Chemically selective membrane optode for Cr(VI) determination in aqueous samples

A methodology for simultaneous preconcentration and determination of Cr(VI) from aqueous samples was developed using a membrane optode formed by physical inclusion of a Cr(VI) selective chromophore 1,5-diphenylcarbazide (DPC) into a plasticized cellulose triacetate matrix. The inclusion of an anion exchanger (Aliquat-336) was found to be effective for immobilization of both DPC and Cr(VI)-DPC complex in the optode matrix itself. The proportionality in intensity of the magenta color on the optodes loaded with varying amounts of Cr(VI) suggests its potential applications for screening of Cr(VI) in aqueous samples by visual colorimetry. On loading high amounts of Cr(VI) in the membrane optode, its color changes from magenta to yellow, which indicates the possibility of using it as a threshold detector for Cr(VI). The membrane optode was optimized in terms of obtaining maximum preconcentration efficiency for Cr(VI) and subsequent stable optical response proportional to the amount of Cr(VI) in the membrane optode sample. The membrane optodes were tested for Cr(VI) determination in tap water and seawater samples. Using this optode, Cr(VI) even at levels of 13.6 ppb could be quantitatively detected. The optodes developed in the present work were found to be stable, cost effective, easy to prepare and efficient for direct preconcentration and determination of Cr(VI) in a variety of aqueous samples using spectrophotometry. However, this membrane optode is for one time use only as the reaction of Cr(VI) with DPC is irreversible.     

Modelling and simulation of integrated membrane processes for recovery of Cr(VI) with Aliquat 336

Extraction processes which employ porous membranes as a barrier between aqueous and organic phases provide a versatile means for selective removal and enrichment of solutes from aqueous streams. They require relatively little maintenance, their energy consumption is very low and the organic liquid losses are negligible if the pressure is controlled properly. The modelling and simulation of a complete plant for the removal and recovery of Cr(VI) with Aliquat 336 using hollow fibre modules have been studied. Both single and dual function membrane modules have been analyzed. Simulated concentration profiles through the module were obtained by solving mass transfer balances corresponding to all the species involved in the process.     

Liquid-supported membranes in chromium(VI) optical sensing: transport modelling

Flat sheet liquid-supported membranes (FSLSM) containing Aliquat 336 as a carrier have been evaluated as sample interface in an optical sensor for Cr(VI) monitoring. A model describing the transport mechanism of Cr(VI) through the membrane is reported. The model considers a diffusion process through a feed aqueous diffusion layer, a fast interfacial chemical reaction and a diffusion of ALQHCrO₄ and (ALQ)₂CrO₄ species through the membrane (Aliquat 336, ALQ). The mathematical equations describing the transport rate are derived and they correlate the membrane permeability coefficient to diffusional and equilibrium parameters as well as to the chemical composition of the system, i.e. extractant concentration in the membrane phase and acidity in the feed phase. The experimental data are explained by the derived equations and the diffusion resistances to mass transfer are evaluated. The influence of other experimental parameters, such as stirring speed in the feed phase and nature of the diluent and stripping agent on the transport is also discussed. Experiments with optical detection demonstrate the suitability of liquid-supported membranes (LSM) containing ALQ as interfaces for optical sensing.     

Determination of Cr(VI) in the presence of Cr(III) and humic acid by cathodic stripping voltammetry

A voltammetric procedure in the flow system for determination of traces of Cr(VI) in the presence of Cr(III) and humic acid is presented. The calibration graph is linear from 5×10⁻¹⁰ to 1×10⁻⁷ mol l⁻¹ for an accumulation time of 120 s. The R.S.D. for 1×10⁻⁸ mol l⁻¹ Cr(VI) is 5.3% (n=5). The detection limit estimated from 3σ for a low concentration of Cr(VI) and accumulation time of 120 s is 2×10⁻¹⁰ mol l⁻¹. The method can be used for Cr(VI) determination in the presence of up to 50 mg l⁻¹ of humic acid. The validation of the method was carried out by studying the recovery of Cr(VI) from spiked river water and by the comparison of the results of determination of Cr(VI) in a soil sample. The method cannot be used for analysis of samples containing high concentrations of chloride ions such as seawater and estuarine water.     

