Biosorption of hexavalent chromium from aqueous solution onto pomegranate seeds: kinetic modeling studies

Hexavalent chromium has been proved to be the reason of several health hazards. This study aimed at evaluating the application of pomegranate seeds powder for chromium adsorption (VI) from aqueous solution. Chromium adsorption percentage (VI) increased with increasing the adsorbent dosage. Chromium adsorption capacity (VI), at pH = 2 and 10 mg/L initial metal concentration, decreased from 3.313 to 1.6 mg/g through increasing dosage of adsorbent from 0.2 to 0.6 g/100 ml. The adsorption rate increased through increase in chromium initial concentration (VI). However, there was a removal percentage reduction of chromium (VI). Chromium adsorption kinetics by different models (pseudo-first-order, modified pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion, Boyd kinetic) was investigated as well. Studies on adsorption kinetic indicated that the experimental data were matched by pseudo-second-order model (R ² = 0.999) better. Obtained results demonstrated the pomegranate seeds can be used as an effective biomaterial and biosorbent for hexavalent chromium adsorption from aqueous solutions.     

Removal of hexavalent chromium from aqueous solution by barium ion cross-linked alginate beads

Barium ion cross-linked alginate beads have shown great affinity to toxic hexavalent chromium ions in aqueous solution, in contrast to the traditionally used calcium alginate beads. Our adsorption experiments were carried out by the batch contact method. The optimal pH for removal was found to be pH 4. The equilibrium was established in 4 h, and the removal efficiency of chromium(VI) was found to be 95 %. The adsorption data were applied to Langmuir, Freundlich, Dubinin–Redushkevich (D–R), and Temkin isotherm equations. Both Langmuir and Freundlich isotherm constants indicated a favorable adsorption. The value of mean sorption energy calculated from D–R isoterm indicates that the adsorption is essentially physical. The high maximum chromium(VI) adsorption capacity was determined from the Langmuir isotherm as 36.5 mg/g dry alginate beads. The chromium(VI) adsorption data were analyzed using several kinetic models such as the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models, and the rate constants were quantified. Our study suggests that barium alginate beads can be used as cost-effective and efficient adsorbents for the removal of chromium(VI) from contaminated waters.     

Ionic solid-impregnated sulphate-crosslinked chitosan for effective adsorption of hexavalent chromium from effluents

Microwave-assisted tetrabutyl ammonium-impregnated sulphate-crosslinked chitosan was synthesized for enhanced adsorption of hexavalent chromium. The adsorbent obtained was extensively characterized using Fourier transform infrared, X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray studies. Various isotherm models such as Langmuir, Freundlich and Dubinin–Radushkevich were studied to comprehend the adsorption mechanism of hexavalent chromium by the adsorbent. Maximum adsorption capacity of 225.9 mg g^?1 was observed at pH 3.0 in accordance with Langmuir isotherm model. The sorption kinetics and thermodynamic studies revealed that adsorption of hexavalent chromium followed pseudo-second-order kinetics with exothermic and spontaneous behaviour. A column packed with 1 g of adsorbent was found to give complete adsorption of Cr(VI) up to 900 mL of 200 mg L^?1 solution which discerns the applicability of the adsorbent material for higher sample volumes in column studies. The effective adsorption results were obtained due to both ion exchange and ion pair interaction of adsorbent with hexavalent chromium. Greener aspect of overall adsorption was regeneration of the adsorbent which was carried out using sodium hydroxide solution. In the present study, the regenerated adsorbent was effectively reused up to ten adsorption–desorption cycles with no loss in adsorption efficiency.     

