Spectrophotometric determination of aluminium and indium with 2,2',3,4-tetrahydroxy-3',5'-disulphoazobenzene

2,2',3,4-Tetrahydroxy-3',5'-disulphoazobenzene (tetrahydroxyazon 2S) has been synthesized for the first time. This reagent has been used for the spectrophotometric determination of aluminium and indium ions. The method is very sensitive and selective for the direct determination of aluminium and indium. The optimum pH and absorbance of complexes formed of tetrahydroxyazon 2S with aluminium and indium are 5; 500 nm and 495 nm for Al and In, respectively. The system obeys Beer's law at 0.05-1.6 microg mL(-1) of aluminium and 0.06-2.1 microg mL(-1) of indium concentration. The molar absorptivity is 6.42 x 10(4)L mol(-1)cm(-1) for aluminium and 7.70 x 10(4)L mol(-1)cm(-1) for indium. The molar compositions of the complexes are 1:1 at optimum conditions. Alkaline and alkaline earth elements, halogens, thiourea, ascorbic acid, Cd(II), Pb(II), Mn(II), Zn(II), Co(II), Ni(II), Cr(III), Bi(III), La(III), Si(IV) do not interfere this method. The method can be applied to the direct spectrophotometric determination of trace amounts of aluminium in steel, alloys, waste water, river waters, spring water and ground water. The method was also successfully applied to the indium determination in artificial mixture.     

Complexing of heavy metals with DNA and new bioaffinity method of their determination based on amperometric DNA-based biosensor

The immobilized single-stranded DNA (ssIDNA) has been found to be a very effective biospecific analytical reagent when used in a newly developed bioaffinity method of the determination of heavy metals based on the amperometric DNA-based biosensor. This has been concluded from the comparative study of the complexing of heavy metals with double-stranded DNA, single-stranded DNA, and ssIDNA, using Fe(III) and Cu(II) as a model (metal/nucleotide ratio and stability constants are maximum for ssIDNA), from the study of adsorption of Fe(III), Cu(II), Pb(II), and Cd(II) on nitrocellulose membranes, containing single-stranded DNA, and from the determination of their binding constants with ssIDNA. According to these data, the chosen heavy metals can be lined up in a series of binding strengths with ssIDNA: Cu(II) > Pb(II) > Fe(III) > Cd(II). The method of the determination of heavy metals is based on biospecific preconcentration of metal ions on the biosensor followed by the destruction of DNA-metal complexes with ethylenediaminetetraacetate and voltammogram recording has been proposed. The lower detection limits are 4.0 x 10(-11), 1.0 x 10(-10), 1.0 x 10(-9), and 5.0 x 10(-9) M for Cu(II), Pb(II), Cd(II), and Fe(III), respectively. The heavy metals have been assayed in multicomponent environmental and biological systems such as natural and drinking water, milk, and blood serum samples.     

Preconcentration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) ions in environmental samples by membrane filtration prior to their flame atomic absorption spectrometric determinations

A method for separation-preconcentration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) ions by membrane filtration has been described. The method based on the collection of analyte metal ions on a cellulose nitrate membrane filter and determination of analytes by flame atomic absorption spectrometry (FAAS). The method was optimized for several parameters including of pH, matrix effects and sample volume. The recoveries of analytes were generally in the range of 93-100%. The detection limits by 3 sigma for analyte ions were 0.02microgL(-1) for Pb(II), 0.3microgL(-1) for Cr(III), 3.1microgL(-1) for Cu(II), 7.8microgL(-1) for Ni(II) and 0.9microgL(-1) for Cd(II). The proposed method was applied to the determination of lead, chromium, copper, nickel and cadmium in tap waters and RM 8704 Buffalo River Sediment standard reference material with satisfactory results. The relative standard deviations of the determinations were below 10%.     

