Harnessing carboxymethyl cellulose and Moringa oleifera seed husks for sustainable treatment of a multi-metal real waste.

This study aimed to evaluate effective treatment strategies for laboratory waste with an initial pH of 1.0, containing Cr6+, Mn2+, Co2+, Fe3+, Ni2+, Cu2+, Zn2+, Sr2+, Hg2+, and Pb2+ ions, focusing on flocculation, precipitation, and adsorption techniques. The study utilized microparticles derived from Moringa oleifera seed husks (MS), cryogels of carboxymethyl cellulose (CMC), and hybrid cryogels combining CMC and MS (CMC-MS25 and CMC-MS50) as adsorbents. The optimal strategy involved raising the pH to 7 using NH4OH, leading to the partial precipitation of metal ions. The remaining supernatant was then passed through columns packed with the aforementioned adsorbents. Utilizing CMC-MS25 and CMC-MS50 adsorbents resulted in the simultaneous removal of over 90% of the targeted metal ions. The adsorption of Cu2+ ions onto the adsorbents was facilitated by electrostatic interactions between Cu2+ ions and carboxylate groups, as well as Cu-OH chelation, as confirmed by X-ray photoelectron spectroscopy. Under optimized conditions, the fixed-bed column adsorption capacity was determined as 88.2 mg g-1. The CMC-MS25 adsorbents proved reusable at least 5 times, with the recovered Cu2+ ions potentially suitable for other processes. The scalability and feasibility of producing these novel adsorbents suggest a promising, cost-effective solution for treating complex matrices and recovering high-value metals, as copper.

Unraveling the mysterious role of palladium in Feigl bis(dimethylglyoximate)nickel(II) spot tests by means of confocal Raman microscopy.

The acid protection effect promoted by traces of PdCl(2) in [Ni(dmgH)(2)] spot tests was elucidated from confocal Raman microscopy imaging, which revealed the formation of protecting layers of [Pd(dmgH)(2)] closing the extremities of the [Ni(dmgH)(2)] filaments.

Hydroponic growth test of maize sprouts to evaluate As, Cd, Cr and Pb translocation from mineral fertilizer and As and Cr speciation.

The present study proposes a maize sprouts hydroponic growth model to evaluate the As, Cd, Cr and Pb translocation from multinutrient fertilizer and to do speciation of As and Cr in this fertilizer and As in parts of plant in order to predict their phytoavailability. X-ray absorption near edge structure (XANES) was employed to speciate As and Cr directly on fertilizer solid sample. Arsenate (AsV) and a solid solution of FeCrO3 were the major species identified in the samples. The sprouts were hydroponically cultivated in water, fertilizer slurry and fertilizer extract media. Concentrations of As, Cd and Pb measured on leaves of maize sprouts ranged from 0.061 to 0.31 mg kg-1, whereas Cr was not translocated to the aerial parts of sprouts. High performance liquid chromatographic with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) analysis was used to determine As speciation in maize sprouts, as well as in the fertilizer extracts and slurries. Arsenate was the only species identified in the initial fertilizer extract and this information is in agreement with the XANES results. However, the reduction of arsenate to arsenite was observed in extracts and slurries collected after sprout growth, probably due to the action of exudates secreted by plant roots. Arsenite was the predominant species identified in sprouts, the high phosphate concentration in the medium may have contributed to reduce arsenate phytoavailability.

Non-chromatographic method for separation and determination of Fe, Ni and V porphyrins in crude oil.

