On-line preconcentration and determination of cobalt by DPTH-gel chelating microcolumn and flow injection inductively coupled plasma atomic emission spectrometry

This paper reports the development of a new methodology for the determination of cobalt in biological samples by using a flow injection system with loaded DPTH-gel as solid phase to preconcentrate analytes. The procedure is based on the on-line preconcentration of cobalt on a microcolumn of 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). The trapped cobalt is then eluted with 1% tartaric acid and 1% citric acid (7.1 mL) and determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The analytical figures of merit for the determination of cobalt are as follows: detection limit (3S), 8.5 ng mL^–1; precision (RSD), 5.8% for 100 ng mL^–1 of cobalt; enrichment factor, 13 (using 7.3 mL of sample); sampling frequency, 40 h^–1 using a 60-s preconcentration time. For a 120-s preconcentration time (14.6 mL of sample volume) a detection limit of 5.7 ng mL^–1, an RSD under 5% at 50 ng mL^–1, an enrichment factor of 25, and a sampling frequency of 24 h^–1 were reported. The precision and accuracy of the method were checked by analysis of biological certified reference materials.     

Determination of cadmium and lead at μg/1 levels in aqueous matrices by chelation ion chromatography

A method for the simultaneous determination of μg/1 or sub-μg/1 levels of cadmium and lead in sea water by chelation ion chromatography is demonstrated. The method consists in the preconcentration of a sea-water sample containing cadmium and lead on an iminodiacetate chelating resin; alkali and alkaline earth metals are removed from the resin with an ammonium acetate buffer, the metals are eluted and separated by cation-exchange chromatography, followed by postcolumn derivatization with 4-(2-pyridylazo)resorcinol and spectrophotometric detection at 520 nm. The concentration and separation steps are automated. The detection limit, when concentrating 200 ml of sea water, was found to be 2 ng for cadmium and 6 ng for lead. Relative standard deviations of 4.5% and 6.8% for 10 μg/1 of cadmium and lead, respectively, were obtained. Transition metals (Fe, Co, Ni, Zn, Cu, Mn) do not interfere in the analysis. An application of the method to the determination of cadmium and lead in sea-water samples collected in the Taranto gulf (Italy) is presented.     

Chelating sorbents based on silica gel and their application in atomic spectrometry

This mini-review covers chelating sorbents anchored to silica gel and their analytical applications for the preconcentration, separation and determination of trace metal ions, focussing mainly on the last 20 years. The article summarizes also the experience gathered by our research group in the synthesis and characterization of new modified silica gels via silanization, and their affinity toward selective extraction and separation of trace elements. The introduction of 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide silica gel (DPTH-gel) and methylthiosalicylate silica gel (TS-gel) chelating sorbents in trace and ultratrace analysis provide vital breakthroughs in preconcentration methods. These home-made materials allow certain analytes to be selectively extracted from complex matrices without matrix interference and good detection limits. The advantages of these new chelating sorbents in comparison with 8-hydroxyquinoline chelating sorbent immobilized on silica gel are discussed.     

Application of flow injection on-line electrothermal atomic absorption spectrometry to the determination of rhodium

A fully automated procedure for the determination of rhodium has been developed using flow injection (FI) on-line microcolumn preconcentration coupled with electrothermal atomic absorption spectrometry (ETAAS). The proposed FI manifold and its operation make possible the introduction of the total eluate volume into the graphite atomizer, avoiding the necessity for optimisation of subsampling the eluate. Rhodium is adsorbed on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). Under the optimum conditions, using a 60 s preconcentration time, a sample flow rate of 3.5 mL min(-1) and an injection volume of eluent of 50 microL, a linear calibration graph was obtained from 1 to at least 40 ng mL(-1) and the detection limit was 1 ng mL(-1). The proposed method has been successfully applied to the analysis of samples. Its performance was investigated against certified reference catalyst sample SRM-2557 and by recovery measurements on spiked samples (soil, foods and beverages).     