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.     

Amperometric Determination of Cr(III) and Cr(VI) by Flow Injection Analysis

Speciation of Cr(III) and Cr(VI) can be attained by flow injection analysis with amperometric detection. Cr(VI) is reduced in an acidic medium to Cr(III) with a glassy carbon electrode at —0.1 V vs. Ag/AgCl and the current is recorded. Cr(III) is oxidised on-line to Cr(VI) with alkaline hydrogen peroxide solution. From the difference of the total chromium and Cr(VI), the amount of Cr(III) was obtained. A linear calibration curve for Cr(VI) was obtained for the concentration ranges 0.01-5.0ppm of Cr(VI) and we have calculated the limit of determination to be about 0.5ppb. We have studied the degree of reproducibility obtained using the solid electrodes under various conditions. The influence of flow rate, coil length, interfenences and the extent of reaction were studied.     

Determination of Cr(III) and Cr(VI) in industrial and environmental liquid samples by EDXRF method

A rapid, sensitive and selective procedure for determination of Cr(III) and Cr(VI) in environmental and industrial liquid samples via preconcentration with ammonium pyrrolidine dithiocarbamate (APDC) and determination by means of the EDXRF was described. The effect of pH in the range of 3-11 on the recovery of Cr(III) and Cr(VI) has been investigated separately and in combination of these two species. The influence of organic matter, carbonate species and elements V, Mn and Fe on the recovery of each chromium specie (separately/in combination) over whole pH range was also tested in order to simulate condition occurring in natural waters that usually contain certain amount of dissolved organic matter and carbonate ions. Cr(VI) and Cr(III) have shown different behaviors in reaction with APDC at different pH ranges and therefore it is possible to separate those two species. It was found that Cr(VI) creates complex with APDC only in the pH range from 3 to 5 with quantitative recovery (app. 98%) at pH 3, but there was no recovery of Cr(III) at that pH. On the contrary, in pH range from 6 to 11, reaction with Cr(III) and APDC reviled that the only reaction product is Cr(OH)₃ instead of the expected Cr(III)-APDC complex. All reaction products were characterized by IR spectroscopy.     

Microcalorimetry as a tool for Cr(VI) toxicity evaluation of human dermal fibroblasts

Occupational exposure to Cr(VI) causes various effects including deep skin ulcerations. Its action mechanisms are not fully understood. In the present study, the evaluation of human dermal fibroblasts heat production was monitored, using microcalorimetry. as part of Cr(VI) toxicity. In control cells, normal heat production was 15±5 pW/cell. Regardless of the Cr(VI) concentration tested (0 to 500 μM), heat production was inhibited over time periods ranging from 3 to 25 h. These results could be correlated with cell mortality and the IC₅₀ for Cr(VI) was 29±4 μM. In the WST-1 bioassay, the IC₅₀ was 35±5 μM (no statistical difference). Thus, Cr(VI) altered the metabolism of the fibroblasts, and led to cellular death. Microcalorimetry can be a useful tool for determining the toxic effect of suspect compounds implicated in the occurrence of pathologies.     

Removal of Cr (VI) from aqueous solution using magnetic biochar synthesized by a single step method

Magnetic biochar, as an adsorbent, was synthesized by a single step method, where iron salt was directly mixed with pinewood sawdust by chemical co-precipitation and subsequently pyrolyzed at 700°C for Cr (VI) removal from aqueous solution. The effects of some important parameters including adsorbent dosage (0.4–2.8?g/L), pH (1–10) of the solution, contact time (0–1440 minutes), initial concentration (30–120?mg/L), and temperature (20–40°C) were investigated in batch experiments. Both pre- and post-adsorbents were characterized by SEM-EDX and XPS to investigate the adsorption mechanism. The maximum adsorption capacity of the tested magnetic biochar under the certain experimental conditions determined as optimal was 42.7?mg/g for Cr (VI). The adsorption data were proved to be suitable for the pseudo-second order model for kinetics and the Langmuir model for isotherms with correlation R²?=?0.9996 andR²?>?0.9980, respectively, after fitting with four kinetic models (pseudo-first order, pseudo-second order, W-M model, and Elovich) and three isotherm models (Langmuir, Freundlich, and Temkin). The characteristic analyses further verified that the efficient particle was a mixture of iron oxides in essence, and it had a strong effect on the spontaneous and endothermic adsorption process.     