Sorption profile of Cd(II) ions onto beach sand from aqueous solutions

Sorption of traces of Cd(II) ions onto beach sand is investigated as a function of nature and concentration of electrolyte (10(-4) to 10(-2)M nitric, hydrochloric and perchloric acids, pH 2-10 buffers and deionized water), shaking time 5-40min, shaking speed 50-200strokes/min, dosage of sand (50-1000mg/15cm(3)), concentration of sorbate (1.04x10(-6) to 1.9x10(-4)M) and temperature (293-323K). Maximum sorption of Cd(II) ions (approximately 66%) is achieved from deionized water using 300mg/15cm(3) sand in 20min. The data are successfully tested by Langmuir, Freundlich and Dubinin-Redushkevich (D-R) sorption isotherms. The values for characteristic Langmuir constants Q=13.31+/-0.20micromol/g and of b=(6.56+/-0.53)x10(3)dm(3)/mol, Freundlich constants A=2.23+/-1.16mmol/g and 1/n=0.70+/-0.05 of (D-R) constants beta=-0.005068+/-0.000328kJ(2)/mol(2), X(m)=46.91+/-11.91micromol/g and energy E=9.92+/-0.32kJ/mol have been estimated. Kinetics of sorption has been studied by applying Morris-Weber, Richenberg and Lagergren equations. The sorption follows first order rate equation resulting 0.182+/-0.004min(-1) The thermodynamic parameters DeltaH=32.09+/-2.92kJ/mol, DeltaS=111.0+/-9.5J/molK and DeltaG=-1.68+/-0.02kJ/mol are evaluated. The influence of common ions on the sorption of Cd(II) ions is also examined. Some common ions reduce the sorption while most of the ions have very little effect. It can be concluded that beach sand may be used as an alternative for the expensive synthetic sorbents.     

Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS)

A new method using a column packed with Amberlite XAD-2010 resin as a solid-phase extractant has been developed for the multi-element preconcentration of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), and Pb(II) ions based on their complex formation with the sodium diethyldithiocarbamate (Na-DDTC) prior to flame atomic absorption spectrometric (FAAS) determinations. Metal complexes sorbed on the resin were eluted by 1 mol L(-1) HNO3 in acetone. Effects of the analytical conditions over the preconcentration yields of the metal ions, such as pH, quantity of Na-DDTC, eluent type, sample volume and flow rate, foreign ions etc. have been investigated. The limits of detection (LOD) of the analytes were found in the range 0.08-0.26 microg L(-1). The method was validated by analyzing three certified reference materials. The method has been applied for the determination of trace elements in some environmental samples.     

Determination of Co(II) in water and soil samples using spectrophotometry coupled with preconcentration on 4-amino methyl pyridine anchored silica gel column

4-amino methyl pyridine anchored silica gel (4-AMPS) was used as a sorbent in a simple sensitive spectrophotometry determination of Co(II) in various samples using piperazine dithiocarbamate as a color developing agent (lambda(max)=390 nm) at pH 5.0+/-0.2. Beer's law was obeyed over the range of 0.1-5.0 microg ml(-1). The molar absorptivity and Sandell's sensitivity were 1.257x10(5) lmol(-1) cm(-1) and 0.006145 microg cm(-2), respectively. Under these conditions, the preconcentration factor obtained was 80, and the detection limit achieved was 5.0 ng ml(-1). The detailed study of various interfering ions made the method more sensitive and selective. The recovery of Co(II) from various samples range from 97.50 to 99.66%. The present method was successfully applied for the determination of Co(II) in various water and soil samples. The proposed method was compared with reported methods in terms of Student's 't'-test and variance ratio 'f'-test which indicates that there is no significant difference between proposed and literature method at 95% confidence level.     

A fast response cadmium-selective polymeric membrane electrode based on N,N'-(4-methyl-1,2-phenylene)diquinoline-2-carboxamide as a new neutral carrier

A new polyvinylchloride membrane sensor for Cd(2+) ions based on N,N'-(4-methyl-1,2-phenylene)diquinoline-2-carboxamide (Mebqb) as a new and excellent neutral ionophore has been prepared. The sensor shows a Nernestian response for cadmium ions over a wide concentration range (1.0 x 10(-6) to 1.0 x 10(-1) M) with the determination coefficient of 0.9964 and slope of 29.9 +/- 0.5 mV decade(-1). The limit of detection is 8 x 10(-7) M. It has a fast response time of 3-8s and can be used for at least 8 weeks without any divergence in potential. The electrode can be used in the pH range from 4.0 to 9.0. The proposed sensor shows a very good discriminating ability towards Cd(2+) ion in comparison to some alkali, alkaline earth, transition and heavy metal ions. It was successfully applied for the direct determination of Cd(2+) in standard and real sample solutions.     

