Protocol for Extraction and Determination of Cr(VI) in Solid Materials with a High Cr(III)/Cr(VI) Ratio Using EDDS as a Leaching Agent for Cr(VI) and a Masking Agent for Cr(III)

A sensitive and selective protocol for the extraction of all forms of Cr(VI) from solid materials followed by determination by catalytic adsorptive stripping voltammetry has been elaborated. Cr(VI) was leached to a solution with 0.2 mol L^?1 (NH₄)₂SO₄/NH₄OH+0.1 mol L^?1 EDDS (pH 9.5) and simultaneously Cr(III) was transferred to a nonactive electrochemical complex with EDDS. The method allows for Cr(VI) determination in solid samples containing even a 1000–2000 fold excess of extractable Cr(III) without its noticeable influence. The effects of several experimental variables such as the composition and pH of the extractant, the time and temperature of the solid sample mixing with the extractant were studied. At the optimized conditions more than 95% of total Cr(VI) recoveries from solid samples were achieved. The validation of the proposed procedure was carried out by Cr(VI) determination in certified reference material CRM 019 Ash, spiked and unspiked with Cr(III), and by comparing the obtained results with those obtained using other common extraction procedures.     

Synthesis of Calcium Silicate Hydrate from Coal Gangue for Cr(VI) and Cu(II) Removal from Aqueous Solution

Both the accumulation of coal gangue and potentially toxic elements in aqueous solution have caused biological damage to the surrounding ecosystem of the Huainan coal mining field. In this study, coal gangue was used to synthesize calcium silicate hydrate (C-S-H) to remove Cr(VI) and Cu(II)from aqueous solutions and aqueous solution. The optimum parameters for C-S-H synthesis were 700 °C for 1 h and a Ca/Si molar ratio of 1.0. Quantitative sorption analysis was done at variable temperature, C-S-H dosages, solution pH, initial concentrations of metals, and reaction time. The solution pH was precisely controlled by a pH meter. The adsorption temperature was controlled by a thermostatic gas bath oscillator. The error of solution temperature was controlled at ± 0.3, compared with the adsorption temperature. For Cr(VI) and Cu(II), the optimum initial concentration, temperature, and reaction time were 200 mg/L, 40 °C and 90 min, pH 2 and 0.1 g C-S-H for Cr(VI), pH 6 and 0.07 g C-S-H for Cu(II), respectively. The maximum adsorption capacities of Cr(VI) and Cu(II) were 68.03 and 70.42 mg·g⁻¹, respectively. Furthermore, the concentrations of Cu(II) and Cr(VI) in aqueous solution could meet the surface water quality standards in China. The adsorption mechanism of Cu(II) and Cr(VI) onto C-S-H were reduction, electrostatic interaction, chelation interaction, and surface complexation. It was found that C-S-H is an environmentally friendly adsorbent for effective removal of metals from aqueous solution through different mechanisms.     

Application of NKF-6 zeolite for the removal of U(VI) from aqueous solution

To better understand the application of NKF-6 zeolite as an adsorbent for the removal of U(VI) from radionuclides and heavy metal ions polluted water, herein, NKF-6 zeolite was employed to remove U(VI) at different experimental conditions. The influence of solid/liquid ratio, contact time, pH, ionic strength, humic substances and temperature on sorption of U(VI) to NKF-6 zeolite was investigated using batch technique under ambient conditions. The experimental results demonstrated that the sorption of U(VI) on NKF-6 zeolite was strongly dependent on pH. The sorption property of U(VI) was influenced by ionic strength at pH < 7.0, whereas was independent of ionic strength at pH > 7.0. The presence of fulvic acid or humic acid promoted the sorption of U(VI) on NKF-6 zeolite at low pH values while restrained the sorption at high pH values. The thermodynamic parameters (i.e., ΔS ⁰, ΔH ⁰, and ΔG ⁰) calculated from the temperature-dependent sorption isotherms demonstrated that the sorption process of U(VI) on NKF-6 zeolite was endothermic and spontaneous. At low pH values, the sorption of U(VI) was dominated by outer-sphere surface complexation and ion exchange with Na⁺/H⁺ on NKF-6 zeolite surfaces, while inner-sphere surface complexation was the main sorption mechanism at high pH values. From the experimental results, one can conclude that NKF-6 zeolite can be used as a potential adsorbent for the preconcentration and solidification of U(VI) from large volumes of aqueous solutions.     

