Analyser of chromium and/or cobalt

Two stopped-flow manifolds have been proposed for individual or simultaneous determination of chromium and cobalt in water samples. Automated procedures based on multicommutation systems have emphasised the differences of their catalytic effect in luminol-hydrogen peroxide chemiluminescence reaction. A more rapid decay of signal was observed for Co for both configurations (flow injection or continuous injection). The influence of chemical and hydrodynamic variables has been studied in order to establish the robustness of method. The analysis rate was lower 1.5 min per replicate.Chemometric tools have been employed for the resolution of their contributions. Partial least squares (PLS) and H-point standard additions method (HPSAM) were used as multivariate calibration models. The percentages of explained variance were 97-99% (two factors). PLS and HPSAM obtained similar results. HPSAM provided a simple calibration model contributing to develop an analyser for chromium and/or cobalt.Standard mixtures, spiked samples and a certified reference material validated the proposed strategy. The applicability has been demonstrated by the determination of Cr and Co concentration in different water samples. The best results have been obtained for continuous injection providing more robust predictions. The achieved detection limit was 0.2 μg/l for both metals.     

Interferences of three elements in flame photometry Cr-Co-Mn system

The correction methods proposed by two of the authors (F.B-M and J.R-M ), for interferential systems of two or three elements in flame photometry, have been applied to the interferential effects that occur in solutions containing chromium, cobalt and manganese, all three elements being present or combinations of two of them.A comparison has been made of the different systems in aqueous and sulphuric acid solutions, with concentrations which varied between 50 and 500 p.p.m. of cobalt or manganese and between 200 and 2000 p.p.m. of chromium.The correction methods that may be applied to experimental values obtained by flame photometry with these systems have been indicated. A series of examples have also been included in order to show the results obtained with prepared solutions of known concentration and with samples previously analysed by chemical methods.Finally, the possibility of increasing the accuracy of the methods by means of a double correction has been considered.     

H-Point Standard Addition Method for Simultaneous Determination of Palladium and Cobalt

The H-point standard addition method (HPSAM) has been applied to simultaneous determination of palladium and cobalt at trace levels, using 1-(2-pyridylazo)-2-naphthol (PAN) as a chromogenic reagent. Palladium and cobalt at neutral pH levels form green colored neutral complexes with PAN which are soluble in aqueous sodium dodecylsulfate (SDS) micellar media and can be monitored spectrophotometrically. Simultaneous determination of cobalt and palladium by HPSAM were performed spectrophotometrically and under optimum conditions. Absorbances at the two pairs of wavelengths, 597 and 650 nm or 566 and 612nm, were monitored while adding standard solutions of cobalt or palladium, respectively. The method is able to accurately determine a cobalt/palladium ratio of between 5:1 and 1:30 (wt/wt). The accuracy and reproducibility of the determination method for various known amounts of cobalt and palladium in their binary mixtures were evaluated. The effects of diverse ions on the determination of cobalt and palladium to investigate the selectivity of the method were also studied. The recommended procedure was applied to real water samples and synthetic sample solutions.     

H-point standard addition method--first derivative spectrophotometry for simultaneous determination of palladium and cobalt

H-point standard addition method (HPSAM) has been applied for simultaneous determination of palladium and cobalt in trace levels, using disodium 1-nitroso-2-naphthol-3, 6-disulphonate (nitroso-R salt) as a selective chromogenic reagent. Palladium and cobalt in the neutral pHs form red color complexes with nitroso-R in aqueous solutions and making spectrophotometric monitoring possible. Simultaneous determination of palladium and cobalt were performed by HPSAM--first derivative spectrophotometry. First derivative signals at the two pairs of wavelengths, 523 and 589 nm or 513 and 554 nm were monitored with the addition of standard solutions of palladium or cobalt, respectively. The method is able to accurately determine palladium/cobalt ratio 1:10 to 15:1 (wt/wt). Accuracy and reproducibility of the determination method on the various amounts of palladium and cobalt known were evaluated in their binary mixtures. To investigate selectivity of the method and to ensure that no serious interferences were observed the effects of diverse ions on the determination of palladium and cobalt were also studied. The recommended procedure was successfully applied to real and synthetic cobalt or palladium alloys, B-complex ampoules, a palladium-charcoal mixture and real water matrices.     