Photocatalytic reduction of hexavalent chromium with commercial Fe/Ti oxide catalyst under UV and visible light irradiation

The photoreduction efficiency of toxic hexavalent chromium into non-toxic trivalent chromium was studied using local low-cost material and modern technology. The materials involved different iron–titanium oxide nanopowders synthesized via simple hydrothermal–hydrolysis process. X-ray diffraction and high-resolution transmission electron microscope were employed to study the structural properties of the as-prepared samples. The effects of molar ratio (Fe/Ti) and hydrothermal temperature on spectroscopic properties have been investigated using Fourier transform infrared FT-IR spectroscopy. The photocatalytic performance of hexavalent chromium was systematically studied at various conditions including initial concentration of Cr(VI), hydrothermal temperature and Fe/Ti ratios of mixed iron–titanium oxide powders. It has been found that the highest photoreduction efficiencies of Cr(VI) were 95.7 and 86.2% at initial concentrations 10 and 60 ppm of Cr(VI), respectively. The synthesized mixed Fe₂O₃–TiO₂ photocatalyst exhibited higher efficiency of about 88% under visible light irradiation. The as-prepared mixed oxide catalyst exhibited high photocatalytic conversion efficiency and recycling stability in comparison with different commercial catalysts.     

Removal of hazardous hexavalent chromium from aqueous solution using divinylbenzene copolymer resin

This paper presents the removal of hazardous hexavalent chromium from liquid waste streams using divinylbenzene copolymer resin Amberlite IRA 96. Important sorption parameters such as contact time, pH, resin dosage and initial metal concentration were studied at 30?°C. The kinetic study was conducted using pseudo-first and pseudo-second-order kinetics at 30?°C. The sorption process was found to be pH dependent. Maximum removal was obtained at pH 2 under optimized conditions. The sorption process was rapid and 99?% of the removal was achieved in first 30?min. The equilibrium data were fitted to both Langmuir and Freundlich models. The better regression coefficient (R ²) in Freundlich model suggests the multilayer sorption process. The value of Gibbs free energy for sorption process was found to be ?12.394?kJmol^?1. The negative value indicated the spontaneity of the sorption process. Scanning electron microscope and energy dispersive X-ray spectroscopy studies were conducted to find the role of surface morphology during sorption process. The Fourier transform infrared study was conducted to identify the functional groups responsible for interaction between the resin and chromium. Desorption and regeneration studies were also carried out.     

Efficient removal of hexavalent chromium from aqueous solutions using autohydrolyzed Scots Pine (Pinus Sylvestris) sawdust as adsorbent

In this work, a low-cost lignocellulosic adsorbent with high biosorption capacity is proposed, suitable for the efficient removal of hexavalent chromium from water and wastewater media. The adsorbent was produced by autohydrolyzing Scots Pine (Pinus Sylvestris) sawdust. The effect of the autohydrolysis conditions, i.e., pretreatment time and temperature, on hexavalent chromium biosorption was investigated using energy-dispersive X-ray spectroscopy (EDS) and UV–visible spectrophotometry. The Freundlich, Langmuir, Sips, Radke-Prausnitz, Modified Radke-Prausnitz, Tóth, UNILAN, Temkin and Dubinin-Radushkevich adsorption capacities and the rate constant values for pseudo-first- and pseudo-second-order kinetics indicated that the autohydrolyzed material exhibits significantly enhanced hexavalent chromium adsorption properties comparing with the untreated sawdust. The Freundlich’s adsorption capacity K _F increased from 2.276 to 8.928 (mg g^?1)(L mg^?1)^1/n , and the amount of hexavalent chromium adsorbed at saturation (Langmuir constant q _m) increased from 87.4 to 345.9 mg g^?1, indicating that autohydrolysis treatment at 240 °C for 50 min optimizes the adsorption behavior of the lignocellulosic material.     