A method combining ultracentrifugation and cloud point extraction is proposed for the separation and determination of Fe, Ni and V porphyrins in crude oil. An emulsion containing about 200 mg of crude oil, 6% (w v-1) of Triton X-100™, 1.6% (v v-1) of chloroform and 0.1 mol L-1 of HCl was prepared. An aliquot (1.5 mL) of this emulsion was ultracentrifuged to separate the crude oil heavy fraction (asphaltene and particulate matter) and inorganic species, organometallic compounds and porphyrins of Fe, Ni and V remained in the supernatant. Another aliquot (1.5 mL) was heated up to 90 °C for 5 min to separate the porphyrins, both heavy and light organics compounds, light organic and particulate matter by cloud point extraction, only the inorganic and ionic organometallic compounds species remained in the aqueous phase. The supernatant and aqueous phase were analysed by simultaneous graphite furnace atomic absorption spectrometry. The concentration determined in the supernatant was subtracted from that determined in the aqueous phase, providing the quantification of Fe, Ni and V porphyrin in the crude sample. The accuracy of the proposed method was checked using SARA reference method. The elemental determinations in the fractions obtained using the proposed method and the comparison by SARA showed an absence of Fe in the aromatics and resins fractions. The results showed that about 40% of Ni and 70% of V in the crude oil sample are bounded to porphyrins.

Feasibility of using solid sampling graphite furnace atomic absorption spectrometry for preparation of spiked filter papers with Cu and Zn as standards for direct solid analysis.

An approach was developed for the preparation of cryogenic ground spiked filter papers with Cu and Zn for use as synthetic calibrating standards for direct solid microanalysis. Solid sampling graphite furnace atomic absorption spectrometry was used to evaluate the microhomogeneity and to check the applicability of the synthetic calibrating standards for the direct determination of Cu and Zn in vegetable certified reference materials. The found concentrations presented no statistical differences at the 95% confidence level. The homogeneity factors ranged from 2.7 to 4.2 for Cu and from 6.4 to 11.5 for Zn.

Analytical Capabilities of the Community Bureau of Reference Protocol to Estimate the Mobility of Nutrients and Toxic Elements from Mineral Fertilizer.

The sequential extraction procedure of the Community Bureau of Reference (BCR) was applied to investigate the mobility of potentially toxic elements (As, Cd, Cr, and Pb) and nutrients (P, Ca, Mg, Cu, Fe, Mn, and Zn) in a multinutrient mineral fertilizer based on phosphate rocks supplemented with 10% (w w-1) micronutrient mixture (raw material used as a micronutrient source). For both samples, As and Cd were more mobile, whereas Cr remained in the solid residue. A higher mobility of Pb was observed in the micronutrient mixture; however, the high concentration of P (8.3% w w-1) in the fertilizer could have decreased Pb mobility as a result of Pb3(PO4)2 formation. The nutrients had great mobility, except Fe, which remained almost totally in the residual fraction in both samples. X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy analyses of solid residues showed that the ways in which elements were distributed in the sample particles could affect their mobility.

Hydroxypropyl Methylcellulose Sponges for the Adsorption of Estrogenic Pollutant.

Hydroxypropyl methylcellulose (HPMC) E4M chains are crosslinked with citric acid and ethylenediaminetetraacetic acid (EDTA), resulting in adsorbent sponges (SpE4M), which are impregnated with magnetic nanoparticles (SpE4M-mag) for the adsorption of 17 α-ethinyl estradiol (EE). The characterization of SpE4M and SpE4M-mag characterization includes X-ray microcomputer tomography (Micro-CT), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) vibrational spectroscopy, elemental analysis, inductively coupled plasma optical emission spectrometry (ICP-OES), and X-ray diffraction (XRD). SpE4M and SpE4M-mag present porosities of 72±6 % and 80±7 %, respectively, and outstanding stability in water, in the pH range 4 to 8, and in alcohols, alkanes, and acetone. The compressive moduli of SpE4M and SpE4M-mag amount to 2.75 and 4.37 MPa, respectively. The adsorption of 17 α-ethinyl estradiol (EE), an estrogenic pollutant, on SpE4M and SpE4M-mag follows the pseudo-first-order kinetic model. The EE removal capacity by SpE4M is 78±5 %, which is twice that presented by SpE4M-mag. The new sponges are recovered successfully either by flotation or by an external magnet, and can be recycled five times keeping 80 % of their initial removal capacity after the fifth cycle, disclosing their potential for environmental remediation.

