Rapid speciation analysis of Cr(VI) and Cr(III) by reversed-phase high-performance liquid chromatography with UV detection

A simple and rapid method is developed for the simultaneous determination of Cr(VI) and Cr(III) based on the formation of their different complexes with ammonium pyrrolidine-dithiocarbamate (APDC). Separation is performed using reversed-phase high-performance liquid chromatography coupled with UV detection. The conditions for complex formation and speciation are determined, such as solution pH, amount of APDC, temperature, and type of mobile phase. In order to substantially reduce the analysis time, the separation is carried out without extraction of chromium-APDC complexes from the mother liquor. Under the optimum analysis conditions, the chromatograms obtained show good peak separation, and the absolute detection limits (3s) are 2.2 microg/L for Cr(VI) and 4.5 microg/L for Cr(III). The calibration curves are linear from 3 to 5000 microg/L for Cr(VI) and 5 to 3000 microg/L for Cr(III). The relative standard deviations of peak areas in five measurements using a sample solution of 200 microg/L are less than 2% for Cr(VI) and 4% for Cr(III), indicating good reproducibility for this analytical method. Furthermore, simultaneous determination of Cr(VI) and Cr(III) is successful with the application of the proposed procedure in the synthetic wastewaters containing common heavy metal ions: Fe(III), Pb(II), Cd(II), Cu(II), and Zn(II).     

Rapid determination of chromium(VI) in electroplating waste water by use of a spectrophotometric flow injection system

A new rapid and sensitive FI method is reported for spectrophotometric determination of trace chromium(VI) in electroplating waste water. The method is based on the reaction of Cr(VI) with sodium diphenylamine sulfonate (DPH) in acidic medium to form a purple complex (lambda(max) = 550 nm). Under the optimized conditions, the calibration curve is linear in the range 0.04-3.8 microg ml(-1) at a sampling rate of 30 h(-1). The detection limit of the method is 0.0217 microg ml(-1), and the relative standard deviation is 1.1% for eight determinations of 2 microg ml(-1) Cr(VI). The proposed method was applied to the determination of chromium in electroplating waste water with satisfactory results.     

快速溶剂萃取-离子色谱法同时测定塑料中的三价铬和六价铬

建立了采用快速溶剂萃取-离子色谱同时测定塑料中三价铬和六价铬的方法。三价铬和六价铬分别以吡啶-2,6-二羧酸(PDCA)和1,5-二苯卡巴肼(DPC)作为络合剂在柱前和柱后进行衍生化,分别在紫外和可见波长下采用紫外检测器进行检测,灵敏度高,基体干扰小。本方法对三价铬和六价铬的检出限分别为5.0 μg/L和0.5 μg/L;分别在50～1000 μg/L和5.0～100 μg/L范围内呈现良好的线性关系,线性相关系数分别为0.9994和0.9998;三价铬和六价铬的回收率范围为90.7%～101.1%,相对标准偏差(RSD)为1.7%～4.4%。该方法分析速度快、灵敏度高、重现性好,可用于塑料中三价铬和六价铬的同时测定。     

Chromium speciation using activated alumina microcolumns and sequential injection analysis-flame atomic absorption spectrometry

A new procedure has been developed for chromium speciation in water by sequential injection analysis and flame atomic absorption spectrometry. The method involves the online retention of Cr(VI) anionic species and Cr(III) cationic species on alumina microcolumns, prepared by packing activated alumina in polytetrafluoroethylene tubes, followed by selective elution of Cr(VI) with 2 mol l⁻¹ NH₄OH and of Cr(III) with 0.2 mol l⁻¹ HNO₃. Studies were carried out on the effect of retention and elution conditions for both Cr species. The limit of detection values, established as the concentration corresponding to three times the standard deviation of blank measurements divided by the slope of the calibration line, achieved were 42 μg l⁻¹ for Cr(VI) and 81 μg l⁻¹ for Cr(III). The relative standard deviation of three independent determination of natural spiked samples were lower than 10% for concentration levels between 0.5 and 2 mg l⁻¹ of Cr. The developed procedure was applied to the analysis of two effluent sewage waters, and results obtained compared well with those obtained by a batch procedure. Recovery studies on natural spiked samples provided results between 93 and 103% for Cr(VI) and from 100 to 106% for Cr(III) for samples spiked with single species. For samples spiked with both Cr(VI) and Cr(III), the average recoveries varied from 86 to 101% for Cr(VI) and from 91 to 117% for Cr(III).     