Preconcentration of nickel and cobalt on algae and determination by slurry graphite-furnace atomic-absorption spectrometry

Unicellular green algae have been utilized to preconcentrate Ni(2+) and Co(2+) ions from sea-water and riverine water samples. Studies have shown that rinsing the algae with 0.12M hydrochloric acid improves the adsorption of nickel and cobalt, and the optimum range of pH of extraction is wide. The maximum extraction efficiencies were 84 and 73% for Ni and Co, respectively, at ng/ml levels. The sea-water matrix and relatively small amounts of many impurities reduce the adsorption efficiency for both nickel and cobalt. The preconcentration is achieved by mixing 6 mg of algae with 50-100 ml of sample, and subsequently isolating the algae by centrifugation. The pellet of algae is then resuspended in 1 ml of 0.08M nitric acid, and analyzed as a slurry by graphite-furnace atomic-absorption spectrometry. The values found for nickel and cobalt in riverine (SLRS-1) and sea-water (CASS-1) standard reference materials are within the limits of certification.     

流动注射在线柱预富集-电感耦合等离子体原子发射光谱测定痕量金属元素

本文报道了流动注射在线柱预富集ICP光谱测定痕量金属的方法,以meso-四(4-磺基苯)卟啉为柱前衍生试剂,硅胶作固定相和盐酸作洗脱液,对痕量金属离子Cu、Mn、Ni、Fe、Pb、Cd进行在线预富集检测。在给定实验条件下,方法的富集倍数为9.3～11.3,检出限和测定的相对标准偏差(n=6)分别在0.32～26.8ng/ml和1.3％～3.0％范围内。方法用于小牛肝和西红柿叶样品分析,结果与参考值吻合。     

Highly selective preconcentration of ultra-trace cadmium by yeast surface engineering

The potential of selective cell-sorption for separation/preconcentration of ultra-trace heavy metals was exploited by surface engineering of Saccharomyces cerevisiae cells. The general idea is to display the cadmium-binding peptide on the cell surface in order to enhance the covalent interaction between cadmium and the yeast cells. By immobilizing the surface-engineered yeast cells onto cytopore(?) microcarrier beads for cadmium adsorption, we demonstrated that with respect to the native yeast 600-fold and 25-1000-fold improvements were observed respectively for the tolerance of ionic strength and the tolerant capability toward various metal cations after surface engineering. Based on these observations, a novel procedure for selective cadmium preconcentration was developed with detection by graphite furnace atomic absorption spectrometry (GFAAS), employing the engineered S. cerevisiae cell-loaded cytopore(?) beads as a renewable sorption medium incorporated into a sequential injection lab-on-valve system. The cadmium retained on the yeast cell surface was eluted with a small amount of nitric acid and quantified with GFAAS. Within a range of 5-100 ng L(-1) and a sample volume of 1 mL, an enrichment factor of 30 was achieved along with a detection limit of 1.1 ng L(-1), a sampling frequency of 20 h(-1) and a precision of 3.3% RSD at 50 ng L(-1). The procedure was validated by analyzing cadmium in certified reference materials and a series of environmental water samples.     

An ion-exchange method for speciation of antimony by flow injection electrothermal atomic absorption spectrometry

In this work, a simple preconcentration system, achieved by replacing the sample tip of the autosampler arm by a micro-column packed with Amberlite IRA-910 or silica gel chelating resin functionalised with 1,5-bis(di-2-pyridyl)methylene tbiocarbohydrazide (DPTH-gel), is developed for the determination of Sb(V) and total antimony, respectively. Different factors including pH of sample solution, ionic strength, concentration and volume of eluent, sample flow rate, sample loading time and matrix effects for preconcentration were investigated. The method has been applied to the determination of antimony species in different samples.     

