A new experimental approach for liquid-liquid extractive spectrophotometric determination of chromium(VI) in tannery wastewater and alloy samples

In this research work, a new approach is developed for the extractive determination of chromium. The principle of this approach is based on the complexation reaction between 4-(4?-chlorobenzylideneimino)-3-methyl-5-mercapto-1,2,4-triazole (CBIMMT) in dichloromethane as a complexing reagent and chromium(III) in presence of potassium iodide to form a yellow coloured complex at room temperature. The 1:2:2 [Cr(III)-CBIMMT-iodide] ternary complex was quantitatively extracted in dichloromethane from 2.5 mol L^?1 of hydrochloric acid medium which showed maximum absorption intensity at λ_max 411 nm and was stable for more than 72 h. The values of molar absorption coefficient and Sandell’s sensitivity of the complex were found to be 0.7019 × 10⁴ L mol^?1 cm^?1 and 0.00748 µg cm^?2, respectively. The system adheres to Beer’s law from 1.5 to 6.0 µg mL^?1; however, Ringbom’s plot suggests optimal concentration range was 1.8–5.8 µg mL^?1. The limit of detection and limit of quantification of the approach is 0.26 and 0.79 µg mL^?1. This approach was successfully used for the determination of chromium from wastewater effluents from the tannery industries (Kolhapur, MS, India), alloy samples and for separation of it from synthetic mixtures. The present experimental approach is apparently much simpler than the conventional method comprising multistep processes.     

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.     

Simple and Highly Selective Catalytic Adsorptive Voltammetric Method for Cr(VI) Determination

A simple and highly selective and sensitive catalytic adsorptive stripping voltammetric procedure for determination of traces of Cr(VI) in the presence of a large excess of Cr(III) in environmental water samples is reported. To obtain a low detection limit the voltammetric procedure of chromium determination in the presence of DTPA and nitrate was exploited. For elimination of interference of Cr(III) ethylenediaminedisuccinic acid was used as a masking agent. At optimized conditions the calibration graph is linear from 2×10^?10 to 2×10^?8 mol L^?1 for accumulation time of 30 s. The validation of the procedure was performed by comparison of the results of analysis of river water samples with those obtained using other accepted voltammetric procedure.     

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.     

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.     

A catalytic adsorptive stripping voltammetric procedure for trace determination of Cr(VI) in natural samples containing high concentrations of humic substances

A simple and fast catalytic adsorptive stripping voltammetric procedure for trace determination of Cr(VI) in natural samples containing high concentrations of humic substances has been developed. The procedure for chromium determination in the presence of DTPA and nitrates was employed as the initial method. In order to enhance the selectivity vs. Cr(III) the measurements were performed at 40°C. Interference from dissolved organic matter such as humic and fulvic acids was drastically decreased by adding Amberlite XAD-7 resin to the voltammetric cell before the deaeration step. The whole procedure was applied to a single cell, which allowed monitoring of the voltammetric scan. Optimum conditions for removing humic and fulvic acids due to their adsorption on XAD-7 resin were evaluated. The use of XAD-7 resin also minimize interferences from various cationic, anionic, and nonionic surfactants. The calibration graph for Cr(VI) for an accumulation time of 30 s was linear in the range 5 × 10⁻¹⁰ to 5 × 10⁻⁸ mol L⁻¹. The relative standard deviation for determination of Cr(VI) at a concentration of 1 × 10⁻⁸ mol L⁻¹ was 3.5% (n = 5). The detection limit estimated from 3 times the standard deviation for low Cr(VI) concentrations and an accumulation time of 30 s was about 1.3 × 10⁻¹⁰ mol L⁻¹. The proposed method was successfully applied to Cr(VI) determination at trace levels in soil samples.     

影响TiO2纳米管光电催化还原Cr(VI)的因素探讨

采用阳极氧化法在Ti基底上生长TiO2纳米管(TNT)阵列薄膜,利用扫描电镜和X射线衍射对样品的形貌和结构进行了表征.以TNT薄膜为光阳极、Ti网为光阴极,在酸性条件下进行紫外光光电催化还原Cr(VI),探讨了外加偏压、NaCl浓度、柠檬酸浓度以及Cr(VI)初始浓度对反应性能的影响.结果表明,外加电压有效地促进了电子...     

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.     

