Determination of low cadmium concentrations in wine by on-line preconcentration in a knotted reactor coupled to an inductively coupled plasma optical emission spectrometer with ultrasonic nebulization

An on-line cadmium preconcentration and determination system implemented with inductively coupled plasma optical emission spectrometry (ICP-OES) associated to flow injection (FI) with ultrasonic nebulization system (USN) was studied. The cadmium was retained as the cadmium-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol, Cd-(5-Br-PADAP), complex, at pH 9.5. The cadmium complex was removed from the knotted reactor (KR) with 3.0 mol/L nitric acid. A total enhancement factor of 216 was obtained with respect to ICP-OES using pneumatic nebulization (12 for USN and 18 for KR) with a preconcentration time of 60 s. The value of the detection limit for the preconcentration of 5 mL of sample solution was 5 ng/L. The precision for 10 replicate determinations at the 5 microg/L Cd level was 2.9% relative standard deviation (RSD), calculated from the peak heights obtained. The calibration graph using the preconcentration system for cadmium was linear with a correlation coefficient of 0.9998 at levels near the detection limits up to at least 1,000 microg/L. The method was successfully applied to the determination of cadmium in wine samples.     

Determination of trace cadmium in waters by flame atomic absorption spectrophotometry after preconcentration with 1-nitroso-2-naphthol-3,6-disulfonic acid on Ambersorb 572

A procedure for the determination of trace amount of cadmium after adsorption of its 1-nitroso-2-naphthol-3,6-disulfonic acid chelate on Ambersorb 572 has been proposed. This chelate is adsorbed on the adsorbent in the pH range 3-8 from large volumes of aqueous solution of water samples with a preconcentration factor of 200. After being sorbed, cadmium was eluted by 5 mL of 2.0 mol L(-1) nitric acid solution and determined directly by flame atomic absorption spectrophotometery (FAAS). The detection limit (3sigma) of cadmium was 0.32 microg L(-1). The precision of the proposed procedure, calculated as the relative standard deviation of recovery in sample solution (100 mL) containing 5 microg of cadmium was satisfactory (1.9%). The adsorption of cadmium onto adsorbent can formally be described by a Langmuir equation with a maximum adsorption capacity of 19.6 mg g(-1) and a binding constant of 6.5 x 10(-3) L mg(-1). Various parameters, such as the effect of pH and the interference of a number of metal ions on the determination of cadmium, have been studied in detail to optimize the conditions for the preconcentration and determination of cadmium in water samples. This procedure was applied to the determination of cadmium in tap and river water samples.     

Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode

A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments.     

Preconcentration and determination of cadmium by GFAAS after solid-phase extraction with synthetic zeolite.

The solid-phase extraction (SPE) method for the preconcentration of trace amounts of cadmium using synthetic zeolite A-4 and its determination by graphite furnace atomic absorption spectrometry (GFAAS) was investigated. The preconcentration conditions, such as the optimum pH range of the sample solution for the adsorption of cadmium and the kind of acid solution for dissolving the cadmium-adsorbed synthetic zeolite A-4, as well as the measurement conditions for the determination of cadmium by GFAAS, e.g., the ashing and atomizing temperature, were investigated. Quantitative recovery of cadmium onto zeolite A-4 from the sample solution over the pH range 2.0 - 9.0 was achieved by the batch method. After the solid-phase (cadmium-adsorbed zeolite A-4) was separated from the sample solution by a membrane filter, it was dissolved in 2.0 cm(3) of 2.0 mol dm(-3) nitric acid. An aliquot of the resulting solution was injected into the graphite furnace. In GFAAS measurements an alternate gas (Ar, 90%; O(2), 10%) was used as a sheath gas, and the ashing temperature and atomizing temperature were 400 degrees C and 1600 degrees C, respectively. The detection limit (3 sigma) for cadmium was 0.002 microg dm(-3). The relative standard deviation at 0.010 microg dm(-3) was 3.5 - 4.5% (n = 5). The proposed method has been successfully applied to the analysis of trace cadmium in environmental water samples.     

