New developments in flow injection separation and preconcentration techniques for electrothermal atomic absorption spectrometry

Flow injection (FI) on-line separation and preconcentration systems for electrothermal atomic absorption spectrometry (ETAAS) are reviewed, highlighting the main developments in the field since 1990 and work achieved in the authors laboratory. These include developments in on-line preconcentration systems based on column techniques, solvent extraction, coprecipitation and hydride sequestration. Advantages, limitations and potentials of the FI-ETAAS combination are discussed.     

New developments in flow injection separation and preconcentration techniques for electrothermal atomic absorption spectrometry

Flow injection (FI) on-line separation and preconcentration systems for electrothermal atomic absorption spectrometry (ETAAS) are reviewed, highlighting the main developments in the field since 1990 and work achieved in the authors' laboratory. These include developments in on-line preconcentration systems based on column techniques, solvent extraction, coprecipitation and hydride sequestration. Advantages, limitations and potentials of the FI-ETAAS combination are discussed.     

Trends and potentials in flow injection on-line separation and preconcentration techniques for electrothermal atomic absorption spectrometry

Recent progress in flow injection on-line separation and preconcentration techniques for electrothermal atomic absorption spectrometry (ETAAS) are reviewed, stressing the advancements made within the past 2 or 3 years. Important trends and potentials for future development are discussed, including the use of air-transport and air-segmentation in on-line separation systems, the use of knotted reactors as a sorption medium, and other designs for on-line coprecipitation and solvent extraction systems to improve the robustness and efficiency of on-line separation systems for ETAAS.     

Determination of selenium in small volumes of blood plasma and serum by electrothermal atomic absorption spectrometry

A graphite-furnace atomic absorption spectrometric method is described for the determination of selenium in blood plasma and serum. Samples are diluted (1 + 9) with a solution containing nickel and nitric acid and measured by a standard additions method. Repeatability for a serum sample containing 87 μg Se l^-1 was 4.4%. The mean recovery of selenium(IV) from a human protein solution was 97.5%. The method was further tested in an interlaboratory comparison study. The standard additions procedure requires a sample volume of 200 μl and a total time of about 7.5 min. A secondary calibration graph can be used, however, resulting in increased throughput up to 13 samples per hour, and a decrease in the sample volume needed to 100 μl.     

Utilization of electrodeposition for electrothermal atomic absorption spectrometry determination of gold

Gold was determined by electrothermal atomic absorption spectrometry after electrochemical preconcentration on the graphite ridge probe used as a working electrode and sample support. The probe surface was electrochemically modified with Pd, Re and the mixture of both. The electrolysis of gold was performed under galvanostatic control at 0.5 mA. Maximum pyrolysis temperature for the probe surface modified with Pd was 1200 °C, with Re 1300 °C. The relative standard deviation for the determination of 2 μg l^− 1 Au was not higher than 5.6% (n = 8) for 2 min electrodeposition. The sensitivity of gold determination was reproducible for 300 electrodeposition and atomization cycles. When the probe surface was modified with a mixture of Pd and Re the detection limit was 31 ng l^− 1 for 2 min electrodeposition, 3.7 ng l^− 1 for 30 min, 1.5 ng l^− 1 for 1 h and 0.4 ng l^− 1 for 4 h electrodeposition, respectively. The procedure was applied to the determination of gold in river water samples. The relative standard deviation for the determination of 2.5 ng l^− 1 Au at 4 h electrodeposition time at 0.5 mA was 7.5%.     

Separation and preconcentration by flow injection coupled to tungsten coil electrothermal atomic absorption spectrometry

A flow injection system coupled to a tungsten coil electrothermal atomizer has been developed for on-line separation and preconcentration, using lead as a model element. The system utilizes three-way solenoid valves for sampling, buffering, washing and reconditioning solution management, and the resin column is inserted in the tip of the autosampler arm of a Varian GTA-96. The solenoid valves and tungsten coil power supply were controlled by a computer program written in Visual Basic, interfaced with the built-in Varian software. The system performance was tested by loading the resin column with the sample flowing at 3 ml min⁻¹ for 60 s. Elution was performed automatically by sampling 20 μl of the eluent from a sample cup of the autosampler, and this aliquot was delivered into a 150 W tungsten coil. With Chelex-100 resin, the separation of concomitants was tested with lead in the presence of as much as 1000 mg l⁻¹ of Ca, Mg, Na or K. The model system presented an enrichment factor of 64 at a sampling rate of 30 samples per hour.     