Determination of 0.1 to 1000 μ g/ml cadmium in a hydrometallurgical zinc refining process stream by a flow injection technique with computer controlled injection method

A computer-controlled flow injection system was developed for the determination of cadmium in a hydrometallurgical zinc refining process stream. An anion-exchange method in acidic potassium iodide medium was used for the on-line separation of cadmium from the matrix zinc. 1-(4-Nitrophenyl)-3-(4-phenylazophenyl)triazene (Cadion) was used as the chromogenic reagent for the spectrophotometric detection of cadmium. In order to expand the dynamic range of the flow injection - spectrophotometry, a computer-aided time-based variable-volume injection method has been employed for the introduction of the sample into the flow injection system. Samples ranging from 0.56 to 350 microl can be delivered by controlling the time period of the sample introduction valve and the flow rate of the carrier solution. The system permits a throughput of 5 samples per hour. The reproducibility has been proven to be satisfactory with a relative standard deviation of less than 6.2% (sample injected: 0.56 microl of 850 microg Cd/ml; n=100) and 5.0% (350 microl of 0.14 microg Cd/ml; n=5). The determination limit was 20 microg Cd/ml with 0.56 microl sample injection and 0.05 microg Cd/ml with 350 microl sample injection (the absolute amount of cadmium injected into the system was 11 ng and 17.5 ng, respectively).     

Use of 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel for automated preconcentration and selective determination of antimony(III) by flow-injection electrothermal atomic absorption spectrometry

Selective sorption of Sb(III) on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel) has been used for determination of Sb(III). A flow-injection system comprising a microcolumn connected to the tip of the autosampler was used for preconcentration. The sorbed antimony was eluted with nitric acid directly into the graphite furnace and determined by AAS. The detection limit for antimony under the optimum conditions was 0.3 ng mL^–1. This procedure was used for determination of antimony in natural water, soil, vegetation, and a certified sample of a city waste incineration ash (BCR 176).     

Determination of Mo(VI) in tap-water and sea-water by differential-pulse polarography and co-flotation

A new method is described for the microdetermination of Mo(VI) in natural waters and sea-water by differential-pulse polarography based on the catalytic wave caused by Mo(VI) in nitrate medium following preconcentration by co-flotation on Fe(III) hydroxide. In the case of sea-water samples, hexadecyltrimethylammonium bromide (HTAB) was used together with octadecylamine as the surfactant. For the analysis of natural water samples only HTAB is needed. Molybdenum in the range 0.7-5.7 ng/ml has been determined.     

Natural analcime zeolite modified with 5-Br-PADAP for the preconcentration and anodic stripping voltammetric determination of trace amount of cadmium.

A procedure for separation and preconcentration of trace amounts of cadmium has been proposed. A column of analcime zeolite modified with benzyldimethyltetradecylammonium chloride and loaded with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) was used for retention of cadmium. The cadmium was quantitatively retained on the column at pH approximately 9 and was recovered from column with 5 ml of 2 M nitric acid with a preconcentration factor of 140. Anodic stripping differential pulse voltammetry was used for determination of cadmium. A 0.05 ng/ml detection limit for the preconcentration of aqueous solution of cadmium was obtained. The relative standard deviation (RSD) for eight replicate determinations at the 1 microg/ml cadmium levels was 0.31% (calculated with the peak height obtained). The calibration graph using the preconcentration system was linear from 0.01 to 150 microg/ml in final solution with a correlation coefficient of 0.9997. For optimization of conditions, various parameters such as the effect of pH, flow rate, instrumental conditions and interference of number of ions, were studied in detail. This method was successfully applied for determination of cadmium in various complex samples.     

On-line preconcentration of mercury by sorption on an anion-exchange resin loaded with 1,5-bis[(2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide and determination by cold-vapour inductively coupled plasma atomic emission

1,5-Bis[(2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide (PSTH) immobilized on an anion-exchange resin (Dowex) has been used for the on-line preconcentration of mercury from biological samples and waters prior to its determination by inductively coupled plasma atomic emission spectroscopy. The metal was eluted from the column using a solution of 2 M HNO(3) and mixed on-line with SnCl(2). The optimum experimental conditions were evaluated for the continuous preconcentration of Hg, the direct generation of mercury vapour and the final determination of this element by ICP-AES. The enrichment, together with low blank levels of the optimized procedure, allow the simple determination of this toxic element at concentrations down to a few nanograms per milliliter. The proposed method has a linear calibration range 5-1000 ng ml(-1) of mercury, with a detection limit of 4 ng ml(-1) (S/N=3) and a sampling rate of 40 h(-1), investigated with a 9 ml sample volume. The precision of the method (evaluated as the relative standard deviation obtained after analyzing ten series of ten replicates) was +/-3.6% at the 10 ng ml(-1) level of Hg(II) and +/-1.3% at the 100 ng ml(-1) level. The accuracy of the method was examined by the analysis of certified reference materials.     