Differential pulse polarographic determination of uranium(VI) in complex materials after adsorption of its trifluoroethylxanthate cetyltrimethylammonium ion-associated complex on naphthalene adsorbent.

Uranium(VI) is adsorbed as a uranium trifluoroethylxanthate (TFEX)-cetyltrimethylammonium (CTMA) ion-pair complex on microcrystalline naphthalene quantitatively in the pH range 4.2 - 7.0. Without cetyltrimethylammonium as the counter ion, the adsorption is hardly 70%. The metal has been desorbed with HCI and determined with a differential pulse polarograph. Uranium can alternatively be quantitatively adsorbed on TFEX-CTMA-naphthalene adsorbent packed in a column at a flow rate of 1 - 5 ml/min and determined similarly. A well-defined peak has been obtained in this medium at -0.20 V versus a saturated calomel electrode. Cyclic voltammetry, differential pulse polarography and D.C. polarography studies indicate that uranium has been reduced irreversibly under these conditions. The detection limit is 0.30 microg/ml at the minimum instrumental settings (signal-to-noise ratio of 2) (with a preconcentration factor of 10, the detection limit would be 30 ng/ml for uranium when the volume in the cell is 15 ml). However if the volume in the cell is 5 ml, it would have been 10 ng/ml with a preconcentration factor of 30. Linearity is maintained in a concentration range of 0.5 - 19.0 microg/ml (2.1 - 79.83 x 10(-9) M) with a correlation factor of 0.9994 and a relative standard deviation of +/-1.1% (in this case 7.5 microg may be concentrated from 150 ml of the aqueous sample where its concentration is as low as 50 ng/ml). Various parameters, such as the effect of the pH, volume of the aqueous phase, flow rate and the interference of a large number of metal ions and anions on the determination of uranium, have been studied in detail to optimize the conditions for its trace determination in various complex materials, like alloys, coal fly ash, biological, synthetic, and waste-water samples.     

Determination of copper at ng levels by in-line preconcentration and flow-injection analysis coupled with flame atomic-absorption spectrometry

Oxine/formaldehyde/resorcinol and oxine/formaldehyde/hydroquinone resins have been synthesized and their physicochemical properties studied. Conditions were optimized for the preconcentration of copper by batch extraction and column chromatography with the resins. A flow-injection analysis (FIA) manifold was constructed for the determination of copper at ng levels by preconcentration on microcolumns containing the resins, stripping, and atomic-absorption spectrometry. For batch preconcentration a pH of about 2.5-3 was optimal whereas in the FIA system a broader pH range (approximately 2-3.5) could be used. Separations of binary mixtures of Cu(II) with Ni(II) or PB(II) at microg/ml level did not show any cross-contamination. In the FIA, a 2 cm long column and 2 ml/min flow-rate were adequate for quantitative uptake of copper; 50 micro1 of 0.1M hydrochloric acid quantitatively eluted the copper.     

Liquid chromatographic determination of trimethylamine in water

A method for the selective determination of trimethylamine (TMA) in aqueous matrices by liquid chromatography is reported. The proposed procedure is based on the derivatization of the analyte with 9-fluorenylmethyl chloroformate (FMOC) in a precolumn (Hypersil C18, 30 microm, 20 mm x 2.1 mm i.d.) connected on-line to the analytical column (LiChrosphere 100 RP18, 5 microm, 125 mm x 4 mm i.d.). Gradient elution was performed with a mixture of acetonitrile-water-0.05 M borate buffer (pH 9.0). The method has been applied to the direct determination of TMA in water within the 0.25-10.0 microg/ml concentration interval, and can also be adapted to the determination of TMA over the range 0.05-1.0 microg/ml by incorporating a preconcentration stage with C18 solid-phase extraction (SPE) cartridges. Good linearity, reproducibility and accuracy was achieved within the tested concentration intervals. The limits of detection at 262 nm were 50 and 5 ng/ml for the direct method and for the method involving preconcentration, respectively. The proposed conditions allowed the selective determination of TMA in the presence of other primary and secondary short-chain aliphatic amines. The utility of the described procedure has been tested by determining TMA in different water samples.     