Comparative Study of Chromium Biosorption by Mesorhizobium amorphae Strain CCNWGS0123 in Single and Binary Mixtures

The appearance of chromium in the aqueous effluent is a major concern for the modern industry. In this work, Mesorhizobium amorphae strain CCNWGS0123 was investigated as a biosorbent to remove chromium from aqueous solutions. The optimum pH for Cr(III) and Cr(VI) biosorption were 4 and 2, respectively. This isolate showed an experimental maximum Cr(III) adsorption capacity of 53.52 mg?L^?1, while the result was 47.67 mg?L^?1 for Cr(VI), with an initial 100 mg?L^?1 Cr ions and 1.0 g?L^?1 biomass. In terms of time equilibrium, Cr(III) ion was more readily adsorbed than Cr(VI) by this isolate. The biosorption data of both ions fit the Langmuir isotherm better than that of Freundlich model. Meanwhile, this organism exhibited a good capability to release Cr ions, with desorption efficiency of 70 % for Cr(III) and 76 % for Cr(VI). Fourier transform infrared spectroscopy analysis showed that –OH, –COO, –NH, amide I, and C=O were involved in Cr(III) and Cr(VI) binding. The biosorbent was further characterized by scanning electron microscopy and energy-dispersive X-ray spectrometry, which indicated an accumulation of chromium on the cellular level. In the binary mixtures, the removal ratio of total Cr and Cr(III) increased from pH?2 to 4. The highest removal ratio of the total Cr was observed in the 25/25 mg?L^?1 mixture at pH?4. In addition, the removal efficiency of Cr(VI) was closely influenced by Cr(III) in the mixture, decreasing to 23.57 mg?g^?1 in the 100/100 mg?L^?1 mixture system, due to the competition of Cr(III). The potential usage of the chromium-resistant rhizobium for the remediation of chromium-contaminated effluents has been demonstrated based on the above results.     

Étude de l’élimination du Cr(VI) par l’oxyde mixte obtenu par calcination de l’hydroxyde double lamellaire MgAl

A magnesium aluminium hydrotalcite-like compound (HT) containing carbonate anions in the interlayer space and with a final Mg/Al ratio of 2 was synthesized by the co-precipitation method. The obtained material was characterized by powder X-ray diffraction (XRD), Fourier-Transform–Infrared spectroscopy (FT–IR), thermal analysis (ATG/ATD), and surface area measurements (BET). The interaction of the clay with Cr(VI) has been studied by ultraviolet–visible (UV–vis) spectroscopy. The calcined hydrotalcite (HT-C) showed the highest capacity of removal of chromium ions, and their sorption capacities for Cr(VI) are 4.85 mmol/g. The effect of various parameters on the preparation conditions for the removal of chromium, such as the contact time, the amount of sorbent, the initial concentration of Cr(VI), and the pH values of aqueous solution were also investigated to identify their influence on Cr(VI) sorption. The characterization of the calcined hydrotalcite (HT-C) after interaction with Cr(VI) ions by FT–IR spectroscopy showed that Cr(VI) was adsorbed and intercalated by the solid.     

Adsorption of51Cr(VI) on manganese dioxide from aqueous solution

Sorption of⁵¹Cr(VI) by MnO₂ has been studied as a function of pH and ionic concentration in the presence of certain added cations and anions. The findings are explained in the light of deprotonation/hydroxyl ion association reaction on oxide surface and its subsequent interaction with the tracer. Infrared spectroscopy has shown the chemical interaction of Cr(VI) on the surface of MnO₂. The influence of certain interfering ions has been shown on the sorption of⁵¹Cr(VI) on MnO₂ surface. An attempt has been made to concentrate traces of⁵¹Cr under optimum experimental conditions. The experimental observation shows that the activity sorbed under specified conditions can be recovered appreciably by leaching the pre-adsorbed carrier.     