胶束介质在速差动力学分析中的应用: 钴、镍的同时测定

研究溴化十六烷基三甲铵表面活性剂对钴(Ⅱ)、镍(Ⅱ)与二甲酚橙配位反应的影响, 测定了反应级数和表观活化能。由于胶束介质的存在, 钴(Ⅱ)、镍(Ⅱ)三元配合物的灵敏度比二元配合物分别提高了4.4和8.6倍, 并扩大了两组分的速率差别, 改善了反应的选择性。基于两组分反应速率的差别, 采用对数外推法计算机处理数据, 建立了速差动力学同时测定钴(Ⅱ)、镍(Ⅱ)的新方法。应用于钴精矿等几种实际样品中钴、镍的同时测定获得了满意结果, 其相对误差和标准偏差分别在4%和3%以内。     

Studies of iron,cobalt and chromium distribution in some continental aquatic ecosystems and biological materials

The aim of the present work was to investigate iron, cobalt and chromium distribution in samples of living and non-living matter by using instrumental neutron activation analysis (INAA). Investigations were carried out starting with water systems components, such also specias living in these systems and biological tissues from rat and human organs. The following conclusions have been drawn for elements distribution in the relation enviromment/living matter: (1) iron, cobalt and chromium contents in plankton are very close to these found in suspended materials; (2) among all the investigated living organisms, the highest contents of investigated elements have been found in fish; (3) inspite of the contents of iron, cobalt and chromium being somewhat lower in bentos and crustacea than in suspended materials, all the obtained values are very close, and (4) human liver has somewhat higher iron- and cobalt-contents than rat liver, which, however, has higher chromium concentration. Of all the investigated living organisms chromium content was the lowest in human liver.     

The Choice of Internal Standards for Measuring Volatile Pollutants in Water

54 volatile pollutants have been examined by static headspace-gas chromatography-mass selective detection in order to find the proper internal standard for each of the pollutants examined. The applicability of the internal standards has been assessed mathematically. For modelling, we prepared 2 × 4 × 4 solutions using blank water with added sodium sulphate and humic acid at four different concentrations for each. These solutions were spiked with two different concentrations of dilute standard solutions. We also examined 44 real water samples for traces of the 54 volatile pollutants, spiking them with dilute standard solutions. The results of a single measurement were 54 quotients for relative extraction efficiency: the area of the pollutant divided by the corresponding area of the spiked blank water measurement. For each pair of pollutants, the Pearson correlation coefficients were calculated for both the model and real water samples. We regarded two pollutants as being the same, if their Pearson correlation coefficient was greater than 0.95. Among similar pollutants we selected candidates for being suitable internal standards based on the highest correlation coefficients. We found, that five compounds are sufficient to cover 49 pollutants. Two pollutants did not exhibit a matrix effect and for these only the external calibration method can be used. For three pollutants, special considerations apply.The measurement data generally verified that structurally similar compounds have high correlation coefficients, but there were exceptions among similar compounds and unexpected similarities were also found. Nothing was found in the literature on determining the proper internal standard using Pearson correlation coefficients.     

On-line column preconcentration for the determination of cobalt in sea water by flow-injection chemiluminescence detection

A flow-injection method for the determination of dissolved cobalt(II) in sea water has been studied based on a combination of column preconcentration using 8-quinolinol immobilized on silica gel, fluoride containing metal alkoxide glass (8HQ-MAF) and chemiluminescence detection with a gallic acid-hydrogen peroxide system. Co(II) is selectively recovered from an acidified sample with 8-quinolinol immobilized on silica gel. After elution with dilute hydrochloric acid the resultant eluent is mixed with the reagent solutions, heated to 60 ( degrees )C and then introduced into the CL cell. The analysis time including the 2-min sample load was 8 min per sea water sample with a corresponding detection limit of 0.62 ng l(-1) (3sigma). The average standard deviation calculated for 10 replicate measurements of artificial sea water samples with a concentration of 10 ng l(-1) cobalt was +/-2.1%. The method has been tested with the standard reference sea waters NASS and CASS.     

A chemometric sensor for determining sulphaguanidine residues in honey samples

The inclusion complex of sulphaguanidine (SGN) in β-cyclodextrin has been investigated. To avoid the problem of the low solubility of β-cyclodextrin in water, solutions of β-cyclodextrin in urea have been used. A 1:1 stoichiometry and an association constant of 450 M⁻¹ have been established for the complex. A new spectrofluorimetric method has been developed for the determination of SGN residues in honey samples. This sulphonamide is widely employed for honey treatment. The method for the determination is based on second-order multivariate calibration, applying parallel factor analysis (PARAFAC). No previous separation or samples pre-treatment were required. The calibration solutions were prepared in water, with concentrations in the range from 0.02 to 0.20 μg mL⁻¹ for SGN. The use of the second-order calibration method in the standard addition mode, using the excitation-emission matrices (EEMs) as analytical signal, allowed its determination in honey samples, even in the presence of interferences, with satisfactory results. The proposed procedure was validated by comparing the obtained results with a HPLC method, with satisfactory results for the assayed method.     