A new flow injection preconcentration method based on multiwalled carbon nanotubes for the ETA-AAS determination of Cd in urine

A new flow injection (FIA) procedure for the preconcentration of cadmium in urine using multiwalled carbon nanotubes (MWCNT) as sorbent and posterior electrothermal atomization atomic absorption spectrometry (ETA-AAS) Cd determination has been developed. Cadmium was retained in a column filled with previously oxidized MWCNTs and it was quantitatively eluted with a nitric acid solution. The parameters influencing the adsorption-elution process such as pH of the sample solution, amount of sorbent and flow rates of sample as well as eluent solutions have been studied. Cd concentration in the eluent was measured by ETA-AAS under the optimized conditions obtained. The results indicated the elimination of urine matrix effect as a consequence of the preconcentration process performed. Total recovery of cadmium from urine at pH 7.2 using a column with 45 mg of MWCNTs as sorbent and employing a HNO₃ 0.5 mol L⁻¹ solution for elution was attained. The detection limit obtained was 0.010 μg L⁻¹ and the preconcentration factor achieved was 3.4. The method showed adequate precision (RSD: 3.4-9.8%) and accuracy (mean recovery: 97.4-100%). The developed method was applied for the determination of cadmium in real urine samples from healthy people (in the range of 0.14-2.94 μg L⁻¹) with satisfactory results.     

Column preconcentration of trace manganese with the ion pair of 2-nitroso-1-naphthol-4-sulfonic acid tetradecyldimethylbenzyl-ammonium chloride supported on naphthalene and determination by derivative spectrophotometry

A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples.     

Determination of trace impurities in some nickel compounds by flame atomic absorption spectrometry after solid phase extraction using Amberlite XAD-16 resin

A simple flame atomic absorption spectrometric (FAAS) procedure for the determination of lead, bismuth, gold, palladium and cadmium as impurities in Raney nickel and nickel oxide was developed using a preconcentration step on an Amberlite XAD-16 resin packed column. Lead, bismuth, gold, palladium and cadmium were quantitatively recovered and separated from a solution containing 1 M HCl and 0.3 M NaI by the column system. Effects of the various parameters such as reagent concentrations, sample volume, matrix effects, etc. have been investigated. Under optimized conditions, the relative standard deviation of the combined method of sample treatment, preconcentration and determination with FAAS (n = 7) is generally lower than 12%. The limit of detection (3s, n = 20) was between 10–270 ng/g. The results were used for separation and preconcentration of five trace elements from nickel matrices.     

On-line complexation of zinc with 5-Br-PADAP and preconcentration using a knotted reactor for inductively coupled plasma atomic emission spectrometric determination in river water samples

An on-line zinc preconcentration and determination system implemented with inductively coupled plasma atomic emission spectrometry (ICP-AES) associated with flow injection (FI) was studied. The zinc was retained as zinc-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Zn-(5-Br-PADAP)) complex at pH 9.2. The zinc complex was removed from the knotted reactor (KR) with 30% v/v nitric acid. An enrichment factor of 42 was obtained for the KR system with respect to ICP-AES using pneumatic nebulization. The detection limit for the preconcentration of 10 mL of aqueous solution was 0.09 microg/L. The precision for 10 replicate determinations at the 5 microg/L Zn level was 2.3% relative standard deviation (RSD), calculated with the peak heights obtained. The calibration graph using the preconcentration system for zinc was linear with a correlation coefficient of 0.9997 at levels near the detection limits up to at least 100 microg/L. The method was succesfully applied to the determination of zinc in river water samples.     

