Guided by efficient utilization of natural plant oil and sulfur as low-cost sorbents, it is desired to tailor the porosity and composition of polysulfides to achieve their optimal applications in the management of aquatic heavy metal pollution. In this study, polysulfides derived from soybean oil and sulfur (PSSs) with improved porosity (10.2-22.9 m2/g) and surface oxygen content (3.1-7.0 wt.%) were prepared with respect to reaction time of 60 min, reaction temperature of 170 °C, and mass ratios of sulfur/soybean oil/NaCl/sodium citrate of 1:1:3:2. The sorption behaviors of PSSs under various hydrochemical conditions such as contact time, pH, ionic strength, coexisting cations and anions, temperature were systematically investigated. PSSs presented a fast sorption kinetic (5.0 h) and obviously improved maximum sorption capacities for Pb(II) (180.5 mg/g), Cu(II) (49.4 mg/g), and Cr(III) (37.0 mg/g) at pH 5.0 and T 298 K, in comparison with polymers made without NaCl/sodium citrate. This study provided a valuable reference for the facile preparation of functional polysulfides as well as a meaningful option for the removal of aquatic heavy metals.
In this work, graphene oxide (GO) and its reduced graphene oxide-zinc oxide nanocomposite (rGO-ZnO) was used for the removal of Cr (VI) from aqueous medium. By employing a variety of characterization techniques, morphological and structural properties of the adsorbents were determined. The adsorption study was done by varying concentration, temperature, pH, time, and amount of adsorbent. The results obtained confirmed that rGO-ZnO is a more economical and promising adsorbent for removing Cr (VI) as compared to GO. Kinetic study was also performed, which suggested that sorption of Cr (VI) follows the pseudo-first-order model. For equilibrium study, non-linear Langmuir was found a better fitted model than its linearized form. The maximum adsorption capacity calculated for GO and rGO-ZnO nanocomposite were 19.49 mg/g and 25.45 mg/g, respectively. Endothermic and spontaneous nature of adsorption was detected with positive values of ΔS (change in entropy), which reflects the structural changes happening at the liquid/solid interface.
The objective of this study was to evaluate the effects ofNi(II) and Cr(VI) individually and in combination on the simultaneous removal of chemical oxygen demand (COD), nitrogen and metals under a sequencing batch reactor (SBR) operation. Three identical laboratory-scale SBRs were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in a ratio of 1:12:1:2:8 for a cycle time of 24 h until the steady state was achieved. Nickel(II) at increasing concentrations up to 35 mg/L was added to one of the reactors; Cr(VI) at increasing concentrations up to 25 mg/L was added to a second reactor; while a combination of Ni(II) and Cr(VI) in equal concentrations up to 10 mg/L was added to a third reactor. The results demonstrate that both Ni(II) and Cr(VI) exerted a more pronounced inhibitory effect on the removal of ammonia nitrogen (AN) than on COD removal. Synergistic and antagonistic inhibitory effects on the rates of COD and AN removal, respectively, were observed for the 50% Ni(II) and 50% Cr(VI) (w/w) mixture in the concentration range between 10 and 20 mg/L. The simultaneous presence of 50% Ni(II) and 50% Cr(VI) at a concentration of 20 mg/L resulted in system failure.
The Cr(III) sorption experiments onto Kappaphycus alvarezii waste biomass were conducted at different pH values (2-6) under the conditions of initial metal concentration of 10-50 mg/L and the chemical compositions of Cr-Cu and Cr-Cd. The Cr(III) sorption capacities were slightly dependent on pH, and the maximum sorption capacity was 0.86 mg/g at pH 3. The sorption capacities increased with increase in the initial metal concentration, whereas it was suppressed by the presence of Cu(II) and Cd(III) in the solution. The Cr(III) sorption equilibrium was evaluated using Langmuir, Freundlich and BET isotherms. The sorption mechanisms were characterised using scanning electron microscopy and Fourier transform infrared spectroscopy. The main mechanisms were ion exchange coupled with a complexation mechanism. Kappaphycus alvarezii waste biomass represents a potential for Cr(III) ion removal from aqueous solution.