Removal of airborne hexavalent chromium mist using chitosan gel beads as a new control approach

Airborne hexavalent chromium is a known human respiratory carcinogen and allergen. Many workers are exposed to hexavalent chromium in various processes which chromium electroplating plants are the most common. In this study, the feasibility of a new control approach to remove this pollutant using chitosan beads as a biosorbent was investigated. Hexavalent chromium sorption was studied relative to pH, pollution concentration, sorbent concentration, temperature, and air velocity using one factor at a time approach and Taguchi experimental design. Polluted air with different chromium mist concentrations (10–5000 μg/m³) was contacted to chitosan beads (3.3–20 g/L), floating in distilled water with adjusted pH (3–7), using an impinger at different temperatures (20 and 35 °C), and various velocities (1.12 and 2.24 m/s). The ANOVA test result showed that, there were statistical significant differences between factor levels except optimized pH levels. The higher ions removal efficiencies were achieved at lower levels of air velocities, pollution concentrations, and higher levels of solution pH values, temperatures, and sorbent concentrations.     

Treatment of Cr(VI) contaminated water with Pannonibacter phragmitetus BB

Pannonibacter phragmitetus BB was utilized to treat hexavalent chromium [Cr(VI)] contaminated water. Cr(VI) concentration of the contaminated water (pH 10.85) was 534 mg/L. With the inoculum size ranging from 1 to 20 %, P. phragmitetus BB completely reduced Cr(VI) within 27 h when the initial medium concentration exceeded 20 g/L. The lag time of bio-reduction by Cr(VI)-induced cells was 24 h, which was longer than the non-Cr(VI)-induced cells. Under the agitation condition, an obvious bio-reduction lag phase existed and Cr(VI) was completely reduced within 24 h. However, the lag phase was not observed under the static condition, Cr(VI) was reduced continuously after inoculation and Cr(VI) was completely reduced after 27 h incubation. The main chromium components after Cr(VI) reduction were Cr(OH)₃, Cr₂O₃ and CrCl₃. The results of this study are fundamentally significant to the application of P. phragmitetus BB in the treatment of Cr(VI) contaminated water.     

Biotransformation potential of hexavalent chromium by Bacillus pumilus-S4, Pseudomonas doudoroffii-S5 and Exiguobacterium-S8 in association with hydrophytes

Three chromium-resistant bacteria Bacillus pumilus-S4, Pseudomonas doudoroffii-S5 and Exiguobacterium-S8 were isolated from chromium-contaminated wastewater/soil and could resist very high concentrations of potassium chromate in Luria agar (up to 25 mg ml^?1) and acetate minimal medium (2 mg ml^?1). The strains showed growth at diverse pH and temperatures and could resist multiple heavy metals. Pseudomonas doudoroffii-S5 reduced (8.27 mg hexavalent chromium 24 h^?1) at a lower initial potassium chromate concentration (100 μg ml^?1), but overall more chromate (28.4 mg hexavalent chromium 24 h^?1) was reduced at a higher initial concentration (1,000 μg ml^?1). The addition of various heavy metals (zinc sulphate, copper sulphate, and manganese sulphate at 50 μg ml^?1) in the chromium reduction media did not significantly affect the hexavalent chromium reduction potential of these isolates. The chromium removal/detoxification potential of these strains increased when used in conjunction with hydrophytes Eichornia crassipes and Pistia stratiotes. Interestingly, the whole process runs automatically with less energy input, that is, the bacterial strains support the growth of plant while in turn the plant releases exudates that help bacterial growth.     

零价铁去除Cr（Ⅵ）的批实验研究

零价铁去除Cr(Ⅵ)的一系列批实验结果表明：水溶液中发生的氧化还原反应符合准一级反应；对于相同粒度的铁屑(比表面积2．89m^2／g)，固液比由05g／100mL增加到2．0g／100mL，Cr(Ⅵ)质量浓度达到排放标准所需反应时间从26．7min降为3．6min；在固液比相同、原水中Cr(Ⅵ)质量浓度不超过30mg／L时，原水质量浓度增大，达到饮用水标准的反应时间增加；其他条件相同，升高温度可提高零价铁与Cr(Ⅵ)的反应速率。     

Biosorption of ammoniacal nitrogen from aqueous solutions with low-cost biomaterials: kinetics and optimization of contact time

