Metal sorption properties of sulfur-chlorinated jojoba wax bound to polystyrene beads

A new solid extractant (designated PS-DETA-JS) in which sulfur-chlorinated jojoba wax is bound via an amine spacer group to polystyrene beads was synthesized. The absorption of mercury cations from acidic solutions and of chromate anions from saline solutions onto PS-DETA-JS was investigated. The sorption of mercury ions by the solid extractant was compared with that by liquid-sulfurized jojoba wax impregnated inside macroporous resins. The static and dynamic properties of dichromate sorption from 2–20 g/L NaCl solutions at pH 4.1 were studied. Selective sorption of Cr(VI) was obtained at low chromate concentrations (∼ 6 ppm) in saline aqueous solutions. Complete regeneration of the PS-DETA-JS resin was achieved after the reduction of Cr(VI) to Cr(III) and the elution of the Cr(III) with 1N HCl. © 1997 John Wiley & Sons, Inc.     

Fabrication of chitosan/polyvinyl alcohol/amine modified carbon nanotube composite films for rapid chromate removal

Composite adsorbent films with amine and hydroxyl functionalities were synthesized from chitosan (CS), polyvinyl alcohol (PVA), and amine-modified carbon nanotubes (a-MWCNT) by solvent casting method. Weight proportions of CS to PVA and weight percent of a-MWCNT were optimized to achieve highest chromate removal capacity. Structural characteristics of the composites were investigated using scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and thermal gravimetric analysis. Accordingly, incorporation of a-MWCNT to CS/PVA structure resulted in the generation of nanochannels, which enhanced adsorption capacity. Moreover, the composite comprising 0.4% wt. a-MWCNT provided over 99% of Cr (VI) removal from 50 mg L⁻¹ Cr (VI) solution within five minutes of contact time. Redlich–Peterson and Radke–Prausnitz isotherm models provided the highest conformity to adsorption data. Maximum chromate sorption capacity of CS/PVA/a-MWCNT composite film was determined as 134.2 mg g⁻¹ being 172% higher than that of CS/PVA. Regeneration was best achieved in 1.0 M NaOH and the composite was shown to retain at least 70% of its original capacity after five consecutive adsorption–desorption cycles.     

Investigations of chromium (VI) ion sorption and reduction on strongly basic anion exchanger

Removal of chromium(VI) ions and their reduction were studied on the anion exchanger Dowex PSR-2 in the pH range from 1.5 to 10. The parameters of Cr(VI) sorption process on the anion exchanger were calculated based on the most popular isotherm models such as: Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich (D-R). The Langmuir isotherm was the most appropriate to describe Cr(VI) sorption. The Cr(VI) uptake by Dowex PSR-2 was found to follow the pseudo-second-order rate kinetics. Reduction of chromium(VI) in the pH range 1.5–10 was observed using the HPLC-ICP-MS (high-performance liquid chromatography–inductively coupled plasma-mass spectrometry) method. Oxidation of tri-n-butyl quaternary ammonium groups during the chromate (VI) removal process was observed.     

Use of bulk liquid membrane for the removal of chromium (VI) from aqueous acidic solution with tri-n-butyl phosphate as a carrier

Tri-n-butyl phosphate (TBP) was used as carrier for the transport of chromium (VI) through a hexane bulk liquid membrane. The transport efficiency of chromium (VI) by TBP was investigated under various experimental conditions such as pH of the feed phase (Cr (VI) solution), concentration of the receiving phase (NaOH solution), concentration of TBP in membrane, rate of stirring, effect of transport time, type of solvent, Cr (VI) concentration in feed phase, and effect of temperature. The transport efficiency increased with increasing carrier concentration from 7.5 × 10^− 2 to 2.25 × 10^− 1 mol/L. At high pH (donor phase) the transport rate of chromate ions decreased. At high stirring speed (300 rpm) the Cr (VI) transport from the feed phase to the strip phase was completed within 5 h at 27 °C. Under optimum conditions: donor phase 4.8 × 10^− 4 mol/L K₂Cr₂O₇ solution at pH 1.0 ± 0.1, acceptor phase 1.0 mol/L NaOH solution, membrane phase 2.25 × 10^− 1 mol/L, stirring speed 300 rpm, and temperature 27 °C, the flux rate was found to be 2.90 × 10^− 7 mol/m² s.     