A simple flow injection spectrophotometric procedure for the determination of diazepam in pharmaceutical formulation.

A single-channel flow injection (FI) manifold with spectrophotometric detection has been designed and fabricated for diazepam determination. A 100 microl sample and/or standard solution containing diazepam was injected into a flowing stream of 0.1 mol L(-1) hydrochloric acid with the optimum flow rate of 6.8 mL min(-1). As soon as the sample reached the detector, the FI signal as a peak was recorded at 360 nm. The optimum conditions for microg amounts of diazepam were achieved. A linear calibration graph over the range of 2-110 mg L(-1) diazepam was obtained with the regression equation Y = 0.2926X + 0.5896 (r2 = 0.9929). The method was very sensitive, since as little as 0.60 mg L(-1) could be detected; very reproducible with an RSD of 3.3% (n=11); and very rapid with a sampling rate of 100 h(-1). The limit of quantitation (10 sigma) was 2.0 mg L(-1). The proposed FI procedure has been satisfactorily applied to the quantitation of diazepam in commercial pharmaceutical formulations. The obtained results were in excellent agreement with those obtained by the conventional spectrophotometric method, verified by the student t-test at the 95% confidence level.     

In-situ separation of chromium(III) and chromium(VI) and sequential ETV-ICP-AES determination using acetylacetone and PTFE as chemical modifiers

Electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry (ETV-ICP-ES) has been used for the sequential determination of Cr(III) and Cr(VI). The method is based on the difference between the chelate reactions of the two Cr species and acetylacetone. Cr(III) chelate was separated from Cr(VI) and determined with use of acetylacetone as chemical modifier. The retained Cr(VI) in graphite tube was analyzed subsequently, after addition of polytetrafluoroethylene (PTFE) as chemical modifier. The different factors affecting the vaporization behavior of Cr(III) acetylacetonate were investigated in detail. The detection limits for Cr (III) and Cr(VI) were 0.56 and 1.4 ng mL(-1), respectively, and relative standard deviations for 0.1 microg mL(-1) Cr(III) and 0.1 microg mL(-1) Cr(VI) were 2.5% (n = 6) and 4.8% (n = 6), respectively. The linear ranges of the calibration curve for both Cr(IIl) and Cr(VI) covered three orders of magnitude. The proposed method was used to analyze water samples with satisfactory results.     

Flow injection atomic absorption spectrometric determination of iodide using an on-line preconcentration technique

A continuous flow atomic absorption spectrometric system was used to develop an efficient on-line preconcentration-elution procedure for the determination of iodide traces. Chromium (VI) is introduced into the flow system and is reduced to chromium (III) in acid medium proportionally to the iodide present in the sample. The Cr(III) reduced by iodide is retained on a minicolumn packed with a poly(aminophosphonic acid) chelating resin, while unreduced Cr(VI) is not retained. Reduced Cr(III) is preconcentrated by passing the sample containing iodide through the system during 3 min, and is then eluted with 0.5 mol L(-1) hydrochloric acid and determined by flame atomic absorption spectrometry (FAAS). The detection limit (3sigma) obtained is 2.5 microg L(-1). Other ions typically present in waters do not interfere. The proposed method allows the determination of iodide in the range 6-220 microg L(-1) with a relative standard deviation of 2.7% at a rate of 17 samples h(-1). The method has been applied to the determination of iodide in tap and sea waters.     

Separation and preconcentration of chromium species by selective absorption on Lemna minor and determination by slurry atomisation electrothermal atomic absorption spectrometry

A novel method for the separation and preconcentration of Cr(III)/Cr(VI) with Lemna minor and determination by slurry atomization electrothermal atomic absorption spectrometry (ETAAS) was developed. A sample solution was added to a polyethylene beaker containing 10 mg of 160 mesh pre-treated Lemna minor, adjusted to pH 1.0, stirred for 8 min for selective absorption of Cr(III) and then centrifuged. The upper layer of solution was transferred into another polyethylene beaker containing 10 mg of 160 mesh pre-treated Lemna minor, adjusted to pH 5.0, stirred for 12 min for adsorption of the residual Cr(VI) and centrifuged. The two residues in two centrifuge tubes were washed twice with water, 2 ml of agar solution added, stirred for 2 min, then two slurries were prepared and used for the determination of Cr(III) and Cr(VI) by ETAAS. Detection limits (3sigma) of 0.01 microg L(-1) for Cr(III) and 0.03 microg L(-1) for Cr(VI) were obtained. The relative standard deviation was 2.8% for Cr(III) and 3.3% for Cr(VI) at the 1 microg L(-1) level. The method was applied to the determination of Cr(III)/Cr(VI) in water samples. The analytical recoveries of Cr(III) and Cr(VI) added to samples were 97-102 and 96-103%, respectively.     

