Speciation of the products from acid reduction of51Cr(VI)

Chromium speciation implies the quantitative determination of Cr(III) and Cr(VI). However, the presence of hydrolytic forms of Cr(III) and the instability of tracer level Cr(VI) in acid media complicates this speciation. The present work describes the stability of several monomeric Cr(III) species formed in the acid reduction of⁵¹Cr(VI). The distribution of Cr(VI) and Cr(X)_n(H₂O) _6–n ^(3–n)+ as a function of time was followed by paired cationic and anionic exchange analyses. The distributions and their time dependences are functions of the initial concentrations of both Cr(VI) and acid. The Cr(III) species eventually level to the hexaaquo form.     

Effect of Mn(II) and Ce(IV) Ions on the Oxidation of Lactic Acid by Chromic Acid

The kinetics and mechanism of lactic acid oxidation in the presence of Mn(II) and Ce(IV) ions by chromic acid were studied spectrophotometrically. The oxidation of lactic acid by Cr(VI) was found to proceed in two measurable steps, both of which gave pyruvic acid as the primary product in the absence of Mn(II). 2Cr(VI)+2CH₃CHOHCOOH → 2CH₃COCOOH+Cr(V)+Cr(III) Cr(V)+CH₃CHOHCOOH → Cr(III)+CH₃COCOOHThe observed kinetics was explained due to the catalytic and inhibitory effects of Mn(II) and Ce(IV) on the lactic acid oxidation by Cr(VI). The reactivity of lactic acid depends upon the experimental conditions. It acts as a two-or three-equivalent reducing agent in the absence or presence of Mn(II). It was examined that Cr(III) products resulting from the direct reduction of Cr(VI) by three-equivalent reducing agents. The oxidation of lactic acid follows the complex order kinetics with respect to [lactic acid]. The activation parameters E_a, ΔH^#, and ΔS^# were calculated and discussed.     

Speciation of Cr(VI)/Cr(III) by electrothermal atomisation AAS after electrodeposition on a L'vov platform

Summary The pyrolysed graphite L'vov platform of a tube furnace is considered as an electrode for the electrodeposition and speciation of chromium by electrothermal atomisation atomic absorption spectrometry (ETA-AAS). Firstly, a preliminary study of the Cr(VI)/Cr(III) voltammetric behavior at pH 4.70 on a glassy-carbon electrode is carried out. Secondly, the L'vov platform is used as a cathodic macro-electrode for the selective preconcentration of Cr(VI)/Cr(III) on a mercury film. Speciation of Cr(VI)/Cr(III) is carried out on the basis of the electrolysis potential (E_e): at pH 4.70 and E_e=–0.30 V, only Cr(VI) is reduced to Cr(III) and accumulated as Cr(OH)₃ by adsorption on a mercury film; at E_e=–1.80 V both Cr(VI) and Cr(III) are accumulated forming an amalgam with added mercury(II) ions. Once the film has been formed, the platform is transferred to a graphite tube to atomise the element. The reliability of the method was tested for the speciation of chromium in natural waters and it proves to be highly sensitive thanks to the electroanalytical step. In all samples, the Cr(VI) concentration was less than the detection limit (0.15 ng ml^–1), and the concentration of Cr(III) agrees with those of total chromium. The analytical recovery of Cr(VI) added to water samples [3.50 ng ml^–1 of Cr(VI)] was 105±6.2%.     

A two-step extraction method for differentiating chromium species in water

The hexavalent Cr species Cr(VI) in natural waters can be quantitatively extracted by diethyldithiocarbamate (DDTC) in the pH range 4.0–4.5 into chloroform, followed by back-extraction into a Hg(II) solution for graphite furnace atomic absorption spectrometry (GFAAS). The trivalent Cr(III) species can be oxidized to Cr(VI) by KMnO₄ and then extracted by the DDTC-Hg(II) procedure. The proposed two-step extraction method combined with GFAAS is suitable for Cr speciation studies in natural water systems.     