Physical adsorption and photocatalytic reduction of Cr(VI) in magnetic separable beads were investigated. In order to elucidate the kinetics of photocatalytic process, operating parameters such as catalyst dosage and the initial concentration were examined in detail. It was observed that the reduction rate of Cr(VI) increased with an increase in the catalyst loading, as this translated into an increase in the number of available active sites. Critical scrutiny of the percentage of the initial reduction rate versus time at various initial concentration of Cr(VI) revealed that the rate of substrate conversion decreased as the initial concentration increased. The kinetic analysis of the photoreduction showed that the removal of Cr(VI) satisfactory obeyed the pseudo first-order kinetic according to the Langmuir-Hinshelwood (L-H) model and the absorption of Cr(VI) on the magnetic beads surfaces was the controlling step in the entire reduction process. Furthermore, desorption experiments by elution of the loaded gels with sodium hydroxide indicated that the magnetic photocatalyst beads could be reused without significant losses of their initial properties even after 3 adsorption-desorption cycles.
Cr(VI) biosorption and bioreduction ability of locally isolated Cr-resistant bacteria was investigated using the shake-flask technique. A mixture of S. epidermidis and B. cereus showed the highest minimum inhibitory concentration (MIC) level at 750 mg/L Cr(VI) followed by S. aureus and Bacillus sp. of 250 mg/L, and A. haemolyticus of 70 mg/L. From the Langmuir adsorption isotherm, the treatment of cells with heat-acid resulted in the highest amount of Cr(VI) adsorped (78.25 mg/g dry wt. for S. epidermidis) compared to heat-acetone (67.93 mg/g dry wt. Bacillus sp.), heat only (36.05 mg/g dry wt. S. epidermidis) or untreated cells (45.40 mg/g dry wt. S. epidermidis and B. cereus). FTIR analysis showed the involvement of amine groups in Cr(VI) adsorption. In the bioreduction study, A. haemolyticus was able to completely reduce Cr(VI) up to 50 mg/L.
The aqueous extract of various plants like Coriandrum sativum (AECS), Alternanthera tenella colla (AEAT), Spermacoce hispida (AESH) and Mollugo verticillata (AEMV) was studied for its hexavalent chromium (CrVI) reduction property. Even though antioxidant activity was present, AEAT, AESH and AEMV did not reduce CrVI. AECS showed rapid and dose-dependent CrVI reduction. The efficient reduction of 50 mg/L of CrVI using AECS was attained in the presence of 250 µg/mL of starting plant material, incubating the reaction mixture at pH 2, 30°C and agitation at 190 rpm. Under such conditions, about 40 mg/L of CrVI was reduced at 3 h of incubation. FT-IR analysis revealed the involvement of phenols, alcohols, alpha-hydroxy acid and flavonoids present in the AECS for the CrVI reduction. These results indicate that not all the plant extracts with rich antioxidants are capable of reducing CrVI. Using the conditions standardized in the present study, AECS reduced about 80% of CrVI present in the tannery effluent. These results signify the application of AECS as an eco-friendly method in the wastewater treatment.
Adsorption is one of the most efficient ways to remove heavy metal from wastewater. In this study, the adsorptive removal of hexavalent chromium, Cr (VI) from aqueous solution was investigated using natural zeolite, clinoptilolite, in the form of hollow fibre ceramic membrane (HFCM). The HFCM sample was prepared using phase inversion-based extrusion technique and followed by sintering process at different sintering temperatures in the range of 900-1050 °C. The fabricated HFCM was characterised using scanning electron microscopy (SEM), contact angle, water permeability, and mechanical strength for all HFCMs sintered at different temperatures. The adsorption and filtration test of Cr (VI) were performed using an in-house water permeation set up with a dead-end cross-flow permeation test. An asymmetric structure with sponge- and finger-like structures across the cross-section of HFCM was observed using SEM. Based on the characterisation data, 1050 °C was chosen to be the best sintering temperature as the water permeability and mechanical strength of this HFCM were 29.14 L/m2∙h and 50.92 MPa, respectively. The performance of the HFCM in adsorption/filtration was 44% of Cr (VI) removal at the Cr (VI) concentration of 40 mg/L and pH 4. In addition, the mathematical model was also performed in simulating the experimental data obtained from this study. All in all, the natural zeolite-based HFCM has a potential as a single-step Cr (VI) removal by membrane adsorption for the wastewater treatment.