Simultaneous spectrophotometric determination of cobalt and nickel by partial least square regression in micellar media

Diphenycarbazone has been used for the simultaneous determination of cobalt and nickel by partial least square regression method. DPC complexes of cobalt and nickel at pH 7-10 are of pink color, which are soluble in TX-100 micellar media. A partial least square multivariate calibration method for the analysis of binary mixtures of cobalt and nickel was developed. The total relative standard error for applying the PLS method was calculated. The accuracy and reproducibility of the determination method for various known amounts of Co(II) and Ni(II) in their binary mixtures were tested. The effects of diverse ions on the determination of cobalt and nickel to investigate the selectivity of the method were also studied. The proposed method was applied to the synthetic binary mixtures, alloys and pharmaceutical samples.     

Chromium speciation by a surfactant-coated alumina microcolumn using electrothermal atomic absorption spectrometry

A simple and convenient method has been developed for the speciation of chromium(III) and chromium(VI) in aqueous solutions using a sodium dodecyl sulphate coated alumina micro-column (1.5 cm x 5 mm i.d.) and graphite furnace-atomic absorption spectrometry (GF-AAS). Under the optimized conditions (pH 0.6, adjusted with hydrochloric acid; flow rate, 1 ml min(-1)) chromium(VI) is retained on the column and chromium(III) is collected and determined by GF-AAS. Total chromium is directly determined by GF-AAS and chromium(VI) is calculated by difference. The relative standard deviations (10 replicate analyses) at the 20 mug l(-1) level for chromium(III) and chromium(VI) and at the 40 mug l(-1) level for total chromium were 1.4%, 3.6% and 1.8%, and the corresponding limits of detection (based on 3sigma) were 0.57 mug ml(-1), 0.61 mug ml(-1) and 0.35 mug l(-1) respectively. No large interference effects have been observed from other investigated species and the method has been successfully applied to a range of water samples.     

Simultaneous spectrophotometric determination of cobalt,copper and nickel using 1-（2-thiazolylazo）-2-naphthol by chemometrics methods

The simultaneous determination of cobalt, copper and nickel using 1-（2-thiazolylazo）-2-naphthol （first figure of this article） by spectrophotometric method is a difficult problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares （PLS） regression, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction （OSC） is a preprocessing technique used for removing the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for PLS calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 550-750-nm range for 21 different mixtures of cobalt, copper and nickel. Calibration matrices were formed from samples containing 0.05-1.05, 0.05-1.30 and 0.05-0.80 μg·mL^-1 for cobalt, copper and nickel, respectively. The root mean square error of prediction （RMSEP） for cobalt, copper and nickel with OSC and without OSC were 0.007, 0.008, 0.011 and 0.031,0.037, 0.032 μg· mL^-1, respectively. This procedure allows the simultaneous determination of cobalt, copper and nickel in synthetic and real samples and good reliability of the determination was proved.     

The computational methods in the development of a novel multianalyte calibration technique for potentiometric integrated sensors systems

In recent years, integration and miniaturization of ion-selective electrodes (ISEs) have brought many benefits resulting in the possibility of simultaneous determination of the ions concentration in small volume samples. One of the key problems related to the preparation of potentiometric integrated sensors systems (PISSs) is a calibration procedure due to the necessity to calibrate each particular sensor separately. The main aim of the research was to develop a novel calibration method for PISSs fabricated with the use of an all-solid-state technology, which has been compared with other types of sensor calibration technique. The proposed algorithm concerns the method of calibration solutions composition determination for miniature ion-selective sensors before measuring in biological samples especially human saliva samples. This article also compares the parameters of ion-selective sensors for two types of PISSs, including ISEs based on gold (Au) and glassy carbon (GC) electrodes. In addition, a series of measurements was performed using PISS with Au-ISEs in samples of human saliva, which were preceded by different types of sensor calibration and compared with the results obtained with the clinical analyzer. Moreover, the effect of the viscosity of calibration solutions on the ISE parameters and the lifetime of the sensors were investigated.

     

Spectrophotometric simultaneous determination of cobalt, copper and nickel using nitroso-R-salt in alloys by partial least squares

Partial least squares modeling as a powerful multivariate statistical tool applied to spectrophotometric simultaneous determination of cobalt, copper, and nickel in aqueous solutions. The concentration range for cobalt, copper and nickel were 0.4-2.6, 0.6-3.4, 0.5-5.5 ppm, respectively. The experimental calibration set was composed with 36 sample solutions using a mixture design for three component mixtures. The absorption spectra were recorded from 470 to 600 nm. The effect of pH on the sensitivity and selectivity was studied according to net analyte signal (NAS). The values of root mean square difference (RMSD) for cobalt, copper and nickel using partial least squares (PLS) were 0.0192, 0.0263 and 0.0446 ppm, respectively. The effects of various cations and anions were investigated. The method was used to determination of cobalt, copper and nickel in two sample alloys based on copper, nickel and cobalt (known as cunico) and based on cobalt, nickel and iron (known as conife).     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定土壤中11种金属元素

称取0.25g样品加入5 mL硝酸和2 mL氢氟酸,用微波消解技术对样品进行前处理.以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下微波消解电感耦合等离子体质谱(ICP-MS)法同时测定土壤中Be、As、Cd、Co、Cr、Cu、...     