Cloud point extraction combined with graphite furnace atomic absorption spectrometry for the determination of chromium species and their distribution in cigarette and cigarette ash

In this article, the contents and distribution of total chromium, Cr(III) and Cr(VI) in various cigarettes and cigarette ashes were determined by using a cloud point extraction (CPE) separation/preconcentration combined with graphite furnace atomic absorption spectrometric (GFAAS) detection. Different extraction reagents, such as tetramethylammonium hydroxide (TMAH), Na₂HPO₄, Na₂CO₃/NaOH, NaOH and H₂O, were tested for the extraction of Cr species, and the extraction efficiency was estimated. The experimental results showed that TMAH was the most efficient extraction reagent for the analyte in cigarette samples. By using the established method, the total chromium, Cr(III) and Cr(VI) in various cigarettes and cigarette ashes were determined and their distribution was studied. It was found that Cr(III) is a main species in cigarettes, but that it can be partly oxidized to Cr(VI) during smoking.     

Reconsideration to the deactivation of TiO2 catalyst during simultaneous photocatalytic reduction of Cr(VI) and oxidation of salicylic acid

Photocatalytic reduction/oxidation and deactivation of TiO₂ photocatalyst was investigated in the systems composed of Cr(VI) and salicylic acid. The selection of analysis method of Cr(IV) was very important to the monitoring of the photocatalytic process. It was found that as previously reported, serious deactivation of TiO₂ catalyst in the simultaneous photo-reduction of Cr(VI) and oxidation of salicylic acid was incorrectly observed if the Cr(VI) level was analyzed by directly monitoring the absorbance at characteristic 348 nm band of Cr(VI), because it seriously suffers from the interferences of the intermediates generated from the degradation of salicylic acid. By using an appropriate method to determine the Cr(VI) concentration, it was observed that all the added Cr(VI) could be reduced, not showing marked deactivation of the photocatalyst. A long time photocatalytic reduction of Cr(VI) under UV illumination induced the deposition of Cr(III) species on the surface of TiO₂ particles, which could cause a mild deactivation of the photocatalyst. However, the accompanied oxidation of salicylic acid was demonstrated to depress the deactivation effect of the deposited Cr(III) species on the photocatalytic activity of the TiO₂ photocatalyst.     

Column chromatographic speciation of chromium for Cr(VI) and several species of Cr(III)

Summary Chromium can be present in aqueous solution as Cr(VI) or in monomeric, dimeric, trimeric and higher polymeric forms of Cr(III). Many monomeric forms of Cr(III) are possible, with the water molecules of Cr(H₂O) ₆ ³⁺ substituted by anionic or neutral species. This proliferation of Cr(III) species makes the complete speciation of chromium a continuing challenge to the analyst. A simple and effective cation exchange procedure for the separation of various of these species uses a small glass column containing 1 mL of pre-treated cation exchange resin (Na⁺ form). Stepwise elution with solutions of perchloric acid, Ca²⁺ (pH=2) and La³⁺ (pH=2) separates Cr(VI) and seven Cr(III) species from CrX₃ to tetramer. Radiometric (Cr-51), spectrophotometric and other detection methods can be employed; the use of radiochromium gives the lowest detection limit.     

An Opportunity for Recycling Semi‐dry Scrubber Residues Directly from Municipal Solid Waste Incineration Plants without Concern of Leaching Toxicity

The leaching behaviors of heavy metals from semi‐dry scrubber (SDS) residues of municipal solid waste incineration (MSWI) plants are re‐investigated. The most leachable heavy metals in semi‐dry scrubber residues from municipal solid waste incinerators are found to be chromium ions (Cr(III) and Cr(VI)), but neither lead nor cadmium. Both of the leachabilities of Cr(III) and Cr(VI) in MSWI scrubber residue are a function of the CaO/Al₂O₃ ratio of residues. The pH‐dependent leaching behaviors are only observed in the case of Cr(III), but not for Cr(VI). Our results show that it is worth recycling SDS residues which possess a lower chemical composition ratio of CaO/Al₂O₃, in order to reduce the potential risk of toxic leaching of chromium species.     