Cr(VI) ion removal from artificial waste water using supported liquid membrane

In this study, a novel flat-type synergic-supported liquid membrane was evaluated with a mixture of N-methyl-N,N,N-trioctylammonium chloride (Aliquat 336) and tributyl phosphate (TBP) as the carrier and kerosene as the diluent to remove Cr(VI) from synthetic waste water. The main parameters involved in the process were identified and optimised. The parameters were divided into two groups, those that were independent and those having an interaction. The parameters of the carrier/kerosene volumetric proportion and stirring rate were optimised individually due to their nature. The optimal values of these parameters were 0.5 and 500 min^?1, respectively, for a constant carrier/kerosene ratio and stirring rate in the designed experiments using the response surface method (RSM). The four parameters of TBP/Aliquat 336, chromium concentration in the feed phase, feed and product pH were optimised using RSM; it was observed that the TBP/Aliquat 336 ratio, feed pH, pH of the stripping phase and interaction of this parameter with feed concentration have the most important effects on the removal of Cr(VI). The optimal levels of these parameters were 0.61, 71.75 mg L^?1, 3.5 and 12.66 for the ratio of TBP/Aliquat 336, feed chromium concentration, pH of the feed and pH of the product, respectively. An experimental removal rate of 94.63 % at the optimized levels was obtained.     

Enhancing Removal of Cr(VI), Pb2+, and Cu2+ from Aqueous Solutions Using Amino-Functionalized Cellulose Nanocrystal

In this work, the amino-functionalized cellulose nanocrystal (ACNC) was prepared using a green route and applied as a biosorbent for adsorption of Cr(VI), Pb²⁺, and Cu²⁺ from aqueous solutions. CNC was firstly oxidized by sodium periodate to yield the dialdehyde nanocellulose (DACNC). Then, DACNC reacted with diethylenetriamine (DETA) to obtain amino-functionalized nanocellulose (ACNC) through a Schiff base reaction. The properties of DACNC and ACNC were characterized by using elemental analysis, Fourier transform infrared spectroscopy (FT-IR), Kaiser test, atomic force microscopy (AFM), X-ray diffraction (XRD), and zeta potential measurement. The presence of free amino groups was evidenced by the FT-IR results and Kaiser test. ACNCs exhibited an amphoteric nature with isoelectric points between pH 8 and 9. After the chemical modification, the cellulose I polymorph of nanocellulose remained, while the crystallinity decreased. The adsorption behavior of ACNC was investigated for the removal of Cr(VI), Pb²⁺, and Cu²⁺ in aqueous solutions. The maximum adsorption capacities were obtained at pH 2 for Cr(VI) and pH 6 for Cu²⁺ and Pb²⁺, respectively. The adsorption all followed pseudo second-order kinetics and Sips adsorption isotherms. The estimated adsorption capacities for Cr(VI), Pb²⁺, and Cu²⁺ were 70.503, 54.115, and 49.600 mg/g, respectively.     

Development of analytical procedures for the determination of hexavalent chromium in corrosion prevention coatings used in the automotive industry

The European directive 2000/53/EC limits the use of Cr(VI) in vehicle manufacturing. Although a maximum of 2 g of Cr(VI) was authorised per vehicle for corrosion prevention coatings of key components, since July 2007 its use has been prohibited except for some particular applications. Therefore, the objective of this work was to develop direct analytical procedures for Cr(VI) determination in the different steel coatings used for screws. Instead of working directly with screws, the optimisation of the procedures was carried out with metallic plates homogeneously coated to improve the data comparability. Extraction of Cr(VI) from the metallic parts was performed by sonication. Two extraction solutions were tested: a direct water extraction solution used in standard protocols and an ammonium/ammonia buffer solution at pH 8.9. The extracts were further analysed for Cr speciation by high-performance liquid chromatography (HPLC) inductively coupled plasma (ICP) atomic emission spectrometry or HPLC ICP mass spectrometry depending on the concentration level. When possible, the coatings were also directly analysed by solid speciation techniques (X-ray photoelectron spectroscopy, XPS, and X-ray absorption near-edge structure, XANES) for validation of the results. Very good results between the different analytical approaches were obtained for the sample of coating made up of a heated paint containing Zn, Al and Cr when using the extracting buffer solution at pH 8.9. After a repeated four-step extraction procedure on the same portion test, taking into account the depth of the surface layer reached, good agreement with XPS and XANES results was obtained. In contrast, for the coatings composed of an alkaline Zn layer where Cr(VI) and Cr(III) are deposited, only the extraction procedure using water allowed the detection of Cr(VI). To elucidate the Cr(VI) reduction during extraction at pH 8.9, the reactivity of Cr(VI) towards different species of Zn generally present in the coatings (metallic Zn and zinc oxide) was studied. The results showed that metallic Zn rapidly reduces Cr(VI), whereas this reaction is less evident in the presence of zinc oxide. Water was then retained for coatings containing metallic Zn.     