In this study, effect of degree of deacetylation on property and adsorption capacity of chitosan/polyvinyl Alcohol electrospun membrane has been investigated. Resulting nanofibers were characterized by FESEM, FTIR, XRD, TGA, tensile testing, weight loss test and adsorption test. FESEM result shows, finer nanofiber was fabricated from 42h hydrolyzed chitosan and PVA blend solution. FTIR and XRD result showed a strong interaction between chitosan and polyvinyl alcohol. Higher tensile strength was observed for the nanofiber having 42h hydrolyzed chitosan. Blend solution of chitosan/PVA having low DD chitosan had higher viscosity. The nanofibrous membrane was stable in distilled water, acidic and basic medium. The isotherm study shows that the adsorption capacity (qm) of nanofiber containing higher DD chitosan was higher for Cr(VI). In contrary, the membrane containing chitosan with lower DD showed the higher adsorption capacity for Fe(III) and methyl orange. Moreover, the effect of DD on removal percentage of adsorbate was dependent on the initial concentration of the adsorbate.
Chromium (Cr) is one of the hazardous heavy metals that is naturally carcinogenic and causes various health problems. Metallic nanoparticles such as silver and copper nanoparticles (Ag NPs and Cu NPs) have gained great attention because of their unique chemical, physical, and biological attributes, serving diverse and significant role in various useful and sustainable applications. In the present study, both of these NPs were synthesized by green method in which Azadirachta indica plant extract was used. These nanoparticles were characterized by using advanced instrumental techniques such as Fourier transmission infrared (FTIR), X-ray diffraction (XRD), scanning electron microscope attached with energy-dispersive spectroscopy (SEM-EDS), and elemental mapping. These environmentally friendly nanoparticles were utilized for the batch removal of Cr from the wastewater. For analysis of adsorption behaviour, a range of kinetic isotherm models (Freundlich, Temkin, Dubinin, and Langmuir) and kinetic models (pseudo-first-order and pseudo-second-order) were used for the Cu-NPs and Ag-NPs. Cu NPs exhibited the highest Cr removal efficiency (96%) within a contact time of 10-15 min, closely followed by Ag NPs which achieved a removal efficiency of 94% under the similar conditions. These optimal outcomes were observed at a sorbent dose of 0.5 g/L for Ag NPs and 0.7 g/L for Cu NPs. After effectively capturing Cr using these nanoparticles, the sorbates were examined through SEM-EDX analysis to observe how much Cr metal was attached to the nanoparticles, potentially for future use. The analysis found that Ag-NPs captured 18% of Cr, while Cu-NPs captured 12% from the aqueous solution. More precise experimental conditions are needed for higher Cr removal from wastewater and determination of the best conditions for industrial-level Cr reuse. Although nanomaterial exhibit high efficiency and selectivity for Cr removal and recovery from wastewater, more research is necessary to optimize their synthesis and performance for industrial-scale applications and develop efficient methods for Cr removal and recovery.
In this study, the synthesis and experimental theoretical evaluation of a new chitosan/alginate/hydrozyapatite nanocomposite doped with Mn2 and Fe2O3 for Cr removal was reported. The physicochemical properties of the obtained materials were analyzed using the following methods: SEM-EDX, XRD, FTIR, XPS, pH drift measurements, and thermal analysis. The adsorption properties were estimated based on equilibrium and adsorption kinetics measurements. The Langmuir, Freundlich and Temkin isotherms were applied to analyze the equilibrium data. The thermodynamic analysis of adsorption isotherms was performed. A number of equations and kinetic models were used to describe the adsorption rate data, including pseudo-first (PFOE) and pseudo-second (PSOE) order kinetic equations. The obtained test results show that the synthesized biomaterial, compared to pure chitosan, is characterized by greater resistance to high temperatures. Moreover, this biomaterial had excellent adsorption properties. For the adsorption of Cr (VI), the equilibrium state was reached after 120 min, and the sorption capacity was 455.9 mg/g. In addition, DFT calculations and NCI analyses were performed to get more light on the adsorption mechanism of Cr (VI) on the prepared biocomposite.
Removal of Cr(VI) ions from aqueous solution was investigated using modified palm shell activated carbon. Low Molecular Weight Polyethyleneimine (LMW PEI) was used for impregnation purpose. The maximum amount of LMW PEI adsorbed on activated carbon was determined to be approximately 228.2mg/g carbon. The adsorption experiments were carried out in a batch system using potassium dichromate K(2)Cr(2)O(7) as the source of Cr(VI) in the synthetic waste water and modified palm shell activated carbon as the adsorbent. The effects of pH, concentration of Cr(VI) and PEI loaded on activated carbon were studied. The adsorption data were found to fit well with the Freundlich isotherm model. This modified Palm shell activated carbon showed high adsorption capacity for chromium ions.