Synthesis and characterization of M-MCM-48 (M = Cr,Ce) from silatrane via sol–gel process

Chromium and cerium incorporated into MCM-48 framework are hydrothermally synthesized via sol–gel process without any additives and characterized by X-ray diffraction, N₂ adsorption/desorption, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Diffuse reflectance UV–vis spectroscopy, and Thermogravimetric analysis. Results indicate that the materials possess a long-range ordered structure, high specific surface area, and narrow pore size distribution. SEM images illustrate the edge-truncated octahedron morphology of Cr-MCM-48 while Ce-MCM-48 preserves the truncated octahedron of the MCM-48 parent material. TEM images show the pore network of Ia3d symmetry after loading metals. Spectroscopic data confirm the existence of metals in the framework and extra-framework. At low Cr content, Cr-MCM-48 contains only Cr(VI) species while rich Cr content loading results in both the Cr(VI) and Cr(III) species. The hydrothermal stability of MCM-48 is enhanced by carefully incorporating metals into the parent material.     

Variations of structure and active species in mesoporous Cr-MSU-x catalyst during the dehydrogenation of ethane with CO<Subscript>2</Subscript>

The dehydrogenation of ethane to ethylene under CO₂ over mesoporous Cr-MSU catalyst was investigated with respect to the time on-stream behavior. When ethane was allowed to react for about 240 min, the meso-structure of catalyst remained nearly unchanged in spite of some decrease of surface area. The Cr(VI) species in tetrahedral coordination in fresh Cr-MSU were reduced to Cr(III) species in octahedral coordination, that was expected to cause the activity decrease of catalyst, together with the structure change. Cr(VI) is more active than Cr(III) for ethane dehydrogenation with CO₂, but Cr(III) represent fairly stable active centers for the reaction. The article is published in the original.     

Application of double-spike isotope dilution for the accurate determination of Cr(III), Cr(VI) and total Cr in yeast

A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate at 95±2 °C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na₂CO₃ for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO₃ and H₂O₂ was used for the determination of total Cr. Concentrations of 2,014±16, 1,952±103 and 76±48 mg kg⁻¹ (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III) to Cr(VI) (24.2±7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6±6.5% Cr(VI) reduced, n=3 ) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition, mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3, 2 and 30 mg kg⁻¹ were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample.     

Separation and Removal of Metal Ionic Species by Polymer Inclusion Membranes

Competitive alkali metal cation transport across polymer inclusion membranes (PIMs) containing sym-(alkyl)dibenzo-16-crown-5-oxyacetic acid carriers provides excellent selectivity for Na⁺ transport with the total fluxes being strongly influenced by the length of the alkyl chain that is attached geminal to the functional side arm in the lariat ether. Removal of chromium(VI) anions by PIMs from acidic aqueous phases was also investigated. Using tri-n-octylamine (TOA) as the ion carrier, Cr(VI) was removed by a PIM to decrease the source phase metal concentration from 1.0 to 0.010 ppm after 30 hours of transport. Competitive transport of Cr(VI) and Cr(III) ions from acidic source phases through PIMs and supported liquid membranes (SLMs) containing TOA and tri-n-octylphosphine oxide (TOPO) as carriers was evaluated and a very high Cr(VI)/Cr(III) separation ratio of 4800 was achieved with a PIM containing TOA. Competitive transport of Zn(II), Cd(II), and Cr(VI) from acidic aqueous solutions through PIMs containing TOA was investigated. The selectivity order for metal ion transport was: HCrO₄ ^–>CdCl₄ ^2–+CdCl₃ ^–>ZnCl₄ ^2–+ ZnCl₃ ^–. Non-contact atomic force microscopy was used to obtain images of the pores in cellulose triacetate membranes containing a plasticizer.     