Adsorptive preconcentration for voltammetric measurements of trace levels of zirconium

This paper describes an electrochemical stripping procedure for ultratrace measurements of zirconium, in which preconcentration is achieved by the adsorption of a zirconium-Solochrome Violet RS complex onto a hanging mercury drop electrode. Cyclic voltammetry was used to characterize the interfacial and redox behaviour. For a 10-min preconcentration time, the detection limit found was 2.3 x 10(-10)M. Optimal experimental conditions were found to be use of a stirred acetate buffer (pH 4.6) solution with Solochrome Violet RS concentration 1.5 x 10(-6)M, a preconcentration potential of -0.3 V and linear scan mode. A 60-fold enhancement of the response is obtained following 5-min preconcentration. With preconcentration for 60 sec, calibration plots for zirconium are linear for the 1.1 x 10(-8)-1.1 x 10(-7)M range. The relative standard deviation at 5.5 x 10(-8)M is 1.7%. Possible interferences by surface-active organic materials and other trace metals have been investigated. Zirconium added to a sea-water sample at the 10 ng/ml level was readily determined.     

On-line preconcentration of inorganic mercury and methylmercury in sea-water by sorbent-extraction and total mercury determination by cold vapour atomic absorption spectrometry

A comparative study of three mercury chelate forming reagents [diethyldithiocarbamate, pyrrolidin-1-yldithioformate and diphenylthiocarbazone (dithizone)] has been carried out for the preconcentration of ultratrace amounts of inorganic mercury and methylmercury in silica C(18) minicolumns as the solid sorbent. Sample flow injection in-line sorbent extraction was coupled with continuous cold vapour atomic absorption spectrometry (CVAAS) for detection. Results showed the superiority of the carbamate type reagents over the dithizone for the on-line formation and preconcentration of the corresponding mercury chelates. Using diethyldithiocarbamate (DDC) as reagent, aqueous sample volumes of 100 ml can be preconcentrated with 100% efficiency for both inorganic mercury and methylmercury. Quantitative release of the retained DDC chelates was obtained for volumes of eluent (ethanol) of 50 microl. Following the proposed procedure, detection limits of 16 ng/l. of mercury were achieved for sample volumes of 25 ml. The relative standard deviation was +/- 3.4% at 0.5 microg/l. Hg(II) levels. The method has been successfully applied to the determination of low levels of mercury in sea-water.     

Determination of trace elements in sea water by graphite-furnace atomic absorption spectrometry after preconcentration by tetrahydroborate reductive precipitation

A method is described for the preconcentration of 16 elements from coastal and deep ocean sea water based on their reductive precipitation by sodium tetrahydroborate. The enrichment factors obtained were sufficient to permit the analysis of a near-shore sea-water reference material (11 elements) and an open ocean sea-water reference material (9 elements). Recoveries from 900 ml of sea water ranged from 80 to 107% (100-ml sample for Mn) with absolute blanks between <1.0 ng (Se) and 20 ng (Cu). Estimated detection limits varied from 0.3 ng l ^?1 (Pb) to 19 ng l^?1 (As) based on a 36-fold concentration of a 900-ml sample.     

Simultaneous spectrophotometric determination of nitrite and nitrate by flow injection analysis.

A new catalytic spectrophotometric method is reported for the simultaneous determination of nitrite and nitrate by flow injection analysis, based on the catalytic effect of nitrite on the redox reaction between pyrogallolsulfonephthalein and potassium bromate in acidic media. Nitrate can also be on-line reduced to nitrite with a modified copper-coated cadmium reduction column. The reaction was monitored spectrophotometrically by measuring the decrease in the absorbance of pyrogallolsulfonephthalein at 465 nm. Various analytical parameters such as effects of acidity, reagent concentrations, flow rates, sample sizes, lengths of the reaction coil and temperatures were studied and were optimized. Under the optimized conditions, the calibration graph was linear for 2.4 to 160 ng ml(-1) of nitrite and 4.0 to 100 ng ml(-1) of nitrate. The influences of potential interfering cations and anions for nitrite and nitrate determination were studied. The method is successfully applied for food and water samples. Up to ten samples can be analyzed per hour.     