Optimization of Parameters for Cr(VI) Adsorption on Used Black Tea Leaves

Dynamic characteristics of Cr(VI) sorption on used black tea leaves (UBTLs) as a low-cost adsorbent are studied. Batch experiments were conducted to evaluate the effects of Cr(VI) concentration, solution pH and temperature on the removal process. Both of adsorption and reduction, involved in the process, are affected by the processing parameters. The adsorption kinetics is described successfully using pseudo-second order rate equation and the rate constant decreases with increasing the initial concentration of Cr(VI) up to 150 mg/L (for 0.1 g/L UBTLs) then becomes slow. Experimental and calculated kinetic data for equilibrium are well expressed by Langmuir isotherm. The solution pH has a profound effect on the adsorption rate. The rate constant increases linearly with an increase in temperature, and the low value of activation energy of adsorption, 16.3 kJ/mol, indicates that Cr(VI) is easily adsorbed on UBTLs. The maximum Cr(VI) adsorptive conditions, with a minimum reduction, were achieved from the dynamics of operational parameters: the initial Cr(VI) concentration < 150 mg/L (for 0.1 g/L UBTLs); the initial solution pH = 1.54–2.00 and the processing temperature < 50 ^∘C, for the possibility of its practical application.     

Determination of Cr(VI) by Catalytic Adsorptive Stripping Voltammetry with Application of Nitrilotriacetic Acid as a Masking Agent

A selective and sensitive method for determination of traces of Cr(VI) in the presence of a large excess of Cr(III) by differential pulse catalytic adsorptive stripping voltammetry is presented. For minimization of Cr(III) interference nitrilotriacetic acid was used as a masking agent. The determinations were performed in a flow system. The calibration plot was linear from 1×10⁻¹⁰ to 1×10⁻⁸ mol L⁻¹ for accumulation time 60 s. The relative standard deviation for 3×10⁻⁹ mol L⁻¹ Cr(VI) was 4.1% (n=5). The detection limit for an accumulation time of 60 s was 4×10⁻¹¹ mol L⁻¹. The influence of common foreign ions is also presented. The performance of the method was verified by analysis of certified reference material for Cr(VI) and comparing the results of analyses of natural water samples with those obtained by another accepted electrochemical method.     

超积累植物李氏禾叶细胞干粉对Cr(VI)的吸附特性研究

借助拟合吸附动力学和等温热力学方程, 研究了湿生超积累植物李氏禾叶细胞干粉对Cr(VI)的吸附性能. 考察了pH值、吸附时间等多种因素对吸附性能的影响; 利用扫描电镜(SEM), X射线能谱(EDS)对李氏禾干粉表面形貌及元素分布进行了表征. 结果表明, 该吸附是单分子吸附的伪二级动力学过程, 吸附过程包含两个步骤: Cr(VI)离子通过静电作用富集在干粉材料表面, 随后干粉表面存在的功能配位官能团会与Cr(VI)发生化学作用. 结合红外光谱图发现对铬起吸附作用的主要是含O, N功能原子的配位官能团, 并且不同功能原子与Cr(VI)的作用方式不同.     

The ION Chromatograhic Determination of Cr(III)-Cr(VI) Using an EDTA ELUANT

Abstract

Recent work in our laboratory has involved the use of ethylene diaminete traacetic acid as an eluant for the ion chromatographic determination of transition metals. We have continued this investigation into the use of EDTA by developing a potential method for the determination of Cr(III) and Cr(VT) in the same solution at the ppm level. The method involves the separation of the species as anions—the monovalent Cr(III)-EDTA anion and the divalent dichromate ion—followed by the detection of the species using a variable wavelength UV detector. The detection limits are approximately 2 ppm and the precision and stability of the system are within 6% RSD over the course of a working day. The linear operating range is in excess of two orders of magnitude.     

电化学传感分析平台测定污水中的Cr(VI)

结合微型电化学仪器,研究了一种快速、便携、灵敏的Cr(VI)电化学传感分析平台,用于污水中Cr(VI)的检测。采用三电极体系,差分脉冲阴极溶出伏安法(DPCSV),记录伏安曲线中Cr(VI)的还原峰。Cr(VI)的溶出峰电流与其浓度在2～500 μmol L-1范围内有良好的线性关系,测得Cr(VI)的检测限为0.55 μmol L-1 (28.60 g L-1),达到了国际卫生组织（WHO）规定的饮用水中Cr(VI)的最高含量50 g L-1。测得镀铬厂废水中Cr(VI)含量为2.03 mol L-1,与国标法中光谱学分析法的结果基本一致。该法重现性好、灵敏度高,使其应用在现场实时监测环境中的Cr(VI)具有很大的潜力。     

Speciation of Cr(III) and Cr(VI) by Means of Melamine-Urea-Formaldehyde Resin and FAAS

 A method is described for the quantitative preconcentration and separation of trace chromium in water by adsorption on melamine-urea-formaldehyde resin. Cr(VI) is enriched from aqueous solutions on the resin. After elution the Cr(VI) is determined by FAAS. The capacity of the resin is maximal at ∼ pH 2. Total chromium can be determined by the method after oxidation of Cr(III) to Cr(VI) by hydrogen peroxide. The relative standard deviations (10 replicate analyses) for 10 mg/L levels of Cr(VI), Cr(III) and total chromium were 1.5, 3.5 and 2.8% respectively. The procedure has been applied to the determination and speciation of chromium in lake water, tap water and chromium-plating baths.     