Preconcentration of trace cobalt with the ion pair of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and tetraphenylborate onto microcrystalline naphthalene or column method and its determination by derivative spectrophotometry

Cobalt-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)-tetraphenylborate ion associated complex is quantitatively adsorbed on microcrystalline naphthalene in the pH range 3.5-9.5 from a fairly large volume of the aqueous samples (preconcentration factor ~30). After filtration, the solid mass consisting of the cobalt complex and naphthalene was dissolved with 5 ml of dimethylformamide (DMF) and the metal determined by first-derivative spectrophotometry. The cobalt-5-Br-PADAP complex can alternatively be quantitatively retained on ammonium tetraphenylborate-naphthalene adsorbent filled in a column (preconcentration factor 120) in the same pH range and determined similarly. The detection limit is 30 ppb (signal-to-noise ratio=2) and the calibration curve is linear over 0.3-8.0 mug of cobalt in 5 ml of the final DMF solution. Eight replicate determinations of 1.0 mug of cobalt gave a mean peak height of 0.208 (at 611.5 nm) with a relative standard deviation of 1.2%. The sensitivity of the method is 1.04 (dA/dnm) ml mug(-1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the determination of cobalt has been studied and the optimized conditions developed were utilized for its trace determination in various standard alloys and biological samples.     

Preparation of a fast-flow agarose-based chelating adsorbent with a novel dioxime derivative for selective column preconcentration of copper.

Fast-flow spherical homogeneous agarose beads were prepared by an emulsification method, and were cross-linked and activated by repeated treatment with allylbromide and bromine/water, followed by alkali. Bis(2-aminopyridyl)dioxime (APD) was synthesized by the reaction of 2-aminopyridine, and dichloroglyoxime and characterized by melting-point as well as IR, 1HNMR, 13CNMR and MS spectroscopies. APD was chemically linked to activated agarose beads to be employed for the column preconcentration of metal ions. Capacity measurements for eight metal ions indicated a high selectivity of the adsorbent towards Cu2+ with a capacity of 25.7 micromol per ml packed adsorbent. A factorial design was used for optimization of the effects of 5 different variables on the recovery of Cu2+. Under the optimized conditions, Cu2+ was quantitatively accumulated on a 0.25 ml packed column of the adsorbent in the pH range of 4 to 6, and simply eluted with 2 ml of a 1 mol 1(-1) hydrochloric acid solution. The column could tolerate salt concentrations up to 0.5 mol 1(-1), sample flow rates up to 15 ml min(-1), and sample volumes beyond 1000 ml. Matrix ions of Na+, Mg2+ and Ca2+ and potentially interfering ions of Ni2+, Cd2+, Zn2+, Fe3+ and Co2+ with relatively high concentrations did not show any significant effect on the analyte's signal. Preconcentration factors up to 500 and a detection limit of 0.16 microg 1(-1) were obtained for the determination of the analyte by flame AAS. Application of the method to the determination of natural and spiked copper in river water and seawater samples resulted in quantitative recoveries.     

Determination of Sn(II) and Sn(IV) after mixed micelle-mediated cloud point extraction using alpha-polyoxometalate as a complexing agent by flame atomic absorption spectrometry

The cloud point extraction behavior of Sn(II) and Sn(IV) using alpha-polyoxometalate and mixed surfactants solution was investigated. The mixture of a nonionic surfactant (Triton X-100) and a cationic surfactant (CTAB) was utilized as a suitable micellar medium for preconcentration and extraction of tin complexes. Sn(II) in the presence of Sn(IV) was extracted with alpha-polyoxometalate, 0.3% (w/v) Triton X-100 and 3.5x10(-5) mol L(-1) CTAB at pH 1.2. Whereas the pH value of 3.7 were used for the individual determination of Sn(II) and Sn(IV) and also for total tin determination at the same conditions. Enrichment factors of 100 were obtained for the preconcentration of both metal ions. Under the optimal conditions, linearity was obeyed in the ranges of 55-670 microg L(-1) of Sn(II) and 46-750 microg L(-1) of Sn(IV) ion concentration. The detection limit of the method was also found to be 12.6 microg L(-1) for Sn(IV) and 8.4 microg L(-1) for Sn(II). The relative standard deviation of seven replicate determination of 100 microg L(-1) both metal ions were obtained about 2.4%. The diverse ion effect of some anions and cations on the extraction efficiency of target ions were tested. Finally, the optimized conditions developed were successfully utilized for the determination of each metal ion in various alloy, juice fruit, tape and waste water samples with satisfactory results.     