Flow injection spectrophotometric determination of tetracycline in a pharmaceutical preparation by complexation with aluminium(III).

A rapid flow injection (FI) spectrophotometric procedure for tetracycline determination is described. It is based on the injection of a 100 microl sample solution containing tetracycline into merged streams of aluminium(III) chloride (0.01 mol 1(-1)) and Tris-buffer in the presence of KCl (0.06 mol l(-1)), pH 7.0, with the same optimum flow rate of 3.2 ml min(-1). A yellow Al(III)-tetracycline complex was monitored at 376 nm. The flow injection system and the experimental conditions were optimized by means of the univariate method. The procedure was applied to the determination of tetracycline in pharmaceutical preparations with a high sampling rate of at least 165 h(-1). A high precision with a relative standard deviation was obtained less than 0.72 and 0.30% of 5.0 and 10 microg ml(-1) (n=11), respectively. The detection limit (3sigma) and the quantification limit (10sigma) were 0.07 and 0.72 mg l(-1), respectively. There were no interference effects from traditional excipients in the dosage forms when the method was applied to pharmaceutical preparations. The matrix effect could be reduced by the standard addition method.     

Speciation of Cr(III) and Cr(VI) in potable waters by using activated neutral alumina as collector and ET-AAS for determination

The speciation of Cr(III) and Cr(VI) has been performed by using activated neutral alumina as adsorbent. Both species were quantitatively adsorbed on a small column filled with neutral alumina. The adsorbed Cr(III) was eluted with 4 mol L(-1) HNO(3) and Cr(VI) with 1.0 mol L(-1) ammonia solution. Recoveries of Cr(III) and Cr(VI) were 99% and 100%, respectively. Using ET-AAS for Cr determination the limit of detection in the sample was 0.01 microg L(-1). The combined procedure is fast and sensitive. It can be applied for routine analysis of water samples at sub-microg L(-1) levels with a relative standard deviation (RSD) of 2-10% (three determinations).     

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.     

Determination of ultra-trace amounts of arsenic(III) by flow-injection hydride generation atomic absorption spectrometry with on-line preconcentration by coprecipitation with lanthanum hydroxide or hafnium hydroxide

A time-based flow-injection (FI) procedure for the determination of ultra-trace amounts of inorganic arsenic(III) is described, which combines hydride generation atomic absorption spectrometry (HG-AAS) with on-line preconcentration of the analyte by inorganic coprecipitation-dissolution in a filterless knotted Microline reactor. The sample and coprecipitating agent are mixed on-line and merged with an ammonium buffer solution, which promotes a controllable and quantitative collection of the generated hydroxide on the inner walls of the knotted reactor incorporated into the FI-HG-AAS system. Subsequently the precipitate is eluted with 1 mol 1(-1) hydrochloric acid, allowing ensuing determination of the analyte via hydride generation. The preconcentration of As(III) was tested by coprecipitation with two different inorganic coprecipitating agents namely La(III) and Hf(IV). It was shown that As(III) is more effectively collected by lanthanum hydroxide than by hafnium hydroxide, the sensitivity achieved by the former being approximately 25% better. With optimal experimental conditions and with a sample consumption of 6.7 ml per assay, an enrichment factor of 32 was obtained at a sample frequency of 33 samples h(-1). The limit of detection (3sigma) was 0.003 microg 1(-1) and the precision (relative standard deviation) was 1.0% (n = 11) at the 0.1 microg 1(-1) level.     

Preconcentration and speciation of chromium in drinking water samples by coupling of on-line sorption on activated carbon to ETAAS determination

An on-line flow injection (FI) preconcentration-electrothermal atomic absorption spectrometry (ETAAS) method is developed for trace determination of chromium in drinking water samples by sorption on a conical minicolumn packed with activated carbon (AC) at pH 5.0. The chromium was removed from the minicolumn with 1.0% (v/v) nitric acid. An enrichment factor (EF) of 35-fold for a sample volume of 10 ml was obtained. The detection limit (DL) value for the preconcentration method proposed was 3.0 ng l⁻¹. The precision for 10 replicate determinations at the 0.5 μg l⁻¹ Cr level was 4.0% relative standard deviation (R.S.D.), calculate with the peak heights obtained. The calibration graph using the preconcentration system for chromium was linear with a correlation coefficient of 0.9992 at levels near the detection limits up to at least 50 μg l⁻¹. The method was successfully applied to the determination of Cr(III) and Cr(VI) in drinking water samples.     

