Removal of Pb(II), Cr(III) and Cr(VI) from Aqueous Solutions Using Alum-Derived Water Treatment Sludge

The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO₃ at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.     

Biosorption of Chromium (III) and Chromium (VI) by Untreated and Pretreated Cassia fistula Biomass from Aqueous Solutions

The present study explained the effect of pretreatments on the biosorption of Cr (III) and Cr (VI) by Cassia fistula biomass from aqueous solutions. For this purpose Cassia fistula biomass was pretreated physically by heating, autoclaving, boiling and chemically with sodium hydroxide, formaldehyde, gluteraldehyde, acetic acid, hydrogen peroxide, commercial laundry detergent, orthophosphoric, sulphuric acid, nitric acid, and hydrochloric acid. The adsorption capacity of biomass for Cr (III) and Cr (VI) was found to be significantly improved by the treatments of gluteraldehyde (95.41 and 96.21 mg/g) and benzene (85.71 and 90.81 mg/g) respectively. The adsorption capacity was found to depend on pH, initial metal concentration, dose, size, kinetics, and temperature. Maximum adsorption of both the Cr (III) and Cr (VI) was observed at pH 5 and 2. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. The kinetic studies showed that the sorption rates could be described better by a second order expression than by a more commonly applied Lagergren equation.     

Fluoride Removal from Aqueous Solutions by Boehmite

Boehmite was used for the removal of fluoride ions from aqueous solutions in a batch system. The pH, contact time, and fluoride concentration in the removal of fluoride ions by boehmite were evaluated. The removal of fluoride ions by boehmite was the highest between the pH values of 4.5 and 7.5. The kinetic fluoride sorption from aqueous solutions by boehmite was best described by the pseudo-second-order model, and equilibrium was reached in about 24 h. The Freundlich model described the isotherm sorption process; the results indicate that the sorption mechanism is chemisorption on a heterogeneous material.     

Removal of Zn from Aqueous Solutions by Low-Rank Coal

The ability of an immature coal (leonardite) to remove zincfrom aqueous solutions was studied as a function of pH,contact time and concentration of metal solutions.Effective removal of Zn²⁺ was demonstrated at pHvalues of 5–6. Kinetic study showed that the adsorption ofZn²⁺ occurs in two phases: a rapid phase followed by aquasi-equilibrium state attained within the first twohours. The adsorption isotherm was measured at 25 °C, using adsorptive solutions at the optimum pH value todetermine the adsorption capacity.     

Adsorptive Removal of Chromium(VI) from Aqueous Solution by an Agricultural Waste-Based Activated Carbon

Activated carbon was prepared from an agricultural waste, coconut coir, and its characteristics were compared with that of a commercial bituminous coal-based activated carbon. The activated carbon possessed higher surface area, micropore area, micropore volume and average pore diameter, and well-developed meso- and micropores. Batch test on adsorption of chromium(VI) by the coconut coir activated carbon showed that the extent of chromium(VI) adsorption was dependent on chromium(VI) concentration, contact time, pH and activated carbon dose. Maximum adsorption occurred at pH 1.0–2.0 and equilibrium adsorption was attained in 2.5 h. Chromium(VI) adsorption followed pseudo second-order kinetics. Equilibrium chromium(VI) adsorption data for the coconut coir activated carbon and the commercial activated carbon were described by the Langmuir and Freundlich isotherm models and indicated higher chromium(VI) adsorption capacity of the coconut coir activated carbon. Chromium(VI) adsorption capacity of the coconut coir activated carbon was compared with that of activated carbon prepared from different waste material and bituminous coal. The coconut coir activated carbon showed high limiting capacity for adsorption of chromium(VI). Coconut coir activated carbon is a suitable substitute for commercial activated carbon in the adsorptive removal of chromium(VI) from water.     

Biosorption of Bromophenol Blue from Aqueous Solutions by Rhizopus Stolonifer Biomass

The removal of bromophenol blue dye (BPB), from aqueous solutions, by biosorption on a non-living biomass of Rhizopus stolonifer was investigated in a batch system. Pretreatment of the biomass with NaOH was found to be the most effective means to enhance the biosorption of BPB. The fungal biomass exhibited the highest dye sorption capacity at pH 2 and the uptake process followed the pseudo-second order reaction model. The equilibrium sorption capacity of the biomass increased as the initial dye concentration increased, and the maximum uptake value was estimated at 1111 mg/g according to Langmuir adsorption isotherm. The adsorbed dye was easily desorbed from a fungal biomass with 0.1 M NaOH solution and the regenerated biomass could be reused for other biosorption essays with similar performances.     