Utilization of industrial waste as a novel adsorbent: Mono/competitive adsorption of chromium(VI) and nickel(II) using diatomite waste modified by EDTA

The adsorption of Cr(VI) and Ni(II) using ethylenediaminetetraacetic acid‐modified diatomite waste (EDTA‐DW) as an adsorbent in single and binary systems was investigated. The EDTA‐DW was characterized using various analytical techniques, including Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer–Emmett–Teller measurements, X‐ray diffraction, scanning electron microscopy and energy‐dispersive spectrometry. The adsorption experiment was conducted by varying pH, adsorbent dosage, initial concentration and temperature. In the single system, the sorption data for Cr(VI) fitted the Langmuir isotherm, but the Ni(II) adsorption data fitted well the Freundlich isotherm. The maximum sorption capacity of Cr(VI) and Ni(II) was 2.9 mg g^?1 at pH = 3 and 3.64 mg g^?1 at pH = 8, respectively. The kinetic data for both Cr(VI) and Ni(II) followed well the pseudo‐second‐order kinetic model in single and binary systems. Meanwhile, the extended Langmuir and extended Freundlich multicomponent isotherm models were found to fit the competitive adsorption data for Cr(VI) and Ni(II). In addition, in the binary system, the existence of Ni(II) hindered the adsorption of Cr(VI), but the presence of Cr(VI) enhanced the removal of Ni(II). This study provides some realistic and valid data about the usage of modified diatomite waste for the removal of metal ions.     

Interaction of U(VI) with Na-attapulgite in the presence and absence of humic acid as a function of pH, ionic strength and temperature

The interaction of U(VI) with Na-attapulgite was studied by using batch technique at different experimental conditions. The effect of contact time, solid content, pH, ionic strength and temperature on the sorption of U(VI) onto Na-attapulgite in the presence and absence of humic acid was also investigated. The results showed that the sorption of U(VI) on Na-attapulgite achieved sorption equilibrium quickly. Sorption of U(VI) on Na-attapulgite increased quickly with increasing pH at pH < 6.5, and then decreased with pH increasing at pH > 6.5. The sorption curves were shifted to left in low NaClO₄ solutions as compared those in high NaClO₄ solutions. The sorption was strongly dependent on pH and ionic strength. The sorption was dominated by ion exchange or outer-sphere surface complexation at low pH values, and by inner-sphere surface complexation or surface precipitation at high pH values. The thermodynamic parameters (i.e., ΔH ⁰, ΔS ⁰, and ΔG ⁰) for the sorption of U(VI) were calculated from the temperature dependent sorption isotherms, and the results suggested that the sorption reaction was an endothermic and spontaneous process. The Na-attapulgite is a suitable material in the removal and preconcentration of U(VI) from large volumes of aqueous solutions in nuclear waste management.     

Chromium retention properties of N-alkyl quaternized poly(4-vinylpyridine)

The ability of solid N-alkyl quaternized poly(4-vinylpyridine) with hexyl, octyl and decyl bromide for the retention of chromate and dichromate forms of Cr(VI) in aqueous solutions is studied. The retention of Cr(VI) was investigated by batch equilibrium procedure and this study was supported by UV-vis spectrophotometry, infrared (IR) spectroscopy and thermal analysis (glass transition temperature and thermal degradation). The retention of Cr(VI) was possible in the range of concentrations between 1 × 10⁻⁶ and 1 × 10⁻³ mol/L and it was dependent on the length of the polyelectrolyte side aliphatic chain. Thermogravimetric analysis (TGA) indicated that solid phase, (N-alkyl quaternized poly(4-vinylpyridine), with Cr(VI) (P4VPyC8-Cr(VI)) is slightly more stable than P4VPyC8 in absence of Cr(VI). Differential scanning calorimetric (DSC) measurements indicate that the segmental movements are restricted due to the presence of chromate and/or dichromate ions in the solid phase.     