CO2 capture solvent selection by combined absorption-desorption analysis

A method was developed for selection of promising solvents based on CO₂ absorption experiments at 40 °C and 9.5 kPa CO₂ partial pressure followed by desorption of the same solvents at 80 °C down to 1.0 kPa CO₂ partial pressure. Experiments conducted on 13 solvent systems under atmospheric conditions revealed the solvents absorption and desorption characteristics and these were compared with 1.0 M, 2.5 M, 5.0 M and 10.0 M MEA. Results showed that absorption or stripping data alone were not sufficient in making robust solvent selection decisions, and that combined data analysis was necessary. 1.0 M tetraethylenepentamine (TEPA) and 5.0 M MEA showed the best performance in terms of absorption rate. 1.5 M Bis-(3-dimethylaminopropyl) amine (TMBPA) was easy to desorb, has high absorption capacity; and when promoted it showed the best performance in terms of CO₂ carrying capacity. At the test conditions, 1.5 M TMBPA promoted with 1.0 M PZ showed the best potential for efficient CO₂ removal at reduced cost of all systems tested. Its cyclic capacity in mol CO₂/mol amine was found to be 70% higher than that of 5 M MEA.     

Coals as sorbents for the removal and reduction of hexavalent chromium from aqueous waste streams

The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g⁻¹. Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca²⁺, Ba²⁺, Zn²⁺, Cd²) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(III) being essentially non-toxic.     

Catalytic adsorptive stripping voltammetric determination of Cr(VI) in EDTA extracts from solid samples

A catalytic adsorptive stripping voltammetric procedure which allows for Cr(VI) determination in EDTA extracts is presented. EDTA used for extraction can be exploited as a masking agent for Cr(III). The calibration graph for Cr(VI) for an accumulation time of 60 s was linear in the range from 2 × 10⁻¹⁰ to 3 × 10⁻⁸ mol L⁻¹. The relative standard deviation for a Cr(VI) concentration of 2 × 10⁻⁹ mol L⁻¹ was 5.1% (n = 5). The detection limit estimated from three times the standard deviation of low Cr(VI) concentration and accumulation time of 60 s was about 7 × 10⁻¹¹ mol L⁻¹. The influence of foreign ions commonly present in extracts from solid samples is presented. The proposed voltammetric procedure was applied to determine Cr(VI) in EDTA extractable chromium from soil certified reference materials CRM 483 and CRM 041. The performance of the method was also verified by studying the recovery of Cr(VI) from spiked river water.     

Sorption equilibrium of Cr(VI) ions by strong base anion exchangers with pyridine structures

Chromate sorption on pyridine strong base anion exchangers with different functional groups (methyl, ethyl, and butyl groups), at the quaternary nitrogen atoms, was studied as a function of various initial concentrations (100–1500 mg Cr/L) and counterion type. The studied resins in the Cl^?[ form have higher Cr(VI)‐retention capacities than those in the SO form. The pyridine strong base anion exchangers showed a selectivity reversal for the sulfate and chromate anions compared to that of the commercial resins. The alkyl substituent length of the quaternary nitrogen atoms exerted a substantial influence on the Cr(VI)‐retention capacity values for the resins in the Cl^? form; the chromate anions preferred resins with methyl functional groups, that is, resins with a greater hydrophilic structure. For the resins in the SO form the length of the substituent at the quaternary nitrogen atom had only a negligible influence on their Cr(VI)‐retention values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1957–1963, 2004     

Hexavalent chromium adsorption on superparamagnetic multi-wall carbon nanotubes and activated carbon composites

Hexavalent chromium (Cr(VI)) adsorption from aqueous solutions on magnetically modified multi-wall carbon nanotubes (M-MWCNT) and activated carbon (M-AC) was investigated. M-MWCNT and M-AC were prepared by co-precipitation method with Fe²⁺:Fe³⁺ salts as precursors. The magnetic adsorbents were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscope (SEM). The effects of amount of adsorbents, contact time, initial pH, temperature and the initial concentration of Cr(VI) solution were determined. The adsorption equilibrium, kinetics, thermodynamics and desorption of Cr(VI) were investigated. Equilibrium data fitted well with the Langmuir isotherm for both of the adsorbents. The theoretical adsorption capacities are 14.28 mg/g of M-MWCNT and 2.84 mg/g of M-AC. Cr(VI) adsorption kinetics was modeled with pseudo-second order model, intra-particle diffusion model and Bangham model. Thermodynamic parameters were calculated and ΔG°, ΔH° and ΔS° indicate that the adsorption of Cr(VI) onto M-MWCNT and M-AC was exothermic and spontaneous in nature. Results revealed that M-MWCNT is an easily separated effective adsorbent for Cr(VI) adsorption from aqueous solution.     