The biosorption of ammoniacal nitrogen (N-NH₄ ⁺) from aqueous solutions by dead biomass of brown seaweed Cystoseira indica and Jatropha oil cake (JOC), which is generated in the process of biodiesel recovery from its seeds, was studied under diverse experimental conditions. The N-NH₄ ⁺ biosorption was strictly pH dependent, and maximum uptake capacity of C. indica (15.21 mg/g) and JOC (13.59 mg/g) was observed at initial pH 7 and 3, respectively. For each biosorbent–N-NH₄ ⁺ system, kinetic models were applied to the experimental data to examine the mechanisms of sorption and potential rate-controlling steps. The generalized rate model and pseudo-second-order kinetic models described the biosorption kinetics accurately, and the sorption process was found to be controlled by pore and surface diffusion for these biosorbents. Results of four-stage batch biosorber design analysis revealed that the required time for the 99 % efficiency removal of 40 mg/L N-NH₄ ⁺ from 500 L of aqueous solution were 76 and 96 min for C. indica and JOC, respectively. The Fourier transform infrared spectroscopy analysis before and after biosorption of ammonium onto C. indica and JOC revealed involvement of carboxylic and hydroxyl functional groups.     

Optimization of a PRB structure with modified chitosan restoring Cr(VI)-contaminated groundwater

Hexavalent chromium is a soluble, mobile, and highly toxic metal ion in groundwater. Adsorption by permeable reactive barriers (PRBs) with special sorbent is a common method to remove hexavalent chromium. A series of experiments have been performed to remove hexavalent chromium in groundwater under PRB with modified chitosan. Therefore, in this paper, the authors first estimated adsorption characteristics of the modified chitosan in a column test, and then calibrated the PRB adsorption parameters in a sandbox test, and finally designed an optimal width, length, and depth of the PRB with the same reactive media in a three-dimensional aquifer. The results showed that the modified chitosan might be a potential adsorption medium. The design schemes can meet the water quality standard of 0.1 mg/L Cr(VI). Heterogeneity of dispersion is a crucial factor when designing the PRB. Therefore, the design of the PRB structures can be appropriate and serve as reference for groundwater remediation.     

几种不同类型的FeOOH吸附水溶液中铬离子研究

采用两种显微结构不同的螺旋状和管状构造的天然铁细菌矿化针铁矿和化学合成的α—FeOOH及两种有机高分子模板矿化结晶的β-FeOOH作为吸附材料，分别在pH=5和6时对含Cr^3 和Cr(Ⅵ)废水进行了吸附实验研究，结果表明，天然生物矿化针铁矿对金属阳离子和阴离子均有明显的吸附作用，其显微结构、大小和形态影响其吸附能力；纯化学合成的针铁矿对铬离子的吸附能力较低；通过有机模板合成的纳米微晶β-FeOOH对Cr^3 和Cr(Ⅵ)均有极高的去除率，这与其表面存在与有机分子络合作用、增大了其表面对金属离子和铬酸根的化学亲合力有关。     

Adsorption of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent prepared from sugarcane bagasse

An iron (III)-impregnated sorbent was prepared from sugarcane bagasse and ferric chloride solution via carbonization/activation in a muffle furnace at 500?°C for 4?h. The adsorption removal of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent was then studied in a batch system. With increasing initial chromium (VI) concentration from 25 to 130?mg/L at an adsorbent dose of 300?mg/50?mL, the amount of adsorbed chromium (VI) increased from 4.15 to 12.20?mg/g at 20?°C, from 4.16 to 12.50?mg/g at 30?°C, and from 4.16 to 13.72?mg/g at 40?°C. The dynamical data fit very well with the pseudo-second-order kinetic model, and the calculated adsorption capacities of 4.16, 8.37, and 13.37?mg/g were equal to the actual values of the experiments at the initial chromium (VI) concentrations of 25, 50, and 100?mg/L, respectively. The Langmuir isotherm could yield better fits than the Freundlich isotherm. The calculated isotherm parameters confirmed the favorable adsorption of chromium (VI) on the iron (III)-impregnated sorbent.     