Coupling of microwave induced plasma optical emission spectrometry with HPLC separation for speciation analysis of Cr(III)/Cr(VI)

Feasibility and limitations of direct coupling of high performance liquid chromatographic (HPLC) separation to microwave induced plasma (MIP)-optical emission spectrometry (OES) for elementspecific detection was tested and compared to inductively coupled plasma (ICP)-optical emission spectrometric detection on the basis of the Cr(III)/Cr(VI) speciation analysis of water samples. Coupling was performed by a hydraulic high pressure nebulizer (HHPN) radiative-heating/watercooling interface which provides about 20 % and 80 % aerosol yield in the case of helium and argon carrier gases, respectively. Desolvation efficiency of aqueous solutions was approximately 80 %. Applying the ion-pair HPLC separation, the organic eluents and reagents in the MIP cause a 50–75 % signal suppression for Cr(VI) and 25–50 % for Cr(III). In a pure aqueous solution the MIP Cr(VI) signal was by 20 % lower than that of Cr(III). These effects were lower using the ICP source, but they cannot be neglected. Easily ionizable matrix elements (Na, Ca) can cause 70 % signal suppression in the MIP, and 20 % in the ICP. Therefore, species dependent calibration is required in both cases. In the case of HPLC detection by MIP-OES, the detection limit was 13 ng for Cr(III), and 18 ng for Cr(VI). Using the ICP-OES detection, the detection limit was 0.2 ng for Cr (III) and 0.4 ng for Cr (VI). The linear dynamic ranges in both cases were two orders of magnitude. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Chromium speciation studies in human plasma and stability studies of Cr(III) and Cr(VI) species in a candidate water reference material

The aim of the research on Cr-speciation in plasma is to study the distribution of Cr over the plasma proteins. Cr is known to be mainly bound to transferrin and albumin. Therefore, a suitable separation procedure was developed for the two proteins. It consisted of a combination of FPLC cation and anion exchange, ensuring a complete resolution of both proteins and a total recovery of the Cr.In order to investigate the environmental impact of Cr(III) and Cr(VI) discharges, an aqueous reference material is needed to assess the quality of measurement between different laboratories. A pilot study was initiated to investigate the stability of a Cr(III) and Cr(VI) mixture in a bicarbonate/ carbonate buffer. Different parameters liable to influence the stability of the solutions have been investigated.     

Removal of Cr(VI) from water by cork waste

The biosorption by cork powder is considered as a promising method for heavy metal removal from industrial waste waters such as chromium tanning factories. The aim of this study is to evaluate the efficiency extent of this method using cork powder as a biosorbent for Cr(VI). The Fourier Transform Infrared spectroscopy (FTIR) analysis permits to distinguish the type of functional groups likely to participate in metal binding. A linear form of BET isotherms for all the three used temperatures (i.e., 25, 35 and 45 °C) and a pseudo-second-order equation of adsorption kinetics are obtained. Other experimental results highlight the meaningful influence of parameters such as contact time, pH, concentration of Cr(VI) and the adsorbent particle size on Cr(VI) adsorption. 97% of Cr(VI) has been removed under definite conditions particularly a particle size of diameter d < 0.08 mm and pH of 2–3 values.     

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).     