A sensitive method for cadmium determination using an on-line polyurethane foam preconcentration system and thermospray flame furnace atomic absorption spectrometry.

A new sensitive and low cost method for cadmium determination at microg l(-1) levels that combines an on-line preconcentration system with the thermospray flame furnace atomic absorption spectrometry technique (TS-FF-AAS) is described in this work. Cadmium is preconcentrated from an acidic medium (pH 2.0) by forming a complex with ammonium O,O-diethyldithiophosphate (DDTP), which is then adsorbed onto polyurethane foam (PUF). The elution step is performed by using 80% (v/v) ethanol. The effects of the chemical and flow variables associated with the preconcentration were studied, such as the pH of formation of the Cd-DDTP complex, the DDTP concentration, the preconcentration and elution flow rate and the mass of adsorbent. The present method was operated in volume-mode (2 ml) and provided a linear range from 0.4 to 15.0 microg l(-1) with a sample throughput of 16 h(-1). The increase of power detection related to TS-FF-AAS by coupling the preconcentration system was confirmed by the enhancement of sensitivity (ca. 5 times), when compared to the value for TS-FF-AAS alone, thus achieving a low detection limit (0.12 microg l(-1)). The accuracy of the method was confirmed from analyses of spiked water samples and by the use of a reference technique (ETAAS). Certified biological materials were also used for the same purpose.     

On-line complexation/preconcentration system for the determination of lead in wine by inductively coupled plasma-atomic emission spectrometry with ultrasonic nebulization

An on-line lead preconcentration and determination system implemented with inductively coupled plasma-atomic emission spectrometry (ICP-AES) with ultrasonic nebulization (USN) in association with flow injection was studied. For the preconcentration of lead, a Pb-quinolin-8-ol complex was formed on-line at pH 6.8 and retained on Amberlite XAD-16 resin. The lead was removed from the microcolumn by countercurrent elution with nitric acid. A total enhancement factor of 225 was obtained with respect to ICP-AES with pneumatic nebulization (15.0 for USN and 15.0 for the column). The detection limit for Pb for the preconcentration of a 10 mL wine sample was 0.15 microg/L. The precision for 10 replicate determinations at a Pb level of 25 microg/L was a relative standard deviation of 2.5%, calculated from the peak heights obtained. The calibration graph obtained by using the preconcentration system for lead was linear with a correlation coefficient of 0.9995 for levels near the detection limit up to > or = 1000 microg/L. The method was successfully applied to the determination of lead in wine samples.     

Determination of trace impurities in some nickel compounds by flame atomic absorption spectrometry after solid phase extraction using Amberlite XAD-16 resin

A simple flame atomic absorption spectrometric (FAAS) procedure for the determination of lead, bismuth, gold, palladium and cadmium as impurities in Raney nickel and nickel oxide was developed using a preconcentration step on an Amberlite XAD-16 resin packed column. Lead, bismuth, gold, palladium and cadmium were quantitatively recovered and separated from a solution containing 1 M HCl and 0.3 M NaI by the column system. Effects of the various parameters such as reagent concentrations, sample volume, matrix effects, etc. have been investigated. Under optimized conditions, the relative standard deviation of the combined method of sample treatment, preconcentration and determination with FAAS (n = 7) is generally lower than 12%. The limit of detection (3s, n = 20) was between 10–270 ng/g. The results were used for separation and preconcentration of five trace elements from nickel matrices. Received: 8 February 2000 / Revised: 31 March 2000 / Accepted: 7 April 2000     

Preconcentration and determination of lead, cadmium and nickel from water samples using a polyethylene glycol dye immobilized on poly(hydroxyethylmethacrylate) microspheres.