Metal speciation by coupled in situ graphite furnace electrodeposition and electrothermal atomic absorption spectrometry

The technique of coupled in situ electrodeposition–electrothermal atomic absorption spectrometry (ED–ETAAS) is applied to the analytes Bi, Pb, Ni and Cu. Bi, Pb, Ni and Cu are deposited quantitatively from their EDTA complexes at E_cell=1.75, 2.0, 3.0 and 2.5 V, respectively (E_cell=E_anode−E_cathode+iR). By varying the cell potential, selective reduction of free metal ions could be achieved in the presence of the EDTA complexes. For Bi³⁺ and Pb²⁺ this utilised the voltage windows E_cell=0.6–1.0 and 1.8–2.0 V, respectively. For Ni, deposition at E_cell=1.7–2.0 V achieved substantial, but not complete, differentiation between Ni²⁺ (ca. 90–100% deposition) and Ni(EDTA)²⁻ (ca. 12–20% deposition). An adequate voltage window was not obtained for Cu. The ability of ED–ETAAS to differentiate between electrochemically labile and inert species was demonstrated by application of both ED–ETAAS and anodic stripping voltammetry to the time-dependent speciation of Pb in freshly mixed Pb²⁺–NaCl media. Application to natural water samples is complicated by adsorption of natural organic matter to the graphite cathode.     

Ion chromatographic preconcentration of Cu and Cd from ultra-high-purity water and determination by electrothermal atomic absorption spectrometry

A method based on preconcentration of Cu and Cd from ultra-high-purity water by ion chromatography (IC) and determination by electrothermal atomic absorption spectrometry is described. A small low-capacity ion-exchange concentrator Dionex HPIC-CG5 and mobile phase of 3 mM pyridine-2,6-dicarboxylic acid (PDCA) are used. Water samples are loaded onto the preconcentration column at a flow-rate ranging from 1 to 3.5 ml min(-1). Large sample volumes (up to 200 ml) can be loaded onto the concentrator without losing metal ions. Elution is carried out in the reverse direction of sample loading and the volumes of effluent are as small as 0.150 and 0.200 ml for copper and cadmium, respectively. Under these conditions the preconcentrated ions coelute. The detection limits, based on the Hubaux-Vos method, for Cu using a 1300-fold preconcentration in the IC step was found to be 1 pg ml(-1), and was limited due to impurity in PDCA, while the detection limit found for Cd using a 1000-fold preconcentration was 0.02 pg ml(-1). Ultra-high-purity water produced by a Millipore system is successfully analysed by the proposed method and the content of Cu and Cd are found to lie in the range 1-10 pg ml(-1).     

Selective preconcentration and determination of tributyltin in fresh water by electrothermal atomic absorption spectrometry

A rapid and simple method for separation and determination of tributyltin (TBT) in mineral and tap water is described. The procedure is based on the selective retention of TBT by a chelating resin, Amberlite XAD-2 impregnated with tropolone. The addition of 0.8% sulfuric acid to the water sample leads to the retention of TBT by the resin while monobutyltin (MBT), dibutyltin (DBT) and inorganic tin remain in solution. TBT is eluted with methyl isobutyl ketone (MIBK) obtaining a preconcentration factor of 80. Tin concentration is determined by ETAAS using zirconium coated tubes. Multi-injection and hot injection techniques are used in order to enhance the sensitivity of the method. A detection limit of 14.4 ng L(-1) is achieved with recoveries near to 100%. The procedure has been successfully applied to TBT determination in various fresh water samples.     

On-line ion-exchange preconcentration and determination of traces of platinum by electrothermal atomic absorption spectrometry