A novel flow injection chemiluminescence determination of Cr(VI) with Dichlorotris(1,10-phenanthroline)ruthenium(II)

A selective novel reverse flow injection system with chemiluminescence detection (rFI-CL) for the determination of Cr(VI) in presence of Cr(III) with Dichlorotris (1,10-phenanthroline)ruthenium(II), (Ru(phen)₃Cl₂), is described in this work. This new method is based on the oxidation capacity of Cr(VI) in H₂SO₄ media. First, the Ruthenium(II) complex is oxidized to Ruthenium(III) complex by Cr(VI) and afterwards it is reduced to the excited state of the Ruthenium(II) complex by a sodium oxalate solution, emitting light inside the detector. The intensity of chemiluminescence (CL) is proportional to the concentration of Cr(VI) and, under optimum conditions, it can be determined over the range of 3-300 μg L⁻¹ with a detection limit of 0.9 μg L⁻¹. The RSD was 8.4% and 1.5% at 5 and 50 μg L⁻¹, respectively. For the rFI-CL method various analytical parameters were optimized: flow rate (1 mL min⁻¹), H₂SO₄ carrier concentration (20% w/V), Ru(phen)₃Cl₂ concentration (5 mM) and sodium oxalate concentration (0.1 M). The effect of Cr(III), Fe(III), Al(III), Cd(II), Zn(II), Hg(II), Pb(II), Ca(II) and Mg(II), was studied. The method is highly sensitive and selective, allowing a fast, on-line determination of Cr(VI) in the presence of Cr(III). Finally, the method was tested in four different water samples (tap, reservoir, well and mineral), with good recovery percentage.     

Studies on extraction of chromium (VI) from acidic solutions containing various metal ions by emulsion liquid membrane using Alamine 336 as extractant

The extraction of chromium (VI) ions from acidic solutions containing various metal ions by emulsion liquid membrane (ELM) was studied. Liquid membrane consists of a diluent, a surfactant, and an extractant. 0.5 M ammonium carbonate solution was used as stripping solution. Effects of acid concentration in feed solution, type and concentration of stripping solution, mixing speed, surfactant concentration, phase ratio and the influence of membrane characteristics were studied and optimum conditions were determined. Under the optimum conditions, extraction of chromium (VI) was tested and it was possible to selectively extract 99% of chromium from the acidic feed solution. This study also examined the effect of extractant concentration and acid type in the feed solution on the extraction of Cr (VI) ions and almost all of Cr (VI) from the acidic feed solution containing 500 mg/L from each of Co (II), Ni (II), Cd (II), Zn (II), and Cu (II) ions, and 100–500 mg/L Cr (VI) was extracted within 5–10 min.     

Hybrid mesoporous materials for on-line preconcentration of Cr(VI) followed by one-step scheme for elution and colorimetric determination at ultratrace levels

An hybrid mesoporous material synthesised in our laboratories for solid phase extraction (SPE) in flow through systems has been used for analytical purposes. The solid was obtained from mesoporous silica MCM-41 functionalized with 3-aminopropyltriethoxy silane by Sol-Gel methodology. In order to exploit the large sorption capacity of the material together with the possibility of modeling it for anions retention, a microcolumn (MC) filled with the solid was inserted in a flow system for preconcentration of Cr(VI) and its determination at ultratrace levels in natural waters. The analytical methodology involved a reverse flow injection system (rFI) holding a MC filled with the solid for the analyte extraction. Elution and colorimetric detection were carried out with 1-5 diphenylcarbazide (DPC) in sulfuric acid. DPC produced the reduction of Cr(VI) to Cr(III) together with the generation of a cationic red complex between Cr(III) and 1-5 diphenylcarbazone which was easily eluted and detected with a visible spectrophotometer. Moreover, the filling material got ready for the next sample loading remaining unspoiled for more than 300 cycles.The effect of several variables on the analytical signal as well as the influence of cationic and anionic interferences were discussed. Particular attention was given to sulfuric acid interference since it is the required media for the complex generation.Under optimal conditions, 99.8% of Cr(VI) recovery was obtained for a preconcentration time of 120 s (sample and DPC flow rates = 1 mL min⁻¹) and an elution volume of 250 μL. The limit of detection (3 s) was found to be 0.09 μg L⁻¹ Cr(VI) with a relative standard deviation (n = 10, 3 μg L⁻¹) of 1.8.Since no Cr(III) was retained by the solid material and Cr(VI) was completely adsorbed, electrothermal atomic absorption spectrometry (ET AAS) determinations of Cr(III) were also performed by simply measuring its concentration at the end of the microcolumn after Cr(VI) retention by the mesoporous solid.Applications to the determination of Cr(VI) and Cr(III) in natural waters and the validation of the methodology were also studied.     