This paper presents the results of research on heavy metals removal from water by filtration using low cost coarse media which could be used as an alternative approach to remove heavy metals from water or selected wastewater. A series of batch studies were conducted using different particle media (particle size 2.36-4.75 mm) shaken with different heavy metal solutions at various pH values to see the removal behaviour for each metal. Each solution of cadmium (Cd), lead (Pb), zinc (Zn), nickel (Ni), copper (Cu) and chromium (Cr(III)) with a concentration of 2 mg/L was shaken with the media. At a final pH of 8.5, limestone has significantly removed more than 90% of most metals followed by 80% and 65% removals using crushed bricks and gravel, respectively. The removal by aeration and settlement methods without solid media was less than 30%. Results indicated that the removal of heavy metals was influenced by the media and not directly by the pH. Investigations on the removal behaviour of these metals indicated that rough solid media with the presence of carbonate were beneficial for the removal process. Adsorption and precipitation as metals oxide and probably as metals carbonate were among the two mechanisms that contributed to the removal of metals from solution.
This study analyzes the effects of toxic, hydraulic, and organic shocks on the performance of a lab-scale sequencing batch reactor (SBR) with a capacity of 5L. Petroleum refinery wastewater (PRWW) was treated with an organic loading rate (OLR) of approximately 0.3 kg chemical oxygen demand (COD)/kg MLSSd at 12.8h hydraulic retention time (HRT). A considerable variation in the COD was observed for organic, toxic, hydraulic, and combined shocks, and the worst values observed were 68.9, 77.1, 70.2, and 57.8%, respectively. Improved control of toxic shock loads of 10 and 20mg/L of chromium (VI) was identified. The system was adversely affected by the organic shock when a shock load thrice the normal value was used, and this behavior was repeated when the hydraulic shock was 4.8h HRT. The empirical recovery period was greater than the theoretical period because of the inhibitory effects of phenols, sulfides, high oil, and grease in the PRWW. The system recovery rates from the shocks were in the following order: toxic, organic, hydraulic, and combined shocks. System failure occurred when the combined shocks of organic and hydraulic were applied. The system was resumed by replacing the PRWW with glucose, and the OLR was reduced to half its initial value.
Spent bleaching earth, an industrial waste produced after the bleaching of crude palm oil, was investigated for its potential in removing Cr(VI) from aqueous solution. The earth was treated with different amounts of sulfuric acid and under different activation temperatures. Results show that the optimum treatment process involved 10% sulfuric acid at 350 degrees C. The effects of contact time, pH, initial concentration, sorbent dosage, temperature, sorption isotherms and the presence of other anions on its sorption capacity were studied. Isotherm data could be fitted into a modified Langmuir isotherm model implying monolayer coverage of Cr(VI) on acid activated spent bleaching earth. The maximum sorption capacity derived from the Langmuir isotherm was 21.2 mg g(-1). This value was compared with those of some other low cost sorbents. Studies of anion effect on the uptake of Cr(VI) on acid activated spent bleaching earth provided the following order of suppression: EDTA >PO4(3-)>SO4(2-)>NO3(-)>Cl(-).
The sorption characteristics of Cr(VI) and Cu(II) by ethylenediamine modified rice hull from single and binary metal ion solutions were evaluated under various experimental conditions. Optimal Cr(VI) and Cu(II) removal from single metal ion solutions occurred at pH 2.0 and 5.5, respectively. Simultaneous removal of Cr(VI) and Cu(II) occurred at pH greater than 3.0. The sorption kinetics of Cr(VI) and Cu(II) from single and binary metal ion solutions were studied with reference to metal concentration, agitation rate and particle size. Sorption of Cr(VI) was more rapid than Cu(II). The kinetics of metal ion sorption fitted a pseudo-second order expression. The variation in the initial uptake rates was very small at an agitation rate beyond 150 rpm and sorption was generally independent of particle size. Equilibrium sorption data could be fitted into the Langmuir isotherm equation. Maximum sorption capacities of ethylenediamine modified rice hull for Cr(VI) at pH 2 and Cu(II) at pH 4 in single metal solutions were 0.45 and 0.06 mmol g(-1), respectively. This corresponds to an enhancement factor of 2.6 and 3 fold for Cr(VI) and Cu(II), respectively, compared to natural rice hull. A synergistic effect was observed for sorption of these ions in binary metal solutions.