Thermolyse de mélanges de chromates et d'oxalates de métaux alcalino-terreux II. Composés du magnésium

The thermolysis of mixtures of chromates and oxalates of magnesium has been studied combining thermal analysis and electron paramagnetic resonance. It is found that both the reduction of Cr(VI) to Cr(III) and that of Cr(VI) to Cr(V) are spontaneous and occur at about 600 and 250°C, respectively, under vacuum. Highly dispersed Cr(V) species are present after activation below 400°C while dispersed Cr(II) species, either as Cr₂O₃ or as Cr(III) in solid solution in the MgO lattice, are observed above 350 and 550°C, respectively. CO evolved during the decomposition of the oxalate is found to play a major role in the reduction of Cr(V) in Cr(III). Contrarily to the observation on the Ba and Sr homologues, no effect of the carbonate has been found.     

Design of BiOBr0.25I0.75for synergy photoreduction Cr（Ⅵ） and capture Cr（Ⅲ） over wide pH range

Conversion of hexavalent chromium (Cr（Ⅵ）) to trivalent chromium (Cr（Ⅲ）) is an effective way to reduce its environmental risk,especially via photoreduction process.However,over a wide range of p H values,it is still a great challenge to achieve a high removal rate,and the disposal of produced Cr（Ⅲ） should be concerned.In this work,we implemented a high removal rate at 98%for Cr（Ⅵ） and total chromium(Cr（T）) over a wide p H range （4–10） through the synergistic effect of adsorption,photoreduction an...     

Simultaneous determination of Cr(III) and Cr(VI) with prechelation of Cr(III) using phthalate by ion interaction chromatography with a C-18 column

Ion interaction chromatography has been successfully used for the simultaneous determination of Cr(III) and Cr(VI) in waste water. A C-18 column which had been dynamically coated with octylamine was used for the separation of Cr(III) and Cr(VI) based on anionic interaction. Cr(III) was chelated with potassium hydrogen phthalate (KHP) before injecting into the column since the Cr(III) did not exist in an anionic form like the Cr(VI) (Cr₂O₇²⁻) presented at the optimum condition. The analytes were detected at 200 nm and linear relationship between absorption with the concentration of Cr(III) or Cr(VI) was 0.1-50 mg/L. Most of the interested interferences including alkali metals, heavy metals and organic materials have no significant effect on Cr(III)-KHP complexation and Cr(VI) stability, only NH₄⁺ and ascorbic acid yielded the serious effect on the Cr(VI) stability. The relative standard deviations calculated from both of peak area and retention time were 0.75-2.20%. The sensitivity of the method at the level concentration of sub mg/L enabled the simultaneous determination of Cr(III) and Cr(VI) contents in waste water samples without any special sample preparation step.     

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.     

Study of chromium(VI) adsorption onto modified activated carbons with respect to analytical application

Two different types of modification of activated carbon, by treatment with concentrated solution of HNO₃ and outgassing treatment at high temperature, were studied in order to obtain the most effective adsorption of chromium(VI) ions from water solution. The basic parameters affecting the adsorption capacity of Cr(VI) ions on modified activated carbons were studied in details and the effect of modifications of activated carbons has been determined by studying the initial runs of adsorption isotherms. The obtained Cr(VI) adsorption isotherms were well fitted in the Freundlich equation. The reduction of Cr(VI) to Cr(III) and further ion exchange mechanism of adsorption onto oxidizing activated carbon and surface precipitation to Cr(OH)₃ in case of outgassing activated carbon were found as the main adsorption mechanisms of Cr(VI) ions onto modified activated carbons. Presence of chlorides and nitrates in studied adsorption system strongly decreased the adsorption ability of Cr(VI) onto outgassing activated carbon and mechanism of this behavior is proposed.     