Experimental design and batch experiments for optimization of Cr(VI) removal from aqueous solutions by hydrous cerium oxide nanoparticles

Hydrous cerium oxide (HCO) was synthesized by intercalation of solutions of cerium(III) nitrate and sodium hydroxide and evaluated as an adsorbent for the removal of hexavalent chromium from aqueous solutions. Simple batch experiments and a 2⁵ factorial experimental design were employed to screen the variables affecting Cr(VI) removal efficiency. The effects of the process variables; solution pH, initial Cr(VI) concentration, temperature, adsorbent dose and ionic strength were examined. Using the experimental results, a linear mathematical model representing the influence of the different variables and their interactions was obtained. Analysis of variance (ANOVA) demonstrated that Cr(VI) adsorption significantly increases with decreased solution pH, initial concentration and amount of adsorbent used (dose), but slightly decreased with an increase in temperature and ionic strength. The optimization study indicates 99% as the maximum removal at pH 2, 20 °C, 1.923 mM of metal concentration and a sorbent dose of 4 g/dm³. At these optimal conditions, Langmuir, Freundlich and Redlich–Peterson isotherm models were obtained. The maximum adsorption capacity of Cr(VI) adsorbed by HCO was 0.828 mmol/g, calculated by the Langmuir isotherm model. Desorption of chromium indicated that the HCO adsorbent can be regenerated using NaOH solution 0.1 M (up to 85%). The adsorption interactions between the surface sites of HCO and the Cr(VI) ions were found to be a combined effect of both anion exchange and surface complexation with the formation of an inner-sphere complex.     

Adsorption of Cr(VI) and As(III) on coaly activated carbon in single and binary systems

In single component system, the adsorption of Cr(VI) and As(III) increase with contact time. Solution pH is found influencing the adsorption. Cr(VI) removal is found to be maximum (98%) at pH = 2. While, As(III) removal is found to be maximum at pH = 6 (77.2%). The adsorption capacity of Cr(VI) is greater than that of As(III) in single component system. Several adsorption isotherms were used to fit the equilibrium data. The adsorption kinetic data of Cr(VI) and As(III) were analyzed and is found fitting well in a pseudo-second-order equation both in single and binary systems. In binary system, the adsorption of As(III) is generally higher than that in single system. The pseudo-second-order rate constant k₂ is 0.5037 g/mg min in binary system larger than 0.0782 g/mg min in single system. However, the presence of As(III) in solution does not significantly influence the capacity of Cr(VI) adsorption on coaly activated carbon (CAC). The complexation between Cr(VI) and As(III) influence the adsorption, resulting in increased adsorption of As(III). The complexation structure of As(III), Cr(VI) and CAC was proposed as A-Cr(VI)-As(III) (A represents the adsorption site on the CAC).     

Comparing the efficacy of a novel waste-based adsorbent with PAC for the simultaneous removal of chromium (VI) and cyanide from electroplating wastewater

The potential of powdered pistachio hull (PHP) for the co-adsorption of Cr(VI) and cyanide from electroplating wastewater was compared to that of powdered activated carbon (PAC). The results of dynamic adsorption experiments indicated that the complete and simultaneous removal of Cr(VI) and cyanide from wastewater was achieved with 2 g/L of PHP after 60 min of contact. Alternatively, with PAC, 69.2 and 77.8% of Cr(VI) and cyanide, respectively, were removed under the same conditions. Adsorption of Cr(VI) and cyanide by PHP and PAC followed pseudo-second order kinetics, and the equilibrium adsorption data best fit the Langmuir isotherm. The maximum capacity of PHP for the co-adsorption of Cr(VI) and cyanide was 117.6 and 151.5 mg/g, respectively, and the maximum capacity of PAC for the adsorption of Cr(VI) and cyanide was 47.6 and 39.4 mg/g, respectively. It was found that which intraparticle diffusion controlled the adsorption of Cr(VI) and cyanide onto PHP and PAC under the selected conditions. Overall, PHP efficiently adsorbed Cr(VI) and cyanide from industrial effluents; thus, PHP is an affordable and cost-effective system for the treatment of wastewater.     

Study on the flocculating properties of quaternized carboxymethyl chitosan

Summary Quaternized carboxymethyl chitosan (QCMC) was prepared through the grafting reaction of carboxymethyl chitosan (CMC) with 3-chloro-2-hydroxypropyl trimethylammonium chloride (CTA) as a quaternizing agent in 2-propanol medium under basic condition. The synthetic conditions for QCMC were as follows: 40.0% of NaOH aqueous solution as catalyst; reaction temperature, 60.0 °C and reaction time, 10.0 h; NaOH/CMC, 0.50; CTA/CMC, 1.50 (mass ratio). The characterization by FT-IR and ¹H NMR demonstrated that QCMC was a typical amphoteric chitosan derivative in which the carboxymethyl group and the quaternary ammonium group were both introduced into the chitosan molecular chain. QCMC was applied to flocculate a simulated wastewater containing 40.15 mg/L Cd(II) or 15.62 mg/L Cr(VI) respectively. The results indicated that the appropriate pH value for removal of Cd(II) and Cr(VI) were ca 8.5 and 5.0, and the appropriate corresponding mass concentrations of QCMC was 140 mg/L and 120.0 mg/L, respectively. Under these conditions, the removal ratio of Cd(II) and Cr(VI) may reach 99.7% and 94.4%, respectively.     