Tartrazine modified activated carbon for the removal of Pb(II), Cd(II) and Cr(III)

A two in one attempt for the removal of tartrazine and metal ions on activated carbon has been developed. The method was based on the modification of activated carbon with tartrazine then its application for the removal of Pb(II), Cd(II) and Cr(III) ions at different pH values. Tartrazine adsorption data were modelled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacities qm were 121.3, 67 and 56.7mgg(-1) at initial pH values of 1.0, 6.0 and 10, respectively. The adsorption of tartrazine onto activated carbon followed second-order kinetic model. The equilibrium time was found to be 240min at pH 1.0 and 120min at pH 10 for 500mgL(-1) tartrazine concentration. A maximum removal of 85% was obtained after 1h of contact time. The presence of tartrazine as modifier enhances attractive electrostatic interactions between metal ions and carbon surface. The adsorption capacity for Pb(II), Cd(II) and Cr(III) ions has been improved with respect to non-modified carbon reaching a maximum of 140%. The adsorption capacity was found to be a pH dependent for both modified and non-modified carbon with a greater adsorption at higher pH values except for Cr(III). The enhancement percent of Pb(II), Cd(II) and Cr(III) at different pH values was varied from 28% to 140% with respect to non-modified carbon. The amount of metal ions adsorbed using static regime was 11-40% higher than that with dynamic mode. The difference between adsorption capacities could be attributed to the applied flow rate.     

Azadirachta indica (Neem) leaf powder as a biosorbent for removal of Cd(II) from aqueous medium

A biosorbent, Neem leaf powder (NLP), was prepared from the mature leaves of the Azadirachta indica (Neem) tree by initial cleaning, drying, grinding, washing to remove pigments and redrying. The powder was characterized with respect to specific surface area (21.45 m2g(-1)), surface topography and surface functional groups and the material was used as an adsorbent in a batch process to remove Cd(II) from aqueous medium under conditions of different concentrations, NLP loadings, pH, agitation time and temperature. Adsorption increased from 8.8% at pH 4.0 to 70.0% at pH 7.0 and 93.6% at pH 9.5, the higher values in alkaline medium being due to removal by precipitation. The adsorption was very fast initially and maximum adsorption was observed within 300 min of agitation. The kinetics of the interactions was tested with pseudo first order Lagergren equation (mean k(1)=1.2x10(-2)min(-1)), simple second order kinetics (mean k2=1.34x10(-3) gmg(-1)min(-1)), Elovich equation, liquid film diffusion model (mean k=1.39x10(-2)min(-1)) and intra-particle diffusion mechanism. The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 158mgg(-1) for the NLP and Freundlich adsorption capacity of 18.7 Lg(-1). A 2.0 g of NLP could remove 86% of Cd(II) at 293 K from a solution containing 158.8 mg Cd(II) per litre. The mean values of the thermodynamic parameters, DeltaH, DeltaS and DeltaG, at 293 K were -73.7 kJmol(-1), -0.24 Jmol(-1)K(-1) and -3.63 kJmol(-1), respectively, showing the adsorption process to be thermodynamically favourable. The results have established good potentiality for the Neem leaf powder to be used as a biosorbent for Cd(II).     

Selective determination of beryllium(II) ion at picomole per decimeter cubed levels by kinetic differentiation mode reversed-phase high-performance liquid chromatography with fluorometric detection using 2-(2'-hydroxyphenyl)-10-hydroxybenzo[H]quinoline as precolumn chelating reagent

A highly sensitive and selective method for the determination of the Be(II) ion has been developed by the use of reversed-phase high-performance liquid chromatography (HPLC) with fluorometric detection using 2-(2'-hydroxyphenyl)-10-hydroxybenzo[h]quinoline (HPHBQ) as a precolumn (off-line) chelating reagent. The reagent HPHBQ has been designed to form the kinetically inert Be chelate compatible with high fluorescence yield, which is appropriate to the HPLC-fluorometric detection system. The Be-HPHBQ chelate is efficiently separated on a LiChrospher 100 RP-18(e) column with a methanol (58.3 wt %)-water eluent containing 20 mmol kg(-1) of tartaric acid and is fluorometrically detected at 520 nm with the excitation at 420 nm. Under the conditions used, the concentration range of 20-8,000 pmol dm(-3) of Be(II) ion can be determined without interferences from 10 micromol dm(-3) each of common metal ions, typically Al(III), Cu(II), Fe(III), and Zn(II), and still more coexistence of Ca(II) and Mg(II) ions at 0.50 mmol dm(-3) and 5.0 mmol dm(-3), respectively, is tolerated. The detection limit (3a baseline fluctuation) is 4.3 pmol dm(-3) (39 fg cm(-3)). The extraordinarily high sensitivity with toughness toward the matrix influence was demonstrated with the successful application to environmental Be analyses, such as determination of Be in rainwater and tap water.     