Speciation of chromium in water samples using dispersive liquid–liquid microextraction and flame atomic absorption spectrometry

A novel method for preconcentration is described for chromium speciation at microgram per liter to sub-microgram per liter levels. It is based on selective complex formation of both Cr(VI) and Cr(III) followed by dispersive liquid–liquid microextraction and determination by microsample introduction-flame atomic absorption spectrometry. Effects influencing complex formation and extraction (such as pH, temperature, time, solvent, salinity and the amount of chelating agent) have been optimized. Enrichment factors up to 275 and 262 were obtained for Cr(VI) and total Cr, respectively. The calibration graph is linear from 0.3 to 20 µg L^?1, and detection limits are 0.07 and 0.08 µg L^?1 for Cr(VI) and total Cr, respectively. Relative standard deviations (RSDs) were obtained to be 2.0% for Cr(VI) and 2.6% for total Cr (n?=?7).     

Cr(III) and Cr(VI) Removal from Aqueous Solutions by Cheaply Available Fruit Waste and Algal Biomass

This study compared the effectiveness of different biosorbents, viz. materials commonly present in natural treatment systems (Scenedesmus quadricauda and reed) and commonly produced fruit wastes (orange and banana peel) to remove Cr(III) and Cr(VI) from a synthetic wastewater simulating tannery wastewater. The Cr(III) removal efficiency followed the order S. quadricauda?>?orange peel?>?banana peel?>?reed, whereas the Cr(VI) removal followed the order banana peel?>?S. quadricauda?>?reed?>?orange peel. The chromium biosorption kinetics were governed by the intraparticle diffusion mechanism. Isotherm data obtained using the different biosorbents were fitted to the Langmuir, Freundlich, and SIPS models, revealing that the experimental data followed most closely the monolayer sorption theory-based Langmuir model than the other models. The maximum Cr(III) sorption capacity, calculated using the Langmuir model, was found to be 12 and 9 mg/g for S. quadricauda and orange peel, respectively, and the maximum Cr(VI) sorption capacity calculated for banana peel was 3 mg/g. The influence of biosorbent size, pH, solid–liquid ratio, and competing ions were examined for Cr(III) biosorption by S. quadricauda and orange peel and for Cr(VI) sorption by banana peel. The solution pH was found to be the most influential parameter affecting the biosorption process: whereas pH 5 was found to be optimum for maximum removal of Cr(III), Cr(VI) was best removed at a pH as low as 3. Interference to chromium sorption by various ions revealed that Cr(III) binding onto orange peel occurs through electrostatic forces, whereas Cr(VI) binding onto banana peel through non-electrostatic forces.     

Flow injection solid phase extraction electrothermal atomic absorption spectrometry for the determination of Cr(VI) by selective separation and preconcentration on a lab-made hybrid mesoporous solid microcolumn

A lab-made hybrid mesoporous solid was employed in a flow injection solid phase extraction electrothermal atomic absorption spectrometric (FI–SPE–ETAAS) system for the selective retention of Cr(VI). The solid was prepared by co-condensation of sodium tetraethylortosilicate and 3-aminopropyltriethoxysilane by sol–gel methodology and one-pot synthesis and characterized by Fourier transform infrared spectroscopy, X ray diffraction spectroscopy, and scanning electronic microscopy. Adsorption capacities at different pH values of both, Cr(VI) and Cr(III), were also measured in order to obtain the optimum retention for Cr(VI) with no interference of Cr(III). The maximum capacity of adsorption (4.35 mmol g^− 1) was observed for pH values between 2–3, whilst Cr(III) was found to remain in solution (adsorption capacity = 0.007 mmol g^− 1). Then, a microcolumn (bed volume: 7.9 µL) was filled with the solid and inserted in the FI–ETAAS system for analytical purposes. Since the analyte was strongly retained by the filling in the anionic form, 0.1 mol L^− 1 hydroxylammonium chloride in 1 mol L^− 1 hydrochloric acid was selected as eluent due to its redox characteristics. In this way, the sorbed Cr(VI) was easily released in the cationic form. The enrichment factor (EF) was found as a compromise between sensitivity and sample throughput and a value of 27 was obtained under optimized conditions: pH 2, sample loading 2 mL min^− 1 (60 s), elution flow rate 0.5 ml min^− 1 (eluent volume: 75 μL).     