Advantage of almond green hull over its resultant ash for chromium(VI) removal from aqueous solutions

The discharge of industrial effluents containing hexavalent chromium can be very harmful for the environment. Therefore, Cr(VI) should be removed from contaminated water, and especially from wastewater, to prevent its discharge into the environment. This study is aimed at analyzing the factors that affect the removal of Cr(VI) with the use of almond green hull and ash adsorbent. The effects of pH (2–10), adsorbent dose (2–24 g/L), Cr(VI) concentration (10–100 mg/L), exposure time (1–60 min), and temperature (5–50 °C) were examined. The surface morphology, pore size of adsorbent surfaces were characterized with SEM, EDX, FTIR. Maximum removal occurred at pH = 2. Results showed that the removal yield increased with the rise of exposure time and temperature. The data indicate that due to limited site on adsorbent surface, the removal efficiency decreased as initial Cr(VI) concentration increased. When the adsorbent dose was increased, the removal yield increased in the case of the bioadsorbent as well; however, in the ash adsorbent, there was an increase followed by a decreasing trend. The study highlights that almond green hull can be more efficient than its ash in the removal of Cr(VI) from aqueous solution. As a general result of study, it can be argued that almond green hull bioadsorbent and the obtained carbon are able to remove Cr(VI) from aqueous solutions; thus, they can be used as efficient and economical substitutes for existing adsorbents like activated carbon, for the removal of chromium from polluted aqueous solutions.     

Formation of one-dimensional composites of poly(<Emphasis Type="Italic">m</Emphasis>-phenylenediamine)s based on <Emphasis Type="Italic">Streptomyces</Emphasis> for adsorption of hexavalent chromium

Here, a novel one-dimensional composite of poly(m-phenylenediamine)s coating on filamentous Streptomyces was successfully constructed via a controllable polymerization reaction. The synthesized composites were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Their adsorption isotherm and kinetics for aqueous hexavalent chromium were also systematically examined. The results of scanning electron microscopy analysis indicated that the obtained composites based on Streptomyces were showed a uniform and stable one-dimensional morphology with distinct core–shell configuration. Moreover, the Langmuir isotherm model (R ² > 0.96) and pseudo-second-order equation (R ² = 0.9996) described well the equilibrium adsorption behavior and kinetics of hexavalent chromium adsorption by the composites. In addition, bath adsorption experiments demonstrated the highest adsorption capacity of hexavalent chromium by the composites reached 320.03 mg g^?1 in an acid solution, which was 5.6 times as that of the pure Streptomyces filaments. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses suggested that the adsorption of hexavalent chromium by the composites possibly involved the protonation, redox, and chelation reactions. Therefore, a promising application of these composites in treating acid hexavalent chromium-contaminated wastewater is expectable.     

Facile sorbent from esterified cellulosic sago waste for engine oil removal in marine environment

This article reports on the utilization of chemically modified cellulosic sago (MCS) from sago bark as a highly potential material for remediating oil spills in marine environment. MCS was prepared via incorporation of hydroxyl-rich cellulosic sago bark (CS) with fatty acid derivative. The sorption capacity, hydrophobicity, and lipophilicity of MCS and CS were evaluated. MCS exhibited higher total pore volume (0.012 cm³/g) and high hydrophobicity (60%) compared to CS. The oil spills adsorption studies was compared in batch system both in deionized water and seawater. MCS showed higher oil sorption capacity in deionized water after 60 min (MCS 3.0 g/g, CS 2.4 g/g). The maximum oil sorption capacity of MCS in dynamic seawater system was 5.7 g/g which was higher than CS (5.0 g/g). The results suggested that MCS is a potential low-cost natural sorbent which work best in the removal of oil spilled from dynamic seawater environment than deionized water.     