The rapid electrochemical preparation of dissolved ferrate(VI): Effects of various operating parameters

The preparation of ferrate(VI) by the anodic dissolution of an iron wire gauze in concentrated NaOH solution is described. An anolyte of 0.35-0.48 M Na₂FeO₄ can be produced during 3-6 h electrolysis in initial 16 M NaOH solution at 35 °C. The experimental results indicate that the Fe(VI) concentration variation rate during electrolysis is close related to the factors such as current density, alkaline concentration, the ratio of effective surface area to anolyte volume, the passivation of iron anode and the decomposition of ferrate(VI), etc., and the relevant empirical equation is given. The alkalinity of anolyte has large effect on the electrogeneration of ferrate(VI), especially during an interval electrolysis.     

Removal of Cr(VI) from water using Fe(II)-modified natural zeolite

In this study, natural zeolite aggregates with the particle size of 1.4–2.4 mm were modified by Fe(II). The unmodified zeolite and Fe(II)-modified zeolite (Fe-eZ) were subjected to batch and column tests to study the Cr(VI) sorption, transport, and retardation. Modification of the natural zeolite with Fe(II) resulted in an increase in Cr(VI) sorption to 6 mmol/kg. The Cr(VI) sorption followed a pseudo-second-order kinetics with a rate of 17 mmol/g h and a rate constant of 0.7 g/mmol h. Cr(VI) removal from solution increased with an increase in ionic strength, but decreased as the solution pH increased. At a Cr(VI) input concentration of 100 mg/L, unmodified zeolite did not show any Cr(VI) retardation at all. In contrast, the observed retardation factor of Fe-eZ for Cr(VI) increased by a factor of 6. The hydraulic conductivity of the zeolite showed little change before and after Fe(II) modification and before and after Cr(VI) sorption, suggesting its good mechanical stability to be used as packing materials for permeable reactive barriers in groundwater remediation.     

Glycerol desorption from ion exchange and adsorbent resin using supercritical fluid technology: An optimization study

In this study, glycerol desorption from Purolite^® PD206 resin was investigated using conventional and supercritical fluids (SCF) techniques. Untreated biodiesel was purified by dry washing using the resin and, after purification, the glycerol desorption was carried out using absolute ethanol under atmospheric conditions at different mass flows (10-30 g/min) or using ethanol-modified supercritical CO₂ (1:3 molar ratio of ethanol:CO₂), under a pressure of 140 bar, within a temperature range of 106-134 °C and with mass flow rates of 6-34 g/min. The results showed that ethanol is an efficient solvent for this process and that the supercritical desorption is much faster than conventional desorption process. Employing the Response Surface Methodology (RSM) it was found that temperature has the greatest effect on the resin regeneration time using supercritical fluids. Optimum conditions obtained were 106.1 °C and 21.9 g/min, in which the resin was regenerated in only 4.17 min.     

A Continuous Stirred Tank Reactor Study on Chromic Acid Removal by Ion Exchange

ABSTRACT

Dilute chromic acid removal by anion exchange was studied using a continuous stirred tank reactor (CSTR) system. A rate model based on film diffusion control was formulated for quantitative study on the chromate removal. For simplicity, the rate and mass balance equations were formulated for total Cr(VI) concentration. Equations were derived for the effluent concentration history as well as the time dependent Cr(VI) concentration in the resin. The derived equations for solid and liquid phase Cr(VI) concentration variations were tested and verified by the experimental results obtained. Effects of various operating conditions, such as resin size, feed concentration, and flow rate, were also discussed.     