Role of Humic Substances on Cr(VI) Removal from Groundwater with Pyrite

Groundwater composition may have a pronounced impact on long-term performance of permeable reactive barriers (PRBs). Here, batch and column experiments were conducted to investigate the effects of humic acid (HA) on Cr(VI) removal by pyrite in systems containing cations such as Ca²⁺ and Mg²⁺. HA was observed to have inhibitory effect on Cr(VI) uptake by pyrite under the experimental conditions studied (e.g., pH 3 to 8). HA sorbed onto pyrite surface and thus (1) competed against Cr(VI) for pyritic surface sites and/or (2) increased electrostatic repulsion between Cr(VI) and pyrite. In systems with HA and Ca²⁺/Mg²⁺, the Cr(VI) uptake by pyrite decreased drastically relative to HA alone due to the aggregation of HA with Ca²⁺/Mg²⁺. The formation of such HA aggregates/precipitates blocked Cr(VI) ions to reach its binding sites, thereby resulting in a substantial decrease in Cr(VI) uptake. Overall, the results have major implications for proper design and operation of PRBs with pyrite as the reactive material.     

Zinc Removal from the Aqueous Solutions by the Chemically Modified Biosorbents

Biosorbents are the natural origin adsorbents, which popularity in environmental engineering is steadily increasing due to their low price, ease of acquisition, and lack of the toxic properties. Presented research aimed to analyze the possibility of chemical modification of the straw, which is a characteristic waste in the Polish agriculture, to improve its biosorption properties with respect to removal of selected metals from aquatic solutions. Biosorbents used during the tests was a barley straw that was shredded to a size in the range of 0.2–1.0 mm. The biosorption process was performed for aqueous solutions of zinc at a pH 5. Two different modifications of straw were analyzed: esterification with methanol and modification using the citric acid at elevated temperature. The results, obtained during the research, show a clear improvement in sorption capacity of the straw modified by the citric acid. In the case of straw modified with methanol, it has been shown that the effectiveness of zinc biosorption process was even a twice lower with respect to the unmodified straw. Moreover, it was concluded that the removal of analyzed metals was based mainly on the ion-exchange adsorption mechanism by releasing a calcium and magnesium ions from the straw surface to the solution.

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Combined Removal of Zinc (II) and Cadmium (II) from Aqueous Solutions by Adsorption onto High-Calcium Turkish Fly Ash

The aim of this work is the investigation of possible use of flyash in the removal of zinc (Zn²⁺) and cadmium (Cd²⁺) contained in aqueous solutions. Batch adsorption experiments wereperformed in order to evaluate the removal efficiency oflignite-based fly ash. The parameters studied include contact time, pH,temperature, initial concentration of the adsorbate and fly ashdosage. The contact time necessary to attain equilibrium was found to be two hours. Maximum adsorption occurred in the pH range of 7.0 to 7.5. The percent adsorption of Zn²⁺ and Cd²⁺ increased with an increase in concentration of Zn²⁺ and Cd²⁺, dosage of fly ash and temperature. Theapplicability of Langmuir isotherm suggests the formation ofmonolayer coverage Zn²⁺ and Cd²⁺ ions at the outer surface of the adsorbent. Thermodynamic parameters suggested the endothermic nature of the adsorption process. The fly ashwas found to be an metal adsorbent as effective as activated carbon.     

Competitive Removal of Heavy Metals from Aqueous Solutions by Montmorillonitic and Calcareous Clays

A batch sorption method was used to study the removal of few toxic metals onto the Late Cretaceous clays of Aleg formation (Coniacian–Lower Campanian system), Tunisia, in single, binary and multi-component systems. The collected clay samples were used as adsorbents for the removal of Pb(II), Cd(II), Cu(II) and Zn(II) from aqueous solutions. Results show that the natural clay samples were mainly composed of silica, alumina, iron and magnesium oxides. N₂-adsorption measurements indicated mesoporous materials with modest specific surface area of <71 m²/g. Carbonate minerals were the most influencing parameters for heavy metal removal by natural clays in both single and multi-element systems. The affinity sequence was Pb(II)>Cu(II)>Zn(II)>Cd(II) due to the variable physical properties of the studied metals. The maximum adsorption capacity reached 131.58 mg/g in single systems, but decreased to <50.10 mg/g in mixed systems. In single, binary and muti-element systems, the studied clay samples removed substantial amounts of heavy metals, showing better effectiveness than the relevant previous studies. These results suggest that the studied clay samples of the Late Cretaceous clays from Tunisia can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.     