Determination of seven trace elements in natural waters by neutron activation analysis after preconcentration with 1-(2-pyridylazo)-2-naphthol

A procedure is described for the preconcentration of Cd(I), Co(II), Cr(III), Cu(II), Mn(II), U(VI) and Zn(II) from 800 ml of water and sea-water samples by coprecipitation with 1-(2-pyridylazo)-2-naphthol (PAN) prior to neutron activation. Chromium is reduced to Cr(III) by hydroxylammonium chloride at pH 4 before the preconcentration step. Coprecipitation of 30 mg of PAN was most effective at pH 9 with final recoveries of 76–91% for six elements and 50% for uranium. The scheme is based on double irradiation of the same samples. Short (10 min) irradiation followed by γ-spectrometry counting for 10 min gives data for Cd (^111mCd), Co, Cu, Mn and U (²³⁹U). A second 16-h irradiation permits determination of zinc and uranium (²³⁹Np) after a waiting time of 6 h, cadmium (¹¹⁵Cd) after 24 h and chromium after a waiting period of 2 weeks followed by counting for 30 min. Detection limits are 0.04 ng g^?1 for Co, 0.8 ng g^?1 for Cd, 0.3 ng g^?1 for Cu, 0.2 ng g^?1 for Cr, 0.006 ng g^?1 for Mn, 0.006 ng g^?1 for U and 0.3 ng g^?1 for Zn. A further decrease of the detection limit for chromium to 0.05 ng g^?1 can be achieved by separation of interfering nuclides and scintillation counting of ⁵¹Cr with a NaI(Tl) well-type detector.     

Atomic absorption determination of traces of cadmium in urine after electrodeposition onto a tungsten wire

A three-coil tungsten wire is used as electrode for the preconcentration of cadmium, which is then placed in a graphite tube for atomization and atomic absorption measurement. The heating parameters of the graphite furnace are optimized using the Modified and Weighted Centroid Simplex Method (MWCS), and computer program for automatic calculation. Sulphuric acid is selected as the supporting electrolyte for electrodeposition. The linear range of the calibration graph is 0.00-0.55 ng/ml. The detection limit is 0.01 ng/ml. For 0.1 ng/ml cadmium the coefficient of variation is 3.35% for ten parallel determinations. No interference occurs in the presence of more than 20 coexisting ions. Traces of cadmium in urine of normal people and in river water and the recoveries for cadmium are determined. The results are satisfactory.     

Differential determination of chromium(VI) and total chromium in natural waters using flow injection on-line separation and preconcentration electrothermal atomic absorption spectrometry.

A rapid, sensitive and selective method for the differential determination of CrIII and CrVI in natural waters is described. Chromium(vi) can be determined directly by flow injection on-line sorbent extraction preconcentration coupled with electrothermal atomic absorption spectrometry using sodium diethyldithiocarbamate as the complexing agent and C18 bonded silica reversed-phase sorbent as the column material. Total Cr can be determined after oxidation of CrIII to CrVI by potassium peroxydisulfate. Chromium(III) can be calculated by difference. The optimum conditions for sorbent extraction of CrVI and oxidation of CrIII to CrVI are evaluated. A 12-fold enhancement in sensitivity compared with direct introduction of 40 microliters samples was achieved after preconcentration for 60 s, giving detection limits of 16 ng l-1 for CrVI and 18 ng l-1 for total Cr (based on 3 sigma). Results obtained for sea-water and river water reference materials were all within the certified range for total Cr with a precision of better than 10% relative standard deviation in the range 100-200 ng l-1. The selectivity of the determination of CrVI was evaluated by analysing spiked reference materials in the presence of CrIII, resulting in quantitative recovery of CrVI.