微波消解-电感耦合等离子体质谱法(ICP-MS)同时测定土壤中11种金属元素

称取0.25 g样品加入5ml硝酸和2ml氢氟酸,用微波消解技术对样品进行前处理。以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下可同时测定土壤中Be、As、Cd、Co、Cr、Cu、Ni、Pb、Tl、V、Zn 11种金属元素的微波消解ICP-MS方法。该方法线性关系良好,线性相关系数均在0.9990以上,检出限为0.002mg/kg-0.054 mg/kg。检测土壤标准物质GSS-17、GSS-18验证方法准确性,结果显示测定值均在标准差允许范围内,相对标准偏差在0.29%-5.33%,是一种快速、可靠的土壤多种金属元素检测方法。     

Preconcentration of chromium(III) and speciation of chromium by electrothermal atomic absorption spectrometry using cellulose adsorbent

A simple and sensitive method has been developed for species selective determination of chromium(III) and chromium(VI) in water by electrothermal atomic absorption spectrometry. The procedure is based on selective absorption of Cr(III) on a cellulose micro column (pH 11, 0.5 mol L(-1) NaCl). Total chromium was subsequently determined after appropriate reduction of Cr(VI) to Cr(III). Recoveries of more than 97% were found. A concentration factor of 100 was achieved. The relative standard deviations (n=10) at the 40 ng L(-1) level for chromium(III) and chromium(VI) were 2.3% and 1.8% and corresponding limits of detection (based on 36) were 1.8 ng L(-1) and 5.1 ng L(-1), respectively. No interference effects have been observed from other investigated species and the method has been successfully applied to natural water samples.     

A facile spectrophotometric method for cobalt determination using alpha-benzilmonoxime in sodium dodecylsulfate micellar solutions.

Alpha-benzilmonoxime in sodium dodecylsulfate micellar media has been used for the spectrophotometric determination of cobalt at pH 9.0. The linear range of calibration is 0.05-1.50 microg cm(-3) of cobalt at 380 nm with molar absorptivity of 3.72 x 10(4) dm3 mol(-1) cm(-1), which is about 1.5-times greater than that of the alpha-benzilmonoxime extraction based method. The relative standard deviations, recoveries, detection limit and effects of diverse ions on the determination of cobalt were studied. These analytical results were satisfactory. The method was successfully applied to the determination of cobalt in the various samples.     

Temperature-induced aggregation ionic liquid dispersive liquid-liquid microextraction method for separation trace amount of cobalt ion

A simple and rapid temperature induced aggregation micro extraction method based on ionic liquid for extraction and preconcentration of cobalt ions from water samples was proposed. In this investigation small amounts of 1-hexyl-3-methylimidazolium hexafluorophosphate [Hmim][PF₆] and 1-hexyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide [Hmim][Tf₂N] (as extractant solvents) were added in a sample solution containing Triton X-114 (as an anti-sticking agent). After centrifuging the cooled solution, analysis was carried out by flame atomic absorption spectrophotometry. Some effective parameters have been optimized. Under the optimum conditions, detection limit of the method was 0.44 ng/mL and the relative standard deviation (RSD) for 100.0 ng/mL cobalt was ±2.3% (n = 7).The calibration curve was linear in the range of 3.0–200.0 ng/mL cobalt and enrichment factor was obtained as 26.5. The applicability of the technique was evaluated by the determination of trace amounts of cobalt in several water samples and synthetic alloys.     

Solid phase extraction of chromium(VI) from aqueous solutions by adsorption of its diphenylcarbazide complex on a mixed bed adsorbent (acid activated montmorillonite-silica gel) column

A novel approach has been developed for the solid phase extraction of chromium(VI) based on the adsorption of its diphenylcarbazide complex on a mixture of acid activated montmorillonite (AAM)-silica gel column. The effect of various parameters such as acidity, stability of the column, sample volume, interfering ions, etc., were studied in detail. The adsorbed complex could be easily eluted using polyethylene glycol-sulfuric acid mixture and the concentration of chromium has been determined using visible spectrophotometry. The calibration graph was linear in the range 0-1microgmL(-1) chromium(VI) with a detection limit of 6microgL(-1). A highest preconcentration factor of 25 could be obtained for 250mL sample volume using glass wool as support for the mixed bed adsorbent. Chromium(VI) could be effectively separated from other ions such as nickel, copper, zinc, chloride, sulfate, nitrate, etc., and the method has been successfully applied to study the recovery of chromium in electroplating waste water and spiked water samples.