Evaluation of calcium alginate beads for Ce, La and Nd preconcentration from groundwater prior to ICP OES analysis.

Analytical methods for the determination of rare earth elements (REE) in natural waters by plasma spectrochemical techniques often require sample preparation procedures for analytes preconcentration as well as for removing matrix constituents, that may interfere on the analytical measurements. In the present work, calcium alginate (CA) beads were used for the first time aiming at Ce, La and Nd preconcentration from groundwater samples for further determination by inductively coupled plasma optical emission spectrometry (ICP OES). Test samples were analyzed in batch mode by transferring a 40mL test portion (pH=5±0.2) into a 50mL polyethylene flask containing 125mg CA beads. After 15min contact, the analytes were quantitatively extracted from the loaded CA beads with 2.0mL of 1.0molL-1 HCl solution for further determination by ICP OES, using Ce (II) 456.236, La (II) 379.478 and Nd (II) 430.358nm emission lines. The proposed approach is a reliable alternative for REE single-stage preconcentration from aqueous samples, as it provided accurate results based on the addition and recovery analysis of groundwater. The results obtained by the proposed method were also compared with those from reference method based on inductively coupled plasma mass spectrometry (ICP-MS) and no significant differences were observed after applying the Student's t-test at 95% confidence level.

Multielement determination of cadmium and lead in urine by simultaneous electrothermal atomic absorption spectrometry with an end-capped graphite tube.

A method for the multielement determination of cadmium and lead in urine is proposed by simultaneous electrothermal atomic absorption spectrometry (SIMAAS) with an end-capped transversely heated graphite atomizer (EC-THGA). The best conditions for cadmium and lead determination were obtained in the presence of NH4H2PO4 as a chemical modifier, using 500 degrees C and 1800 degrees C as the pyrolysis and atomization temperatures, respectively. Urine samples were diluted 1 + 4 directly in autosampler cups with a mixture of 0.125% (w/v) Triton X-100 + 2.5% (v/v) HNO3 + 0.31% (w/v) NH4H2PO4. The optimized heating program was carried out in 57 s, and the instrument calibration was done with aqueous reference solutions. The use of EC-THGA increased the sensitivity of cadmium and lead by 14% and 25%, respectively. The detection limits (n = 20, 3delta) were 0.03 microg L(-1) (0.36 pg) for cadmium and 0.57 microg L(-1) (6.8 pg) for lead. The performance of EC-THGA was acceptable up to 500 heating cycles. The reliability of the entire procedure was checked with the analysis of a lyophilized urine certified reference material. The found concentrations were in agreement with the recommended values (95% confidence level).

Fast emulsion-based method for simultaneous determination of Co, Cu, Pb and Se in crude oil, gasoline and diesel by graphite furnace atomic absorption spectrometry.

A method for the simultaneous determination of Co, Cu, Pb and Se in crude oil, gasoline and diesel samples using emulsion-based sampling and GF AAS is proposed. 400mg of sample was weighted in volumetric flask following the sequential addition of 125 µL of hexane and 7.5 mL of Triton X-100(®) (20% mv(-1)). Subsequently, the mixture was stirred in ultrasonic bath, during 30 min, before dilution to 25 mL with deionized water. Aliquots of 20 µL of reference solution or sample emulsion were co-injected into the graphite tube with 10 µL of 2 g L(-1) Pd(NO3)2. The pyrolysis and atomization temperatures were 1300°C and 2250°C, respectively. The limits of detection (n=10, 3σ) and characteristic masses were 0.02 µg g(-1) (0.32 µg L(-1)) and 18 pg for Co, 0.03 µg g(-1) (0.48 µg L(-1)) and 15 pg for Cu, 0.04 µg g(-1) (0.64 µg L(-1)) and 48 pg for Pb, and 0.11 µg g(-1) (1.76 µg L(-1)) and 47 pg for Se. The reliabilities of the proposed method for Co and Se were checked by SRM(®) 1634c Residual Oil analysis. The found values are in accordance to the SRM at 95% confidence level (Student's t-test). Each sample was spiked with 0.18 µg g(-1) of Co, Cu, Pb and Se and the recoveries varied from 92% to 116% for Co, 83% to 117% for Cu, 72% to 117% for Pb, and 82% to 122% for Se.