Removal of Arsenic from Aqueous Solutions by Sorption onto Sewage Sludge-Based Sorbent

This study aimed at evaluating and comparing the removal of arsenic from solutions by a low-cost waste-based sorbent, produced by pyrolysing sewage sludge under appropriate conditions, and by a commercially activated carbon. Batch sorption experiments were performed under isothermal conditions (20°C), in order to evaluate the effect of pH on the arsenic sorption kinetics and on the equilibrium sorption capacity of the materials under study. Kinetic data revealed that the arsenic sorption was faster onto the activated carbon than onto the pyrolysed sludge. The sorption process was well described by both the pseudo-first and pseudo-second-order kinetics equations for both materials. Changes in the initial solution pH have distinct effects on the removal of arsenic onto pyrolysed sludge and activated carbon. While for pyrolysed sludge, pH affects essentially the equilibrium time, for activated carbon it affects the sorption capacity. Equilibrium results were well described by both Freundlich and Langmuir isotherm models, although fittings corresponding to the Langmuir isotherm were slightly better. The Langmuir maximum sorption capacity determined for the pyrolysed sludge was 71???g?g^?1, while for activated carbon was 229???g?g^?1. Despite the relative lower capacity of the pyrolysed sludge, the considerable lower cost and the valorisation of the sludge may justify further research on its use for water decontamination.     

The Monitoring of Cr(III) and Cr(VI) in Natural Water and Synthetic Solutions: An Assessment of the Performance of the Dgt and Dpc Methods

The technique of diffusive gradients in thin films or diffusive gradient in thin films (DGT) has been used in this work for the in situ measurement of labile Cr(III) and Cr(VI) species. Direct measurement of Cr(VI) was also carried out in parallel with a field-based colourimetric technique based on the EPA 7196 diphenyl-carbohydrazide (DPC) method. The efficiency of the DGT and DPC methods were tested (a) in the laboratory, using synthetic solutions in the presence of realistic concentrations of Cr, humic substances (HS), and ethylenediaminetetraacetic acid (EDTA), and (b) in the field, in river water affected by effluents discharged by the tannery industry. The main advantage of the DGT method is that it allows the in situ separation of labile species of Cr(III) and Cr(VI), though there are still uncertainties about its performance in field conditions. The DPC method proved to be a fast, accurate, and relatively economical option for the field-based determination of Cr(VI). Sample acidification and ageing of unacidified samples from contaminated aquatic environments, produced significant errors in the determination of ‘dissolved’ Cr. The concentration of Cr(VI) determined by either the DGT or the DPC method exceeds recommended international guidelines.     

Adsorptive Potential of 2-Mercaptobenzimidazole-Immobilized Organophilic Hydrotalcite for Mercury(II) Ions from Aqueous Phase and Its Kinetic and Equilibrium Profiles

An organophilic calcined hydrotalcite (OHTC) was prepared by treating calcined hydrotalcite (HTC) with sodium dodecylbenzene sulphonate (an anionic surfactant) to achieve a high loading of thiol functionality through the immobilization of 2-mercaptobenzimidazole (MBI) as a chelating agent. The adsorbent (MBI-OHTC) obtained was characterized using XRD, FTIR, SEM, TG/DTG, surface area analysis and potentiometric titration. The adsorption of MBI-OHTC to remove Hg(II) ions from aqueous solutions was studied as a function of pH, contact time, metal ion concentration, ionic strength and adsorbent dose. The optimum pH range for the maximum removal of Hg(II) was 6.0–8.0. The maximum value of Hg(II) adsorption was found to be 11.63 and 21.52 mg g^?1 for an initial concentration of 25 and 50 mg l^?1, respectively at pH 8.0. The equilibrium conditions were achieved within 3 h under the mixing conditions employed. A reversible pseudo-first-order used to test the adsorption kinetics. The adsorption mechanism consisted of external diffusion and intraparticle diffusion and the intraparticle mass transfer diffusion was predominated after 20 min of experiment. Extent of adsorption decreased with increase of ionic strength. The experimental isotherm was analyzed with two parameters (Langmuir and Freundlich) and three parameters (Redlich–Peterson) equations. The isotherm data were best modeled by the Freundlich isotherm equation. Complete removal (≈100%) of Hg(II) from 1.0 l of chlor-alkali industry wastewater containing 9.86 mg Hg(II) ions, was possible with 3 g of the adsorbent dose at pH 8.0. About 95.0% of Hg(II) can be recovered from the spent adsorbent using 0.1 M HCl.     