Photothermal deflection determination of iron(II) with ferrozine with sorption preconcentration on Silufol plates

Photothermal deflection spectroscopy was applied to the selective detection of iron(II) chelate with ferrozine by its sorption preconcentration on Silufol plates. The linearity range was 1 x 10(-11) - 6 x 10(-8) mol cm(-2) of chelate at the plate surface, which corresponded to 1 x 10(-9) -4 x 10(-6) M of chelate in solution. The limits of detection and quantification are 8 x 10(-12) and 2.5 x 10(-11) mol cm(-2) at the plate from 15 microL of test solution (0.5 nM and 1.5 nM in solution, respectively), and the absolute detection limit is 8 fmol in the whole spot applied to a plate. Characteristics and features of photothermal deflection detection are discussed.     

An optical fiber chemical sensor for mercury ions based on a porphyrin dimer

The synthesis of a novel fluoroionophore, 5-p-[[4-(10',15',20'-triphenyl-5'-porphinato) phenyloxyl]-1-butyloxyl]phenyl-10,15,20-triphenylporphine (DTPP), and its application for preparation of a Hg(II)-sensitive optical fiber chemical sensor are described. The response of the sensor is based on the fluorescence quenching of DTPP by coordination with Hg(II). The porphyrin dimer-based sensor shows a linear response toward Hg(II) in the concentration range 5.2 x 10(-7)-3.1 x 10(-4) mol x L(-1), with a working pH range from 2.4 to 8.0. The sensor shows excellent selectivity for Hg(II) over transition metal cations including Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II), and Fe(III). As a sensing agent, the porphyrin dimer shows obviously better fluorescence response characteristics toward Hg(II) compared to porphyrin monomer or metalloporphyrin. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for determination of Hg(II) in water samples.     

Ultrasensitive Pb(II) potentiometric sensor based on copolyaniline nanoparticles in a plasticizer-free membrane with a long lifetime

A newly designed Pb(II) potentiometric sensor based on intrinsically conducting nanoparticles of solid poly(aniline-co-2-hydroxy-5-sulfonic aniline) possessing many ligating functional groups like -NH-, -N=, -OH, -SO(3)H, -NH(2) as ionophores in plasticizer-free vinyl resin solid membranes has been fabricated. A linear Nernstian response is obtained within a wide Pb(II) activity range from 1.0 × 10(-3) to 1.0 × 10(-10) M with a detection limit as low as 2.2 × 10(-11) M. The pH independent plateau ranges between 3.5 and 7.0. After 15 months' usage, the sensor maintains 95% performance parameters. Its anti-interference ability to Cu(II), Cd(II), Ag(I), and Hg(II) is much stronger than other sensors with a detection limit at (sub)nanomolar level. Electrochemical impedance spectroscopy reveals that the solid sensing membrane has a diffusion coefficient of around 5 × 10(-14) to 1 × 10(-13) cm(2) s(-1). The much lower diffusion coefficient for Pb(II) is highly beneficial for the elimination of Pb(II) flux across the membrane. The wide detection concentration range, low detection limit, high selectivity, extensive pH window, and long lifetime make for a robust sensor giving reliable measurement of Pb(II) content with potential application in real-world samples at trace levels.     

Simultaneous determination of trace cadmium and arsenic in biological samples by hydride generation-double channel atomic fluorescence spectrometry

Hydride generation atomic fluorescence spectrometry (HG-AFS) has been used for determination of hydride-forming elements because of its high sensitivity, simplicity, and low costs, but most of such work has been concentrated on single element analysis, and reports dealing with multielement determination by HG-nondispersive (ND)AFS are rare. In this work, a sensitive HG-NDAFS method was developed for simultaneous determination of trace cadmium and arsenic in biological materials. The conditions for the generation of volatile cadmium and arsenic species from the reaction with KBH4 in aqueous solution were investigated using a double-channel AFS integrated with an intermittent flow reactor. Like thiourea and Co(II), ascorbic acid was found to significantly enhance the generation efficiency of volatile Cd and As species. The interferences of coexisting ions were evaluated. Under optimal conditions, the detection limits for Cd and As were determined to be 10 and 150 ng L(-1), respectively. The precision for 11 replicate determinations at the 1 microg L(-1) Cd level and the 10 microg L(-1) As level were 3.5 and 2.7% (RSD), respectively. The recoveries of spike analytes in the biological samples studied ranged from 94 to 109%. The proposed method was successfully applied to the simultaneous determination of Cd and As in a variety of biological samples.     