Studies on permeation of uranium (VI) from phosphoric acid medium through supported liquid membrane comprising a binary mixture of PC88A and Cyanex 923 in n-dodecane as carrier

Present studies deal with the application of supported liquid membrane (SLM) technique for the separation of uranium (VI) from phosphoric acid medium using a binary mixture of 2-ethyl hexyl phosphoric acid-mono-2-ethyl hexyl ester (PC88A) and neutral donor which is a mixture of four tri-alkyl phosphine oxide better known as Cyanex 923 in n-dodecane as a carrier and (NH₄)₂CO₃ as a receiving phase. Various parameters like feed acidity, nature of strippant, carrier concentration, membrane pore size, membrane thickness etc. which affect the transport of U(VI) have been studied in detail. Experiments have also been carried out to see the transport behaviour of different fission products from a diluted High Level Waste (HLW) solution. Stability of the membrane against the leaching of the extractant and stability of the membrane support have also been investigated. We have tried to model the physicochemical transport of U(VI) in SLM as well as establishing the mechanism (Diffusion controlled) of transport. More than 95% uranium (VI) is recovered in 360 min using a binary mixture of 0.60 M PC88A and 0.15 M Cyanex 923 in n-dodecane as carrier and 0.5 M (NH₄)₂CO₃ as stripping phase from the 0.5 M H₃PO₄ feed. Lower concentration of H₃PO₄ (0.5 M) and optimum carrier concentration (0.60 M PC88A + 0.15 M Cyanex 923) in the mole ratio of 4:1 is found to be the most suitable condition for maximum transport of uranium (VI). The optimum conditions obtained from this study was also applied to recover uranium from analytical waste in phosphoric acid medium generated in the laboratory.     

Chromate Reductase YieF from Escherichia coli Enhances Hexavalent Chromium Resistance of Human HepG2 Cells

Hexavalent chromium (Cr(VI)) is a serious environmental pollutant and human toxicant. Mammalian cells are very sensitive to chromate as they lack efficient chromate detoxifying strategy, e.g., chromate-reducing genes that are widely present in prokaryotes. To test whether introduction of prokaryotic chromate-reducing gene into mammalian cells could render higher chromate resistance, an Escherichia coli chromate-reducing gene yieF was transfected into human HepG2 cells. The expression of yieF was measured in stably transfected cells HepG2-YieF by quantitative RT-PCR and found up-regulated by 3.89-fold upon Cr(VI) induction. In chromate-reducing ability test, HepG2-YieF cells that harbored the reductase showed significantly higher reducing ability of Cr(VI) than HepG2 control cells. This result was further supported by the evidence of increased Cr(VI)-removing ability of crude cell extract of HepG2-YieF. Moreover, HepG2-YieF demonstrated 10% higher viability and decreased expression of GSH synthesizing enzymes under Cr(VI) stress. Subcellular localization of YieF was determined by tracing GFP-YieF fusion protein that was detected in both nucleus and cytoplasm by laser confocal microscopy. Altogether, this study successfully demonstrated that the expression of a prokaryotic Cr(VI)-reducing gene yieF endowed mammalian cell HepG2 with enhanced chromate resistance, which brought new insight of Cr(VI) detoxification in mammalian cells.     

Photoredox processes in the Cr(VI)–Cr(III)–oxalate system and their environmental relevance

Irradiation of the [Cr(C₂O₄)₃]³⁻ complex or the chromate(VI)–oxalate mixture, or the ternary system composed of Cr(III), Cr(VI) and oxalate, leads to chromium photoreductions in consequence of the ligand to metal charge transfer (LMCT) excitations induced by artificial solar radiation. In the case of the Cr(III) complex, the photoreduction involves the innersphere electron transfer leading to the formation of the Cr(II) species and the C₂O₄⁻ radicals. On reacting with molecular oxygen, Cr(II) is oxidised to Cr(III) catalysing thereby the oxalate substitution reaction. Moreover, under specific conditions, Cr(II) can be also oxidised to Cr(VI). Chromate(VI) is not photoreducible, but in the presence of oxalate, or other sacrificial electron donor, the outersphere photoinduced electron transfer (PET) produces Cr(V) species and the C₂O₄⁻ radicals. This initiates a series of thermal reactions leading to the formation of Cr(III) and oxidized oxalate (CO₂). In the system composed of [Cr(C₂O₄)₃]³⁻ and chromate(VI), the acidic medium and anoxic conditions favour the Cr(VI) photoreduction, whereas alkaline oxygenated solutions assist the Cr(VI) photoproduction. When an approximately neutral solution equilibrated with the ambient air is irradiated intermittently, Cr(VI) is consumed and/or produced, accordingly to the time sequence of exposure and dark periods. The oscillations of Cr(VI) concentrations are accompanied by continuous oxidation of oxalate, playing the role of the sacrificial electron donor. The effects of solution pH, molecular oxygen, concentrations of reagents and cations on the reaction rates were investigated. The results of this paper revealed that the Cr(III)/Cr(VI) system under environmental conditions behaves as the photocatalytic one catalysing the oxidation of oxalate or other organic matter by molecular oxygen, contributing thereby to the abatement of pollution.