Speciation analysis of chromium by separation on a 5-palmitoyl oxine-functionalized XAD-2 resin and spectrophotometric determination with diphenylcarbazide

The method developed in this work for the separation and preconcentration of Cr(III) is based on its retention by an Amberlite XAD-2 copolymer resin functionalized with 5-palmitoyl-8-hydroxyquinoline (oxine), abbreviated XAD-POx, with the ligand covalently bound to the copolymer. Cr(III) sorption was quantitative within the pH range 4.5–7.0 and Cr(VI) was not retained. The Cr(III) held by the resin column was eluted with a hot solution of H₂O₂ in pH9.0 aqueous NH₃–NH₄Cl buffer, and Cr oxidized to CrO₄^2– was rejected by the chelating cation-exchanger column. Any Cr(VI) originally present with Cr(III) could be reduced with an acidic solution of H₂O₂, and retained by the column yielding total Cr results, Cr(VI) being determined from the difference. The resin showed a maximal preconcentration factor of 60 for Cr(III), the LOD and LOQ being 9.3 and 30.1 nmol L^–1, respectively. The developed preconcentration-speciation analysis was finished with a diphenylcarbazide (DPC) spectrophotometric procedure suitable for conventional laboratories. The resin showed excellent salt tolerance, enabling Cr analysis in seawater, and was stable over extended use. All the interferents of this procedure that normally occur in an electroplating effluent, a blended coal CRM, and a standard steel sample could be removed by the recommended procedure, by use of partial and total selectivity at the adsorption and desorption stages, respectively, enabling preconcentration and colorimetric determination of chromium in various complex matrices.     

Sorption of chromium(VI) and chromium(III) on aluminium hydroxide

Factors that influence the sorption of Cr(VI) and Cr(III) on aluminium hydroxide were investigated. The sorption of chromates decreases as the pH of the suspension increases. The mechanism of CrO ₄ ^2– sorption was interpreted in terms of reactions between chromates and –OH and/or H₂O groups at the hydroxide/liquid interface. It has been shown that chromates are more tightly sorbed on aluminium hydroxide compared to other anions, e.g. chlorides. On the other hand, specifically absorbed anions, such as molybdates, compete strongly with chromates for the sorption sites. The sorption of chromium(III) increases with the pH of the suspension. Also, the sorption of chromium(III) is suppressed in the presence of citrate ions. The best conditions for the fixation of Cr(VI) and Cr(III) by aluminium hydroxide are presented.     

Microcalorimetric Study on Effect of Chromium(III) and Chromium(VI) Species on the Growth of Escherichia coli

The effects of Cr(III) and Cr(VI) species (Cr₂O₇^2?, CrO₄^2? and Cr³⁺) on the growth of Escherichia coli (E. coli) have been investigated in detail by microcalorimetry at 37 °C. Parameters including the growth rate constant (k), inhibitory ratio (I), half‐inhibitory concentration (IC₅₀), total heat output (Q_total), time of the maximum heat production (t_log) in the log phase have been obtained. The results showed that Cr(VI) and Cr(III) had the inhibition effect on the growth of E. coli in aquatic environment; however, the inhibitory ratio of Cr(III) to E. coli was smaller than that of Cr(VI). The k values of E. coli in the presence of Cr(VI) and at high concentrations of Cr(III) were decreased with increasing the concentrations of these chromium species. Among the three chromium species investigated, Cr₂O₇^2? was found to be the most poisonous species against E. coli with an IC₅₀ value of 35.52 µg·mL^?1. CrO₄^2? exhibited moderate toxicity on E. coli with an IC₅₀ of 50.24 µg·mL^?1, and Cr³⁺ had the lowest toxicity with an IC₅₀ of 84.30 µg·mL^?1. Microcalorimetry can provide a convenient, sensitive and reliable method to study the effect of various metal species on the growth of bacteria or other microorganisms.