A comprehensive study for selective removal of Cr(VI) by asymmetric imidazolium bromide salts as environmentally-friendly extractant

The study was to determine selective removal and recovery of Cr(VI) from acidic media by solvent extraction (SX) using asymmetric imidazolium-based room temperature imidazolium bromide salts (ARTILs) as the extractants. The relevant parameters on the extraction and the stripping of Cr(VI) were investigated to identify optimum conditions. The optimum conditions were determined as equilibration time 5 minutes, acid concentration and type 0.5?mol/L H₂SO₄, stirring speed 1200?rpm, extractant concentration and type 0.5?mol/L ARTIL5, phase ratio 2.0 and stripping reagent type, and concentration 2.0?mol/L NH₃. In optimum conditions, decyl substituted ARTIL was best in extraction process about 99.7% of extraction rate, whereas moderately hydrophobic pentyl substituted ARTIL was best in stripping process about 70.0% of stripping rate. Also, the optimized process was found as so selective toward Cr(VI) in the presence of the other metal ions with an environmental-friendly liquid–liquid–based SX method.     

Flow injection fluorimetric determination of chromium(VI) in electroplating baths by luminescence quenching of tris(2,2'-bipyridyl) ruthenium(II)

A sensitive and selective luminescence quenching method is developed and used for manual and flow injection analysis (FIA) of chromium(VI) by reaction with [Ru(bpy)₃]²⁺. The emission peak of ruthenium(II) at 595 nm is linearly decreased as a function of Cr(VI) concentration. This permits determination of chromium(VI) ion over the concentration range 0.1-20 μg ml⁻¹ with a detection limit of 33 ng ml⁻¹. The quenching process is due to an electron transfer from the luminescent [Ru(bpy)₃]²⁺ complex ion to Cr(VI) resulting in the formation of the non-luminescent [Ru(bpy)₃]³⁺ complex ion. Selectivity for Cr(VI) over many anions and transition, alkali and alkaline earth metal cations is demonstrated. High concentration levels of sulphate, chloride, borate, acetate, phosphate, nitrate, cyanide, Pb²⁺, Zn²⁺, Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺ and Mn²⁺ ions are tolerated. The effects of solution pH and [Ru(bpy)₃]²⁺ reagent concentration are examined and the reaction conditions are optimized. Validation of the method according to the quality assurance standards show suitability of the proposed method for use in the quality control assessment of Cr(VI) in complex matrices without prior treatment. The method is successfully applied to determine chromium(VI) in electroplating baths using flow injection analysis. Results with a mean standard deviation of ±0.6% are obtained which compare fairly well with data obtained using atomic absorption spectrometry.     

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.     

Extraction and determination of hexavalent chromium in soil samples

A procedure for the extraction of Cr(VI) from solid soil-like samples was presented in which the complexing properties of diethylenetriaminepentaacetic acid (DTPA) were exploited to extract insoluble compounds of Cr(VI). A concentration of DTPA in an ammonium sulphate/ammonium hydroxide buffer equal to 0.02 mol l⁻¹ was chosen. The conditions of extraction of insoluble Cr(VI) from solid samples were optimised using soil certified reference material spiked with known concentration of insoluble Cr(VI) added as PbCrO₄. The extracts were analysed by adsorptive stripping voltammetry. Validation of the proposed procedure of extraction was carried out by analysis of certified reference material (CRM) 545 and comparison of the results obtained using the proposed and other methods of extraction in the course of analysis of natural soil samples.     

DAPPA grafted polymer: an efficient solid phase extractant for U(VI), Th(IV) and La(III) from acidic waste streams and environmental samples

A new class of polymeric resin has been synthesized by grafting Merrifield chloromethylated resin with (dimethyl amino-phosphono-methyl)-phosphonic acid (MCM-DAPPA), for the preconcentration of U(VI), Th(IV) and La(III) from both acidic wastes and environmental samples. The various chemical modification steps involved during grafting process are characterized by FT-IR spectroscopy, ³¹P and ¹³C-CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNS/O elemental analysis. The water regain capacity data for the grafted polymer are obtained from thermo-gravimetric (TG) analysis. The influence of various physico-chemical parameters during the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The significant feature of this grafted polymer is its ability to extract both actinides and lanthanides from high-level acidities as well as from near neutral conditions. The resin shows very high sorption capacity values of 2.02, 0.89 and 0.54 mmol g⁻¹ for U(VI), 1.98, 0.63 and 0.42 mmol g⁻¹ for Th(IV) and 1.22, 0.39 and 0.39 mmol g⁻¹ for La(III) under optimum pH, HNO₃ and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (<5 min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, all the analyte ions are quantitatively eluted from the resin phase with >99.5% recovery using 1 M (NH₄)₂CO₃, as eluent. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) from sea water and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.9% R.S.D. reflecting the reproducibility and reliability of the developed method.     

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.