Automation of liquid-liquid extraction-spectrophotometry using prolonged pseudo-liquid drops and handheld CCD for speciation of Cr(VI) and Cr(III) in water samples.

A simple spectrophotometric system, based on a prolonged pseudo-liquid drop device as an optical cell and a handheld charge coupled device (CCD) as a detector, was constructed for automatic liquid-liquid extraction and spectrophotometric speciation of trace Cr(VI) and Cr(III) in water samples. A tungsten halogen lamp was used as the light source, and a laboratory-constructed T-tube with two open ends was used to form the prolonged pseudo-liquid drop inside the tube. In the medium of perchloric acid solution, Cr(VI) reacted with 1,5-diphenylcarbazide (DPC); the formed complex was automatically extracted into n-pentanol, with a preconcentration ratio of about 5. The organic phase with extracted chromium complex was then pumped through the optical cell for absorbance measurement at 548 nm. Under optimal conditions, the calibration curve was linear in the range of 7.5 - 350 microg L(-1), with a correlation coefficient of 0.9993. The limit of detection (3sigma) was 7.5 microg L(-1). That Cr(III) species cannot react with DPC, but can be oxidized to Cr(VI) prior to determination, is the basis of the speciation analysis. The proposed speciation analysis was sensitive, yet simple, labor-effective, and cost-effective. It has been preliminarily applied for the speciation of Cr(VI) and Cr(III) in spiked river and tap water samples. It can also be used for other automatic liquid-liquid extraction-spectrophotometric determinations.     

Determination of hexavalent chromium by on-line dialysis ion chromatography in a matrix of strong colourants and trivalent chromium

Hexavalent chromium detection in the presence of a high load of colourants without any false positive and in-procedure oxidation of Cr(III) is an important area of study. Colourants are a class of interfering substances in many spectroscopic analyses and chromatographic separations and detection. A purification method using an on-line dialysis technique for ion chromatography (IC) has been developed to remove water-soluble anionic dyes and particulate colourants and other substances to facilitate Cr(VI) quantification and the method is discussed. The dialysis was optimized with Cr(VI) standard solutions for quantification. The efficacy of the procedure for the removal of anionic dyes and detection of Cr(VI) was checked with a Cr(VI) spiked synthetic preparation containing a water-soluble dye and trivalent chromium. Soluble Cr(VI) extracted with organic dyes from environmental samples was analyzed. The method has a detection limit of 5 microg/l, recovery rate of 100% and analysis time less than 20 min.     

On-line filtration system for determining total chromium and chromium in the soluble fraction of industrial effluents by flow injection flame atomic absorption spectrometry

Two manifolds were assessed for the purpose of determining both the total chromium content and that present as a soluble form in industrial effluents by flow injection flame atomic absorption spectrometry (FI-FAAS). To determine the chromium content in the soluble fraction the samples were used without additional treatment, a 0.45 microm filter being included in the FI system. To determine the total chromium content, the samples were acidified with nitric acid 20% (v/v) and heated for 30 s in a microwave oven (temperatures of about 70 degrees C were reached). The problem posed by the very different concentration range in which total and soluble chromium are present was overcome by using programmed flow rate methodology and by only partially emptying the sample loop. A personal computer controlled both the rotation speed of a peristaltic pump and the volume of sample injected into the system, thus obtaining the dispersion degree required. Using the manifold proposed, the chromium content in the soluble fraction can be determined in the 0.5-20 microg mL(-1) range using a 10 microg mL(-1) single standard for calibration. To determine the total chromium content, a calibration line in the 20-200 microg mL(-1) range was obtained using a single 50 microg mL(-1) chromium standard solution. The reliability of the semi-automatic devices was verified by comparing the results obtained with those found by treating the samples and using both FAAS in a conventional way and a spectrophotometric method using diphenylcarbazide at the 95% confidence level (ANOVA test). The proposed procedures showed a RSD lower than +/-3%.     