In vivo bioavailability of selenium in enriched Pleurotus ostreatus mushrooms.

The in vivo bioavailability of Se was investigated in enriched Pleurotus ostreatus mushrooms. A bioavailability study was performed using 64 Wistar male rats separated in 8 groups and fed with different diets: without Se, with mushrooms without Se, with enriched mushrooms containing 0.15, 0.30 or 0.45 mg kg(-1) Se and a normal diet containing 0.15 mg kg(-1) of Se using sodium selenate. The experiment was performed in two periods: depletion (14 days) and repletion (21 days), according to the Association of Official Analytical Chemists. After five weeks, the rats were sacrificed under carbon dioxide, and blood was drawn by heart puncture. Blood plasma was separated by centrifugation. The total Se concentration in the plasma of rats fed with enriched mushrooms was higher than in rats fed with a normal diet containing sodium selenate. The plasma protein profiles were obtained using size exclusion chromatography (SEC) and UV detectors. Aliquots of effluents (0.5 mL per minute) were collected throughout in the end of the chromatographic column. However, Se was determined by graphite furnace atomic absorption spectrometry (GF AAS) only in the aliquots where proteins were detected by SEC-UV. The plasma protein profile of rats fed with different diets was similar. The highest Se concentration was observed in a peptide presenting 8 kDa. Furthermore, the higher Se concentration in this peptide was obtained for rats fed with a diet using enriched mushrooms (7 µg L(-1) Se) compared to other diets (2-5 µg L(-1) Se). These results showed that Se-enriched mushrooms can be considered as an alternative Se food source for humans, due to their high bioavailability.

Surface dental enamel lead levels and antisocial behavior in Brazilian adolescents.

Lead poisoning has been reportedly linked to a high risk of learning disabilities, aggression and criminal offenses. To study the association between lead exposure and antisocial/delinquent behavior, a cross-sectional study was conducted with 173 Brazilian youths aged 14-18 and their parents (n=93), living in impoverished neighborhoods of Bauru-SP, with high criminality indices. Self-Reported Delinquency (SRD) and Child Behavior Checklist (CBCL) questionnaires were used to evaluate delinquent/antisocial behavior. Body lead burdens were evaluated in surface dental enamel acid microbiopsies. The dental enamel lead levels (DELL) were quantified by graphite furnace atomic absorption spectrometry (GFAAS) and phosphorus content was measured using inductively coupled plasma optical emission spectrometry (ICP-OES). Logistic regression was used to identify associations between DELL and each scale defined by CBCL and SRD scores. Odd ratios adjusted for familial and social covariates, considering a group of youths exposed to high lead levels (>or=75 percentile), indicated that high DELL is associated with increased risk of exceeding the clinical score for somatic complaints, social problems, rule-breaking behavior and externalizing problems (CI 95%). High DELL was not found to be associated with elevated SRD scores. In conclusion, our data support the hypothesis that high-level lead exposure can trigger antisocial behavior, which calls for public policies to prevent lead poisoning.

Cloud point extraction to avoid interferences by structured background on determination in plant materials by FAAS.

An analytical procedure based on microwave-assisted digestion with diluted acid and a double cloud point extraction is proposed for nickel determination in plant materials by flame atomic absorption spectrometry. Extraction in micellar medium was successfully applied for sample clean up, aiming to remove organic species containing phosphorous that caused spectral interferences by structured background attributed to the formation of PO species in the flame. Cloud point extraction of nickel complexes formed with 1,2-thiazolylazo-2-naphthol was explored for pre-concentration, with enrichment factor estimated as 30, detection limit of 5 µg L-1 (99.7% confidence level) and linear response up to 80 µg L-1. The accuracy of the procedure was evaluated by nickel determinations in reference materials and the results agreed with the certified values at the 95% confidence level.