A method to determine trace amounts of platinum in different samples based on electrothermal atomic absorption spectrometry is described. The preconcentration step is performed on a chelating resin microcolumn [1,5-bis(2-pyridyl)-3-sulfophenyl methylene thiocarbonohydrazide (PSTH) immobilized on an anion-exchange resin (Dowex 1x8-200)] placed in the autosampler arm. The combination of a peristaltic pump for sample loading and the atomic absorption spectrometer pumps for elution through a selection valve simplifies the hardware. The peristaltic pump and the selection valve are easily controlled electronically with two switches placed in the autosampler, which are activated when the autosampler arm is down. Thus, the process is fully automated without any modification of the software of the atomic absorption spectrometer. Under the optimum conditions with a 60-s preconcentration time, a sample flow rate of 2.4 mL min(-1), and an injection volume of eluent of 40 microL, a linear calibration graph was obtained in the range 0-100 ng mL(-1). The enrichment factor was 14. The detection limit under these conditions is 1 ng mL(-1), and the relative standard deviation (RSD) is 1.6% for 10 ng mL(-1) of Pt. The method has been applied to the determination of platinum in catalyst, vegetation, soil, and natural water samples. The results showed good agreement with the certified value and the recoveries of Pt added to samples were 98-105%.     

Evaluation of in situ electrodeposition technique in electrothermal atomic absorption spectrometry

Conventional electrothermal atomic absorption spectrometric (ETAAS) equipment was extensively modified to enable automated in situ electrodeposition. The original autosampler injection Teflon capillary was replaced by a composite Pt/Teflon capillary which served as an anode in the electrodeposition circuit. Incorporation of a peristaltic pump and of a three-way solenoid under computer control into the sample dispenser circuit provided all necessary steps for automated electrodeposition-ETAAS determination. The automated sequence controlled addition of Pd modifier and of the analyte, electrolysis, withdrawal of spent electrolyte, rinsing, drying and atomization. Performance of the system was evaluated by analyzing Pb in 3% m/v NaCl. Optimization using factorial design yielded 3sigma detection limit of 20 pg Pb and reproducibility of 1.0-1.4% (for constant current electrodeposition), these values being superior to the results of conventional ETAAS of Pb in 0.5% m/v NaCl. Sensitivity of Pb determination is not affected by NaCl, NaOH, NaNO3 and NH4H2PO4, up to 4.6% m/v, demonstrating efficient matrix removal in the electrodeposition step.     

On-line bi-directional electrostacking for As speciation/preconcentration using electrothermal atomic absorption spectrometry

A method using bi-directional electrostacking (BDES) in a flow system is presented for As preconcentration and speciation analysis. Some parameters such as electrostacking time and applied voltage, support buffers and their concentrations were investigated. Boric acid plus sodium hydroxide at 0.1 mol/l concentration was selected as support buffer to improve the pre-concentration factor (PF) for As(V). An analytical range from 2.0 to 50.0 μg l⁻¹, and 0.35 μg l⁻¹ as limit of detection, when applied 750 V for 20 min, were achieved. Under these conditions, a pre-concentration factor of 4.8 was obtained. The proposed method was applied to determine As(V) in mineral water and natural water samples (river, fountain and gold mine) from Ouro Preto city. Recoveries from 93.5 to 106.4% were achieved at 10 μg l⁻¹ added As level (R.S.D.s between 3 and 7%). Potassium permanganate (10 mg l⁻¹) was used for oxidising As species in order to determine total As, being established the concentration of As(III) from the difference between total As and As(V).     

A new furnace design for constant temperature electrothermal atomic absorption spectroscopy

A new concept is described for the production of atomic vapour with a constant temperature graphite furnace. Samples are manually or automatically dosed into a graphite cup which is fastened tightly to an aperture of a graphite tube. For atomization, the tube is heated to a preselected temperature followed by heating of the cup by means of a separate power supply. Experimental results are given to characterize the performance of the furnace with regard to sensitivity, non-specific absorption and interference effects. Possible applications of the system are discussed.     

Analyte stabilization by electrodeposited palladium modifier for electrothermal atomic absorption spectrometry: characterization by scanning electron microscopy and anodic stripping voltammetry

In electrothermal atomic absorption spectroscopy (ETAAS) effective stabilization of analytes can be achieved by an initial in situ electrodeposition of 0.2 mug of Pd. This amount of Pd is on average a factor of 50 lower than that typically used for conventional chemical modification. The surface features of this modifier have been characterized by scanning electron microscopy (SEM) measurements on sectioned pyrolytic graphite furnaces and contrasted with those for modifier produced from thermally reduced Pd salts. Electrodeposition produces a uniform array of Pd domains stretching approximately 2 mm from the centrally positioned Pt/Ir anode (which doubles as the autosampler sample delivery tube). In contrast, thermally reduced Pd salts produce a modifier which concentrates in domains near the drying edge of the modifier solution. Anodic stripping voltammetry (ASV) established that Pb electrodeposited onto Pd-modified pyrolytic graphite affixes to the Pd rather than the graphite. ASV measurements using a basal plane pyrolytic graphite working electrode also established that (i) the stripping potentials for monolayer and multilayer Pb are shifted anodically by 0.16 and 0.18 V, respectively by binding to Pd rather than graphite and (ii) deposition of Pb from dilute acidic medium (1% HNO(3)) leads only to monolayer Pb, in contrast to deposition from acetate buffer (pH 4.0-4.4) which produces predominantly multilayer Pb.     