Sawdust--a green and economical sorbent for the removal of cadmium (II) ions

The ability of sawdust (treated and untreated) waste, a waste material derived from the commercial processing of cedrus deodar wood for furniture production, to remove/preconcentrate Cd(II) ions from aqueous solution was determined. Sorption was found to be rapid (approximately 97% within 8 min). The binding of metal ions was found to be pH dependent, optimal sorption accruing at around pH 4-8. Potentiometric titrations of sawdust revealed two distinct pK(a) values, the first having the value similar to carboxylic groups (3.3-4.8) and second comparable with that of amines (8.53-10.2) with the densities 1.99 x 10(-4) and 7.94 x 10(-5), respectively. Retained Cd(II) ions were eluted with 5 ml of 0.1 mol l(-1) HCl. Detection limit of 0.016 microg ml(-1) was achieved with enrichment factors of 120. Recovery was quantitative using sample volume of 600 ml. The Langmuir and D-R isotherm equations were used to describe partitioning behavior for the system at different temperatures. Kinetic and thermodynamic behavior of sawdust for Cd(II) ions removal was also studied.     

On-line solid phase selective separation and preconcentration of Cd(II) by solid-phase extraction using carbon active modified with methyl thymol blue

An on-line flow system was used to develop a selective and efficient on-line sorbent extraction preconcentration system for cadmium. The method is based on adsorption of cadmium ions onto the activated carbon modified with methyl thymol blue. Then the adsorbed ions were washed using 0.5M HNO(3) and the eluent was used to determine the Cd(II) ions using flame atomic absorption spectrometry. The results obtained show that the modified activated carbon has the greatest adsorption capacity of 80 microg of Cd(II) per 1.0 g of the solid phase. The optimal pH value for the quantitative preconcentration was 9.0 and full desorption is achieved by using 0.5M HNO(3) solution. It is established that the solid phase can be used repeatedly without a considerable adsorption capacity loss. The detection limit was less than 1 ngmL(-1) Cd(II), with an enrichment factor of 1000. The calibration graph was linear in the range of 1-2000 ngmL(-1) Cd(II). The developed method has been applied to the determination of trace cadmium (II) in water samples and in the following reference materials: sewage sludge (CRM144R), and sea water (CASS.4) with satisfactory results. The accuracy was assessed through recovery experiments.     

Adsorption of Pb(II) and Cd(II) from aqueous solutions using titanate nanotubes prepared via hydrothermal method

Titanate nanotubes (TNs) with specific surface areas of 272.31 m(2)g(-1) and pore volumes of 1.264 cm(3)g(-1) were synthesized by alkaline hydrothermal method. The TNs were investigated as adsorbents for the removal of Pb(II) and Cd(II) from aqueous solutions. The FT-IR analysis indicated that Pb(II) and Cd(II) adsorption were mainly ascribed to the hydroxyl groups in the TNs. Batch experiments were conducted by varying contact time, pH and adsorbent dosage. It was shown that the initial uptake of each metal ion was very fast in the first 5 min, and adsorption equilibrium was reached after 180 min. The adsorption of Pb(II) and Cd(II) were found to be maximum at pH in the range of 5.0-6.0. The adsorption kinetics of both metal ions followed the pseudo-second-order model. Equilibrium data were best fitted with the Langmuir isotherm model, and the maximum adsorption capacities of Pb(II) and Cd(II) were determined to be 520.83 and 238.61 mg g(-1), respectively. Moreover, more than 80% of Pb(II) and 85% of Cd(II) adsorbed onto TNs can be desorbed with 0.1M HCl after 3h. Thus, TNs were considered to be effective and promising materials for the removal of both Pb(II) and Cd(II) from wastewater.     

