理外,其余淹水处理的水稻幼苗生物量明显高于不淹水处理的。土壤添加Cr(Ⅲ)处理的水稻,在不淹水条件下水稻空壳率比较高,淹水条件下,随着土壤中添加Cr(Ⅲ)浓度水平的增加,水稻各部位Cr含量有增加的趋势,但增加不显著,秸秆最高Cr含量达到33.80 mg·kg-1,籽粒中Cr含量最高0.30 mg·kg-1。土壤固定Cr(Ⅲ)的能力远强于Cr(Ⅵ),添加Cr(Ⅵ)处理的土壤溶液中Cr(Ⅵ)的浓度很高,对水稻表现出较强的生长抑制。