Selective ion-imprinted polymers for preconcentration and determination of silver in water and hair by electrothermal atomic absorption spectrometry

A new Ag(I)-ion imprinted polymer (IIP) was prepared by formation of 2-(4-hydroxypent-3-en-2-ylideneamine) phenol complex for selective extraction and preconcentration of silver ions. Polymerization was performed with ethylene glycol dimethacrylate as crosslinking monomer and methacrylic acid as functional monomer in the presence of 2,2-azobis(isobutyronitrile) as initiator via bulk polymerization method. The Ag(I)-imprinted polymeric particles were characterized by scanning electron microscopy and infrared spectroscopy. The template silver ion was removed from the polymeric matrix using 2.0 M HNO₃. Optimum pH for maximum sorption was 6.0. Maximum sorbent capacity and enrichment factor for Ag(I) were 12.5 mg/g and 50, respectively. The relative standard deviation and detection limit of the method were evaluated as ±4% and 2.3 ng/L, respectively. The developed IIP has also been tested for preconcentration and recovery of Ag(I) ions from water and hair samples.     

Direct determination of cadmium in urine by electrothermal atomic absorption spectrometry after in situ electrodeposition

Determination of cadmium in urine by ETAAS suffers from severe interferences deteriorating the precision and accuracy of the analysis. Electrodeposition step prior to ETAAS allows to avoid interferences and makes cadmium determination possible even at ultratrace levels. The proposed procedures involve electrolytic deposition of cadmium from acidified urine on previously electrolytically deposited palladium film on a graphite atomizer tube, followed by removal of residual solution, pyrolysis and atomization. Both electrodeposition processes take place in a drop of the respective solution (palladium nitrate modifier and acidified urine, respectively), when Pt/Ir dosing capillary serves as an anode and the graphite tube represents a cathode. The voltage is held at −3.0 V. Matrix removal is then accomplished by withdrawal of the depleted sample solution from the tube (procedure A) or the same but followed by rinsing of the deposit with 0.2 mol l⁻¹ HNO₃ (procedure B). The accuracy of both procedures was verified by recovery test. Detection limits 0.025 and 0.030 μg Cd/l of urine were achieved for A and B procedures, respectively. Both procedures are time consuming. The measurement cycle represents 5 and 7 min for A and B procedures, respectively.     

The determination of platinum in biological materials by electrothermal atomic absorption spectroscopy

Methods for determination of platinum in body tissues and fluids by electrothermal atomic absorption spectroscopy are described. Serum and urine could be analyzed without pretreatment or dilution. Wet and dry ashing techniques for tissue digestion were compared. Dry ashing tissues in a furnace resulted in significant and unexplained losses of analyte, whereas there was complete recovery of platinum added to the tissues when the tissues were wet ashed. The wet ashing technique is fast and convenient and requires minimal sample treatment.     

Determination of heavy metals by electrothermal atomic absorption spectrometry after electrodeposition on a graphite probe

Traces of heavy metals were separated and preconcentrated electrochemically at a controlled potential on the graphite ridge probe. After the electrolysis, the electrode-probe was inserted in the graphite furnace for atomization of metal deposit by an automatic system. Conditions for the electrodeposition, such as pH of solutions, the deposition potential and concentration of electrolyte, were optimized. Detection limits improved with increased time of electrodeposition and were 16 ng l⁻¹ Cu, 1.0 ng l⁻¹ Cd, 6.0 ng l⁻¹ Pb, 64 ng l⁻¹ Ni, 14 ng l⁻¹ Cr (III) and 17 ng l⁻¹ Cr (VI) for a 10-min deposition. This method was applied for the determination of copper, cadmium, lead, nickel and of chromium species in seawater.     

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

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