A study on soil physico-chemical, microbial and metal content in Sukinda chromite mine of Odisha, India

Soil samples from chromite mining site and its adjacent overburden dumps and fallow land of Sukinda, Odisha, were analysed for their physico-chemical, microbial and metal contents. Chromite mine soils were heterogenous mixture of clay, mud, minerals and rocks. The pH of the soils ranges between 5.87 and 7.36. The nutrient contents of the mine soils (N, P, K and organic C) were found to be extremely low. Analysis of chromite mine soils revealed accumulation of a number of metals in high concentrations (Fe > Cr > Mn > Ni > Zn > Pb > Sr) which exceeded ecotoxicological limits in soil. Correlation and cluster analysis of metals revealed a strong relation between Cr, Ni, Fe, Mn among the different attributes studied. Assessment of different microbial groups such as fungi, actinomycetes and bacteria (heterotrophic, spore forming, free-living nitrogen fixing, phosphate solubilising and cellulose degrading) from mine soils were found to be either extremely low or absent in some soil samples. Further chromium tolerant bacteria (CTB) were isolated using 100 mg/L Cr(VI) enriched nutrient agar medium and were screened for their tolerance towards increasing concentrations of hexavalent chromium and other toxic metals. Out of 23 CTB isolates, three bacteria tolerated up to 900 mg/L, 6 up to 500 mg/L, 20 up to 200 mg/L of Cr(VI). These bacteria were also found to be sensitive towards Cu > Co > Cd and very few CTB strains could show multiple metal tolerance. These strains have great scope for their application in bioremediation of toxic chromium ions in presence of other metals ions, which needs to be explored for their biotechnological applications.     

Removal of dyes by adsorption on magnetically modified activated sludge

The ability of magnetically modified activated sludge affected by thermal treatment to remove water-soluble organic dyes was examined. Twelve different dyes were tested. Based on the results of the initial sorption study, four dyes (namely aniline blue, Nile blue, Bismarck brown Y and safranin O) were chosen for further experiments due to their promising binding onto magnetic activated sludge. Significant factors influencing adsorption efficiency such as dependence of contact time, initial pH or temperature were studied in detail. The adsorption process was very fast; more than 88 % of dye content (55 mg/L) was adsorbed within 15 min under experimental conditions used. The equilibrium adsorption data were analyzed by Freundlich, Langmuir and Sips adsorption isotherm models, and the fitting of each isotherm model to experimental data was assessed on the basis of error functions. The maximum adsorption capacities of magnetic activated sludge were 768.2, 246.9, 515.1 and 326.8 mg/g for aniline blue, Bismarck brown Y, Nile blue and safranin O, respectively. The kinetic studies indicated that adsorption of all selected dyes could be well described by the pseudo-second-order kinetic model, and the thermodynamic data suggested the spontaneous and endothermic process.     

Chromium contamination from chromite mine

Among the dominant species of chromium, the trivalent form widely occurs in nature in chromite ores or in silicate minerals and is extremely immobile. The higher oxidation state Cr(VI), is, however, rarely found in nature, is more mobile, and several times more toxic than Cr(III). Cr(VI) occurs in chromates and dichromates manufactured from chromite ores. The hexavalent state is stable in an oxidizing alkaline environment, whereas the trivalent state is stable in a reducing acidic environment. Serpentinization and Mg release during deuteric alteration of ultramafic rocks create alkaline pore water and lateritization is an intensive oxidation process. Chromite ore bodies in oxidized serpentinite therefore may generate hexavalent chromium from the inert chromites and cause hazardous chromium pollution of the water. With this end in view, a combined field and laboratory study has been made on chromite-bearing oxidized serpentinite rocks of Sukinda in Orissa, India. Laboratory leaching studies on mine overburden samples, chemical analyses of streamwater, and hydrolysate incrustation on detrital grains taken from stream beds have indicated the possibility of chromium mobilization from the chromite ores into the waterbodies.