Electrokinetic process has emerged as an important tool for remediating heavy metal-contaminated soil. The process can concentrate heavy metals into smaller soil volume even in the absence of hydraulic flow. This makes it an attractive soil pre-treatment method before other remediation techniques are applied such that the chemical consumption in the latter stage can be reduced. The present study evaluates the feasibility of electrokinetic process in concentrating lead (Pb) and chromium (Cr) in a co-contaminated soil using different types of wetting agents, namely 0.01 M NaNO3, 0.1 M citric acid and 0.1 M EDTA. The data obtained showed that NaNO3 and citric acid resulted in poor Pb electromigration in this study. As for Cr migration, these agents were also found to give lower electromigration rate especially at low pH region as a result of Cr(VI) adsorption and possible reduction into Cr(III). In contrast, EDTA emerged as the best wetting agent in this study as it formed water-soluble anionic complexes with both Pb and Cr. This provided effective one-way electromigration towards the anode for both ions, and they were accumulated into smaller soil volume with an enrichment ratio of 1.55-1.82. A further study on the application of approaching cathode in EDTA test showed that soil alkalisation was achieved, but this did not provide significant enhancement on electromigration for Pb and Cr. Nevertheless, the power consumption for electrokinetic process was decreased by 22.5%.
The effluent discharge treatment for controlling the environment from non biodegradable metal contaminants using plant extract is an efficient technique. The reduction of hexavalent chromium by abundantly available weed, Aerva lanata L. was investigated using batch equilibrium technique. The variables studied were Cr(VI) concentration, Aerva lanata L. dose, contact time, pH, temperature and agitation speed. Cyclic voltammetry and ICP-MS analysis confirmed the reduction of Cr(VI) to Cr(III). Electrochemical analysis proved that, the chromium has not been degraded and the valency of the chromium has only been changed. ICP-MS analysis shows that 100ng/L of hexavalent chromium was reduced to 97.01ng/L trivalent chromium. These results suggest that components present in the Aerva lanata L. are responsible for the reduction of Cr(VI) to Cr(III). The prime components ferulic acid, kaempherol and β-carboline present in the Aerva lanata L. may be responsible for the reduction of Cr(VI) as evident from LC-MS analysis.
In this study magnetic separable photocatalyst beads containing maghemite nanoparticles (γ-Fe(2)O(3)) in polyvinyl alcohol (PVA) polymer were prepared and used in the reduction of Cr(VI) to Cr(III) in an aqueous solution under sunlight. The unique superparamagnetic property of the photocatalyst contributed by the γ-Fe(2)O(3) and robust property of PVA polymer allow the magnetic beads to be recovered easily and reused for at least 7 times without washing. The concentration of γ-Fe(2)O(3) was varied from 8% (v/v) to 27% (v/v) and the results revealed that the beads with 8% (v/v) γ-Fe(2)O(3) exhibited the best performance where Cr(VI) was reduced to Cr(III) in only 30 min under sunlight. The use of the PVA has improved the bead properties and life cycle of beads which is in line with sustainable practices.
The potential use of non-viable biomass of a Gram negative bacterium i.e. Acinetobacter haemolyticus to remove Cr(III) species from aqueous environment was investigated. Highest Cr(III) removal of 198.80 mg g(-1) was obtained at pH 5, biomass dosage of 15 mg cell dry weight, initial Cr(III) of 100 mg L(-1) and 30 min of contact time. The Langmuir and Freundlich models fit the experimental data (R(2)>0.95) while the kinetic data was best described using the pseudo second-order kinetic model (R(2)>0.99). Cr(III) was successfully recovered from the bacterial biomass using either 1M of CH(3)COOH, HNO(3) or H(2)SO(4) with 90% recovery. TEM and FTIR suggested the involvement of amine, carboxyl, hydroxyl and phosphate groups during the biosorption of Cr(III) onto the cell surface of A. haemolyticus. A. haemolyticus was also capable to remove 79.87 mg g(-1) Cr(III) (around 22.75%) from raw leather tanning wastewater. This study demonstrates the potential of using A. haemolyticus as biosorbent to remove Cr(III) from both synthetic and industrial wastewater.