Preparation of fluorescent polyvinyl alcohol keto-derivatives nanoparticles and selective determination of chromium(VI)

A novel fluorescent polyvinyl alcohol keto-derivatives nanoparticle (PVAK) has been prepared in one-step method. The nanoparticles has excitation and emission maxima at 349 and 462 nm, respectively. Based on the fluorescence quenching of PVAK by Cr(VI), we established a simple and selective fluorimetric method for the determination of Cr(VI) without separation of Cr(III) in water. The reaction conditions between Cr(VI) and PVAK were investigated in detail. Furthermore, the reaction mechanism between PVAK and Cr(VI) was also discussed. Under optimal experimental conditions, a limit of detection of 0.02 microg mL(-1) was achieved. The calibration curve was linear over the concentration range 0.1-13.2 microg mL(-1) with a correlation coefficient of 0.9987. The proposed method has been applied to the selective quantification of Cr(VI) in synthetic samples and waste-water samples with the satisfactory results.     

Influence of water sample storage protocols in chemiluminescence detection of trace elements

This paper shows the influence of different sample storage protocols, on the chemiluminescence signal of some metal ions. The storage protocols studied were: acid addition (HCl or HNO(3)) and no reagent addition to filtered and refrigerated (T=4 degrees C) samples. Light emission was produced for the chemiluminescence reaction between luminol and hydrogen peroxide in buffer carbonate conditions (pH 10.8) catalysed by Cr(III), Co(II) and Cu(II). Batch and/or flow modes in different conditions were tested. Fe(II), Fe(III), Ni(II) and Mn(II) did not give chemiluminescence in the studied conditions. A parallel study of sensitivity and selectivity was performed. Then the presence or absence of the masking agent EDTA, added to samples or used in the carrier stream, is assayed. If the samples are acidified with HNO(3), a previous neutralisation is needed using batch mode. The determination of Cr(III) is independent of storage protocol by flow injection (FI) method; however, the determination of Co(II) or Cu(II) or total determination of three metals requires the conditioning of standards. Detection limits achieved are ranged between 0.5 and 2 mug l(-1). For batch mode, detection limits are better for unacidified samples and worse for carbonate-neutralised samples. The influence of storage protocols was validated using standard metal mixtures and calibration solutions. The use of standard reference material (SRM(c) 1640) (Trace elements in natural water) corroborates the previous statements and validates the accuracy of the different approaches underlined. This paper demonstrates that it is possible to determine Cr(III) selectively in natural waters.     

Determination of ethanol in liquor by near-infrared spectrophotometry with flow injection

A simple procedure for the determination of ethanol in a liquor by near-infrared (NIR) spectrophotometry with flow injection (FI) is proposed. A liquor sample is equilibrated off-line with dried chloroform to extract ethanol into the organic phase. The extract is injected into a carrier stream of dried chloroform passing through a home-made flow through cell (1 mm path length) sitting in a NIR spectrophotometer for continuous monitoring of absorbance at 2305 or 2636 nm. The ethanol content can be evaluated from a calibration established by a plot of change in absorbance versus concentration of ethanol standard solutions. Optimization of the system will be discussed. A calibration is linear in the range of 20–50% (v/v) ethanol. A throughput of 240 injections h⁻¹ can be obtained. The procedure is validated by comparing the results with an analysis using gas chromatography.     

Selective fluorescence determination of chromium (VI) in water samples with terbium composite nanoparticles

The strong fluorescence Tb/acetyl acetone (acac)/Poly (Acrylamide) (PAM) composite nanoparticles have been prepared under ultrasonic radiation. The nanoparticles were water-soluble, stable and have extremely narrow emission bands and high internal quantum efficiencies. Based on the fluorescence quenching of Tb/acac/PAM by Cr (VI), a method for the selective determination of Cr (VI), without separation of Cr (III) in water, was developed. The reaction condition between Cr (VI) and Tb/acac/PAM were investigated in detail. Under optimal experimental conditions, the linear calibration curve was obtained over the concentration range of 5-600 ng mL(-1) with a correlation coefficient of 0.9939. The corresponding detection limit is 0.8 ng mL(-1) and the relative standard deviation is 1.5% for 0.05 microg mL(-1) (n=7). The proposed method has been applied to the selective quantification of Cr (VI) in synthetic samples and waste-water samples with the satisfactory results. The assay is characterized by short reaction time, very few interference, stable fluorescence signals, simple instrument and simplicity.