Biomonitoring method for the simultaneous determination of cadmium and lead in whole blood by electrothermal atomic absorption spectrometry for assessment of environmental exposure.

The aim of this work is to propose a biomonitoring method for the simultaneous determination of Cd and Pb in whole blood by simultaneous electrothermal atomic absorption spectrometry for assessment of environmental levels. A volume of 200 microL of whole blood was diluted in 500 microL of 0.2% (wv(-1)) Triton) X-100+2.0% (vv(-1)) HNO3. Trichloroacetic acid was added for protein precipitation and the supernatant analyzed. A mixture of 250 microg W+200 microg Rh as permanent and 2.0% (wv(-1)) NH4H2PO4 as co-injected modifiers were used. Characteristic masses and limits of detections (n=20, 3s) for Cd and Pb were 1.26 and 33 pg and 0.026 microg L(-1) and 0.65 microg L(-1), respectively. Repeatability ranged from 1.8 to 6.8% for Cd and 1.2 to 1.7% for Pb. The trueness of method was checked by the analysis of three Reference Materials: Lyphocheck Whole Blood Metals Control level 1 and Seronorm Trace Elements in Whole Blood levels 1 and 2. The found concentrations presented no statistical differences at the 95% confidence level. Blood samples from 40 volunteers without occupational exposure were analyzed and the concentrations ranged from 0.13 to 0.71 microg L(-1) (0.32+/-0.19 microg L(-1)) for Cd and 9.3 to 56.7 microg L(-1) (25.1+/-10.8 microgL(-1)) for Pb.

Combination of ultrasonic extraction and stripping analysis: an effective and reliable way for the determination of Cu and Pb in lubricating oils.

The determination of metals in lubricating oil has been used as an important way to prevent components failures, to provide environmental information and in some cases, to identify adulteration. In this work, an effective and simple procedure is proposed for Cu and Pb determination in lubricating oils. An ultrasonic bath was employed for extraction of these elements from oil samples in a mixture 1:1 (v/v) of concentrated HCl and H(2)O(2). A very efficient extraction of Cu and Pb (approximately 100%) was attained after 30 min of ultrasound, allowing the simultaneous determination of both metals using square-wave anodic stripping voltammetry at thin-film gold electrodes. The extraction procedure was performed in 4 mL polypropylene closed vessels and dozens of samples could be treated simultaneously in the same ultrasonic bath. The regions of the ultrasonic bath, where the maximum efficiency of extraction was attained were evaluated. Over the optimized region, 30 samples can be treated simultaneously. Used lubricating oils from automotive engines were analyzed by using the optimized extraction procedure.

Cobalt as internal standard for arsenic and selenium determination in urine by simultaneous atomic absorption spectrometry.

The effectiveness of internal standardization for simultaneous atomic absorption spectrometry (SIMAAS) was investigated for As and Se determination in urine. Co and Sn were selected as internal standard (IS) candidates based on the evaluation of some physico-chemical parameters related to the atomization. Correlation graphs, plotted from the normalized absorbance signals (n=20) of internal standard (axis y) versus analyte (axis x), precision, and accuracy of the analytical results were the supportive parameters to choose Co as the most appropriate IS. The urine samples were diluted 1+2 to 1.0% (v/v) HNO(3)+80mugL(-1) Co(2+). The mixture 20mug Pd+3mug Mg was used as chemical modifier and the optimized temperatures for pyrolysis and atomization steps were 1400 and 2300 degrees C, respectively. The characteristic masses for As (47+/-1pg) and Se (72+/-2pg) were estimated from the analytical curves. The detection limits (n=20, 3delta) were 1.8+/-0.1 and 2.6+/-0.1mugL(-1) for As and Se, respectively. The reliability of the entire procedure was checked with the analysis of certified reference material from Sero AS(Seronormtrade mark Trace Elements in Urine). The obtained results showed the matrix interference disallowed the instrument calibration with aqueous standards. The best analytical condition was achieved when matrix-matched standards were used in combination with Co as IS, which improved the recoveries obtained for As. Under this experimental condition, eight urine samples were analysed and spiked with 10 and 25mugL(-1) As and Se. The mean recoveries were 96+/-6% (10mugL(-1) As), 95+/-6% (25mugL(-1) As), 101+/-7% (10mugL(-1) Se), and 97+/-4% (25mugL(-1) Se).