Critical Influence of Culture Medium and Cr(III) Quantification Protocols on the Interpretation of Cr(VI) Bioremediation by Environmental Fungal Isolates

The influence of culture medium composition on chromium(VI) quantification according to diphenylcarbazide (DPC) colorimetric determination was evaluated. Considering the eventual biospeciation of Cr(VI) as a mechanism of microbial bioremediation, the possibility to quantify Cr(III) in culture medium was also explored. Yeast nitrogen base (YNB) was identified as the least interferent culture medium for Cr(VI) quantification by DPC and it was applied to compare different strategies for Cr(III) oxidation. The most appropriate oxidation protocol consisted in the reaction with 80 mM KIO₄ at room temperature for 30 min prior to DPC. Parameters like basal culture medium (vitamins + salts + oligoelements), C and N source were systematically evaluated, either independently or in combination. Results demonstrated that C source was the most interferent culture medium component, being the use of sucrose preferable to glucose. A medium arbitrarily named as YNB′ (YNB without amino acids and ammonium sulfate plus 50 g L^?1 sucrose and 0.6 g L^?1 (NH₄)₂SO₄) was defined for Cr(VI)-amended fungal cultures. Kinetics of growth, Cr(VI) removal, and nutrient consumption for isolates A. pullulans VR-8, filamentous fungus PMF-1, and Lecythophora sp. NGV-1 were obtained. The order of Cr(VI) removal efficiency was as follows: A. pullulans VR-8 > Lecythophora sp. NGV-1 > filamentous fungus PMF-1, and a similar trend was observed for biomass yield and nutrients consumption. Studies on biospeciation by means of the selected Cr(III) oxidation protocol were unsuccessful, leading to Cr(VI) values much lower than expected. It revealed that this kind of protocols should be cautiously evaluated when studying microbial Cr(VI) bioremediation.     

Polydopamine Nanoparticles as a New and Highly Selective Biosorbent for the Removal of Copper (II) Ions from Aqueous Solutions

The adsorption and desorption of copper (II) ions from aqueous solutions were investigated using polydopamine (PD) nanoparticles. The nanoscale PD nanoparticles with mean diameter of 75?nm as adsorbent were synthesized from alkaline solution of dopamine and confirmed using scanning electron microscopy and X-ray diffraction analysis. The effects of pH (2?C6), adsorbent dosage (0.2?C0.8?g?L^?1), temperature (298?C323?K), initial concentration (20?C100?mg?L^?1), foreign ions (Zn²⁺, Ni²⁺, Cd²⁺, Fe²⁺, and Ag⁺), and contact time (0?C360?min) on adsorption of copper ions were investigated through batch experiments. The isotherm adsorption data were well described by the Langmuir isotherm model. The maximum uptake capacity of Cu²⁺ ions onto PD nanoparticles was found to 34.4?mg/g. The kinetic data were fitted well to pseudo-second-order model. Moreover, the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy) were studied.     

Biosorption of Methylene Blue from Aqueous Solutions by Hazelnut Shells: Equilibrium, Parameters and Isotherms

This paper presents a study on the batch adsorption of a basic dye, methylene blue (MB), from aqueous solution onto ground hazelnut shell in order to explore its potential use as a low-cost adsorbent for wastewater dye removal. A contact time of 24 h was required to reach equilibrium. Batch adsorption studies were carried out by varying initial dye concentration, initial pH value (3–9), ionic strength (0.0–0.1 mol L^?1), particle size (0–200 μm) and temperature (25–55°C). The extent of the MB removal increased with increasing in the solution pH, ionic strength and temperature but decreased with increase in the particle size. The equilibrium data were analysed using the Langmuir and Freundlich isotherms. The characteristic parameters for each isotherm were determined. By considering the experimental results and adsorption models applied in this study, it can be concluded that equilibrium data were represented well by Langmuir isotherm equation. The maximum adsorption capacities for MB were 2.14?×?10^?4, 2.17?×?10^?4, 2.20?×?10^?4 and 2.31?×?10^?4 mol g^?1 at temperature of 25, 35, 45 and 55°C, respectively. Adsorption heat revealed that the adsorption of MB is endothermic in nature. The results indicated that the MB strongly interacts with the hazelnut shell powder.