Neutron activation analysis for chromium(III) and (VI) in lixiviated liquid through a calcined chromium(VI) adsorbed hydrotalcite

Summary Electrophoresis followed by neutron activation analysis was utilized to determine chromium(III) and (VI) in mixed solutions. These solutions proceeded from Cr(VI) adsorbed hydrotalcites heated at 800 °C to partially immobilize Cr in the Mg-Al oxide solid solution. Immobilization was studied by Cr lixiviation with NaCl solutions through the heated hydrotalcites. The results have shown that Cr lixiviated was in the form of CrO₄^2- ions, mainly because some Cr(VI) was not completely reduced to Cr(III) during heating. Chromium lixiviated from HT-Cr sample, heated at 800 °C and γ-irradiated at 1000 kGys, was found, as well, in the form of CrO₄^2- ions. Although γ-irradiation increases Cr immobilization in the solid, it does not reduce completely all CrO₄^2- ions present in the solid and, therefore, some Cr is lixiviated through the solid in the form of CrO₄^2- ion.     

Adsorption of chromium from aqueous solution using chitosan beads

A basic investigation on the removal of Cr(III) and Cr(VI) ions from aqueous solution by chitosan beads was conducted in a batch adsorption system. The chitosan beads were prepared by casting an acidic chitosan solution into an alkaline solution. The influence of different experimental parameters; pH, agitation period and different concentration of Cr(III) and Cr(VI) ions was evaluated. A pH 5.0 was found to be an optimum pH for Cr(III) adsorption, and meanwhile pH 3.0 was the optimum pH for the adsorption of Cr(VI) onto chitosan beads. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherms and isotherm constants for the adsorption of Cr(III) and Cr(VI) onto chitosan beads. Results indicated that Cr(III) and Cr(VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacities of Cr(III) and Cr(VI) ions onto chitosan beads were 30.03 and 76.92 mg g⁻¹, respectively. Results showed that chitosan beads are favourable adsorbents. The Cr(III) and Cr(VI) ions can be removed from the chitosan beads by treatment with an aqueous EDTA solution.     

石墨烯负载零价纳米铁材料的合成及去除水中Cr(VI)的研究

以石墨粉为原料,采用改良Hummers方法合成石墨烯,然后通过液相还原法制备出石墨烯负载纳米铁材料(Graphene-supported nanoscale zero-valent iron,G-nZVI),借助扫描电子显微镜(SEM)、红外光谱分析仪(FTIR)进行表征,并以G-nZVI为反应材料,研究其对水体中Cr(VI)的去除效率,结果显示:室温下,当G-nZVI投加量为0.4g/L,Cr(VI)的初始浓度为20 mg/L,初始pH值为3.0时,Cr(VI)的去除率在2h内可以达到95%以上。G-nZVI具有磁性,使用后可通过外加磁力除去,以防对水体的二次污染,具有较好的应用前景。     

Removal of hexavalent chromium from wastewaters by bone charcoal

The adsorption of hexavalent chromium onto bone charcoal was studied as a function of time, amount of charcoal, pH, concentration of chromium and sample volume. The cross interference with other elements was also investigated. Tests were carried out with solutions of chromium(VI) at concentrations between 5 and 25 mg · L^–1. Chromium removal efficiencies higher than 90% were achieved at pH = 1 using 2 g of bone charcoal and a stirring time in the order of 30 min. Acid and alkaline pretreatments of bone charcoal did not improve the sorption capacity of bone charcoal against Cr(VI). The presence of other ions had practically no influence on the chromium removal. The presence of a matrix of tannery effluents did not reduce the removal capacity of bone charcoal for Cr(VI), but it was confirmed that only 47% of Cr(III) can be removed using these conditions. Received: 20 July 1998 / Revised: 4 October 1998 / Accepted: 10 October 1998