A simple and sensitive preconcentration analysis-atomic absorption spectrometric procedure is described for the determination of lead, cadmium and nickel. The method is based upon on-line preconcentration of metal ions on a minicolumn of Cibacron Blue F3-GA immobilized on poly(hydroxyethylmethacrylate), poly(HEMA). The enrichment factors obtained were 42 for lead, 52 for cadmium and 63 for nickel (sample volume 10 mL and sample flow rate 5 mL/min). The relative standard deviations (n = 10), in 10 mL sample solutions containing 100 microg/L Pb(2+), 10 microg/L Cd(2+) and 100 microg/L Ni(2+) were 8.9, 3.7 and 3.5%, respectively. The limits of detection (blank + 3s) (n = 10), were found to be 12.01 microg/L for Pb(2+), 1.34 microg/L for Cd(2+) and 28.73 microg/L for Ni(2+). The accuracy of the system was checked with certified and tap water samples spiked with known amounts of metal ions. No significant difference was found between the achieved results and the certified values.     

Comparison of two sample preconcentration strategies for the sensitivity enhancement of flavonoids found in Chinese herbal medicine in micellar electrokinetic chromatography with UV detection

Two on-column preconcentration techniques named stacking with reverse migrating micelles (SRMM) and anion selective electrokinetic injection and a water plug-sweeping with reverse migrating micelles (ASIW-sweep-RMM) were used and compared for concentration and separation of flavonoids in Chinese herbs using reverse migration micellar electrokinetic chromatography (RM-MEKC). The optimal background electrolyte (BGE) used for separation and preconcentration was a solution composed of 20mM phosphoric acid (H(3)PO(4))-100mM sodium dodecyl sulfate (SDS)-20% (v/v) acetonitrile (ACN) buffer (pH 2.0), the applied voltage was -15kV. To achieve reasonable results of the two techniques, the conditions which affected preconcentration were examined. A comparison of used techniques with normal hydrodynamic injection (5s), concerning enhancement factors and limits of detection (LODs) was presented. Under the optimum stacking conditions, about 27-37- and 45-194-fold improvement in the detection sensitivity was obtained for SRMM and ASIW-sweep-RMM, respectively, compared to usual hydrodynamic sample injection (5s). The LODs (S/N=3) for SRMM and ASIW-sweep-RMM in terms of peak height, can reach down to 1.15 x 10(-2) microg/ml for hesperetin and 2.4 x 10(-3) microg/ml for nobiletin, respectively. Finally, the amounts of the six flavonoids in extract of Fructus aurantii Immaturus were successfully determined using ASIW-sweep-RMM. The six analytes were baseline separated with sample matrix under the optimum ASIW-sweep-RMM conditions and the experimental results showed that preconcentration was well achieved after the dilution of sample solutions.     

On-line complexation/cloud point preconcentration for the sensitive determination of dysprosium in urine by flow injection inductively coupled plasma–optical emission spectrometry

An on-line dysprosium preconcentration and determination system based on the hyphenation of cloud point extraction (CPE) to flow injection analysis (FIA) associated with ICP-OES was studied. For the preconcentration of dysprosium, a Dy(III)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex was formed on-line at pH 9.22 in the presence of nonionic micelles of PONPE-7.5. The micellar system containing the complex was thermostated at 30 degrees C in order to promote phase separation, and the surfactant-rich phase was retained in a microcolumn packed with cotton at pH 9.2. The surfactant-rich phase was eluted with 4 mol L(-1) nitric acid at a flow rate of 1.5 mL min(-1), directly in the nebulizer of the plasma. An enhancement factor of 50 was obtained for the preconcentration of 50 mL of sample solution. The detection limit value for the preconcentration of 50 mL of aqueous solution of Dy was 0.03 microg L(-1). The precision for 10 replicate determinations at the 2.0 microg L(-1)Dy level was 2.2% relative standard deviation (RSD), calculated from the peak heights obtained. The calibration graph using the preconcentration system for dysprosium was linear with a correlation coefficient of 0.9994 at levels near the detection limits up to at least 100 microg L(-1). The method was successfully applied to the determination of dysprosium in urine.