An ion-imprinted functionalized silica gel sorbent prepared by a surface imprinting technique combined with a sol-gel process for selective solid-phase extraction of cadmium(II)

A new ion-imprinted thiol-functionalized silica gel sorbent was synthesized by a surface imprinting technique in combination with a sol-gel process for selective on-line, solid-phase extraction of Cd(II). The Cd(II)-imprinted thiol-functionalized silica sorbent was characterized by FT-IR, the static adsorption-desorption experiment, and the dynamic adsorption-desorption method. The maximum static adsorption capacity of the ion-imprinted functionalized sorbent was 284 micromol g(-1). The largest selectivity coefficient for Cd(II) in the presence of Pb(II) was over 220. The static uptake capacity and selectivity coefficient of the ion-imprinted functionalized sorbent are higher than those of the nonimprinted sorbent. The breakthrough capacity and dynamic capacity of the imprinted functionalized silica gel sorbent for 4 mg L(-1) of Cd(II) at 5.2 mL min(-1) of sample flow rate were 11.7 and 64.3 micromol g(-1), respectively. No remarkable effect of sample flow rate on the dynamic capacity was observed as the sample flow rate increased from 1.7 to 6.8 mL min(-1). The imprinted functionalized silica gel sorbent offered a fast kinetics for the adsorption and desorption of Cd(II). The prepared ion-imprinted functionalized sorbent was shown to be promising for on-line, solid-phase extraction coupled with flame atomic absorption spectrometry for the determination of trace cadmium in environmental and biological samples. All competitive ions studied did not interfere with the determination of Cd(II). With a sample loading flow rate of 8.8 mL min(-1) for 45-s preconcentration, an enhancement factor of 56, and a detection limit (3sigma) of 0.07 microg L(-1) were achieved at a sampling frequency of 55 h(-1). The precision (RSD) for 11 replicate on-line sorbent extractions of 8 mug L(-1) Cd(II) was 0.9%. The sorbent also offered good linearity (r = 0.9997) for on-line, solid-phase extraction of trace Cd(II).     

Determination of hydrocarbons using sapphire fibers coated with poly(dimethylsiloxane)

A poly(dimethylsiloxane) (PDMS) coated sapphire fiber has been investigated as a sensor for hydrocarbons (HCs) in the mid-infrared region around 3000 cm(-1). In order to optimize and predict sensor response, the diffusion behavior of the analytes into the PDMS preconcentration medium has been examined. A diffusion model based on Fickian diffusion was used to quantify diffusion. The model incorporated such factors as film thickness, refractive index of the polymer and the fiber core, and principal wavelength at which the analyte absorbs. A range of hydrocarbons, from hexane to pentadecane, was analyzed at 2930 cm(-1) using both fiber-coupled Fourier transform infrared spectroscopy and a modular prototype system. Diffusion coefficients were determined for these compounds and diffusion behavior examined and related to factors such as analyte polarity and molecular size. The diffusion coefficients were found to range from 6.41 x 10(-11) 5 x 10(-12) to 5.25 x 10(-11) +/- 9 x 10(-13) cm2 s(-1) for hexane and pentadecane into a 2.9 microm PDMS film, respectively. The diffusion model was also used to examine the effect of changing system parameters such as film thickness in order to characterize sensor response.     

Determination of Cd, Co, Ni and Pb in biological samples by microcolumn packed with black stone (Pierre noire) online coupled with ICP-OES

A simple and sensitive method using microcolumn (20-mm length x 2.0-mm i.d.) packed with black stone (Pierre noire) for the separation/preconcentration of Cd, Co, Ni and Pb in biological samples prior to their online determination by inductively coupled plasma optical emission spectrometry (ICP-OES) has been developed. Optimal experimental conditions including pH, eluent concentration and volume, sample volume and sample flow rate were investigated and established. The adsorption capacity of black stone for Cd, Co, Ni and Pb were found to be 23.4, 21.2, 18.1 and 22.2 mg g(-1), respectively. With a preconcentration time of 72 s and an elution time of 4s, an enrichment factor of 20 and a sampling frequency of 25 h(-1) were obtained. The detection limits corresponding to three times the standard deviations of the blank for Cd, Co, Ni and Pb were found to be 0.3, 0.4, 0.4 and 1.1 ng mL(-1). The precision for seven replicate determinations of Cd, Co, Ni and Pb gave relative standard deviations (RSDs) of 5.9, 4.8, 2.7 and 1.1%, respectively (n=7, C=10 ng mL(-1)). The method was validated with certified reference material GBW09103 human urine and the results obtained were in good agreement with the certified values. The method was also applied to the determination of the target analytes in biological samples with satisfactory results.