CdSe量子点荧光探针检测生活饮用水中的痕量六价铬

采用胶体化学方法合成还原性谷胱甘肽(GSH)稳定的Cd Se纳米量子点,所合成的Cd Se量子点对痕量的六价铬具有灵敏的荧光猝灭作用。以Cd Se量子点为荧光探针,建立一种简单快速测定生活饮用水中痕量六价铬的检测方法。在0.05~2.0μg·L-1范围内,Cd Se量子点的荧光强度变化值与生活饮用水中六价铬的含量呈线性关系,方法的检出限为0.01μg·L-1,样品测定的相对标准偏差小于5%,加标回收率在97~104%之间。该方法能够快速灵敏检测生活饮用水中的痕量六价铬,具有重现性好,定量准确灵敏等优点。     

Potentiality of methyltrioctylammonium chloride ligand for selective extraction of the Uranium(VI) metal ions from selective carbonate leach liquor

In the present study, the use of 5% Aliquat-336/kerosene was evaluated in the liquid–liquid extraction of Uranium(VI) and some impurities of Thorium(IV) and rare earth elements (REEs(III)). Experiments were carried out to determine the factors affecting U(VI) and some impurities of Th(IV) and REEs(III) extraction. McCabe–Thiele diagram was constructed to define the theoretical stages for extraction mixer settler process. The effect of stripping factors from the loaded extractant was also tested. Uranium cake was finally obtained from the strip solution and a workable flow sheet was then formulated.     

Selective flow injection analysis of ultra-trace amounts of Cr(VI), preconcentration of it by solvent extraction, and determination by electrothermal atomic absorption spectrometry (ETAAS)

A rapid, robust, sensitive and selective time-based flow injection (FI) on-line solvent extraction system interfaced with electrothermal atomic absorption spectrometry (ETAAS) is described for analyzing ultra-trace amounts of Cr(VI). The sample is initially mixed on-line with isobutyl methyl ketone (IBMK). The Cr(VI) is complexed by reaction with ammonium pyrrolidine dithiocarbamate (APDC), and the non-charged Cr(VI)–PDC chelate formed is extracted into IBMK in a knotted reactor made from PTFE tubing. The organic extractant is separated from the aqueous phase by a gravity phase separator with a small conical cavity and delivered into a collector tube, from which 55 μl organic concentrate is subsequently introduced via an air flow into the graphite tube of the ETAAS instrument. The operations of the FI-system and the ETAAS detector are synchronously coupled. A significant advantage of the approach is that matrix constituents, such as high salt contents, effectively are eliminated. The extraction procedure was optimized by a simplex approach. A central composite design was subsequently employed to verify the estimated operational optimum. An 18-fold enhancement in sensitivity of Cr(VI) was achieved after preconcentration for 99 s at a sample flow rate of 5.5 ml min⁻¹, as compared to direct introduction of 55 μl of sample, yielding a detection limit (3σ) of 3.3 ng l⁻¹. The sampling frequency was 24.2 samples h⁻¹. The proposed method was successfully evaluated by analyzing a NIST Cr(VI)-reference material, synthetic seawater and waste waters, and waste water samples from an incineration plant and a desulphurization plant, respectively.     

Spectrophotometric Determination of Trace Chromium(VI) in Mass Chromium(III)

There is little conclusive evidence of the toxic effects of Cr(III) so far, but Cr(VI) has carcinogenic activity, so the analysis of the chromine ions is very important in environmental research and the quality control of industry products. Usually Cr(III) and Cr(VI) interfere with each other in the species analysis, the measurement of Cr(VI) of numerous previous papers is related to the Cr(VI) samples, which contain a little Cr(III). When the amount of trivalent chromine exceeds ten …