Iron overload in patients with chronic hepatitis C virus infection: clinical and histological study.

BACKGROUND: Recently it has been found that iron is an important element in the natural history of hepatitis C. Serum markers of iron stores are frequently increased in chronic hepatitis C virus (HCV)-infected carriers but the real impact of the hepatic iron overload is poorly understood. The purpose of the present paper was to determine the prevalence of iron overload and to study the relationship between hepatic iron concentration (HIC) and clinical, biochemical and histological characteristics in chronic HCV-infected carriers. METHODS: Patients presenting with anti-HCV and HCV-RNA were included. Hepatic iron concentration was determined in liver tissue by atomic absorption spectrophotometry. The association between HIC and age, gender, risk factor of transmission, duration of infection, aspartate aminotransferase (AST) and alanine aminotransferase (ALT) levels, iron and serum ferritin, transferrin saturation, HCV-RNA level, grading of inflammatory activity, staging of fibrosis, hepatic steatosis, and stainable iron was analyzed. Statistical analysis included the Mann-Whitney test and a multiple linear regression model. RESULTS: Ninety-six patients (58% male) with a mean age of 44 +/- 10 years were studied. Serum iron, ferritin and transferrin saturation were elevated in 28%, 27% and 12.5% of patients, respectively. Stainable iron was detected in few patients (15.6%). Higher grades of stainable iron (2 and 3) were observed in only 7%. The HIC (>30 mmol/g dry weight) was elevated in five patients (5%). Neither grading nor staging were related to HIC. Higher HIC were observed in male patients (P < 0.001), in patients with elevated serum ferritin (P = 0.001) and in patients with stainable iron (grades 2 and 3; P = 0.001). Multiple linear regression analysis showed that only stainable iron was independently correlated with HIC (P = 0.003). CONCLUSIONS: Iron overload in chronically HCV-infected patients was uncommon and hepatic iron content seemed not to be related to the liver damage process. In the eventuality of iron overload, histochemical liver iron is a useful marker to estimate HIC.

Simultaneous determination of manganese and selenium in serum by electrothermal atomic absorption spectrometry.

A method for determination of manganese and selenium in serum by simultaneous atomic absorption spectrometry (SIMAAS) is proposed. The samples (30 mul) were diluted (1+3) to 1.0% v/v HNO(3)+0.10% w/v Triton X-100 directly in the autosampler cups. A total of 20 mug Pd+10 mug Mg(NO(3))(2) was used as chemical modifier. The pyrolysis and atomization temperatures for the simultaneous heating program were 1200 and 2300 degrees C, respectively. The addition of an oxidant mixture (15% w/w H(2)O(2)+1.0% v/v HNO(3)) and the inclusion of a low temperature pyrolysis step (400 degrees C) attenuated the build-up of carbonaceous residues onto the integrated platform. An aliquot of 15 mul of the reference or sample solution was introduced into the graphite tube and heated at 80 degrees C; subsequently, 10 mul of oxidant mixture+10 mul of chemical modifier was introduced over that aliquot and the remaining heating program steps were executed. This strategy allowed at least 250 heating cycles for each THGA tube without analytical signal deterioration. The characteristic masses for manganese (6 pg) and selenium (46 pg) were estimated from the analytical curves. The detection limits were 6.5 pg (n=20, 3delta) for manganese and 50 pg (n=20, 3delta) for selenium. The reliability of the entire procedure was checked with the analysis of serum from Seronormtrade mark Trace Elements in Serum (Sero AS) and by addition and recovery tests (97+/-9% for manganese and 96+/-7% for selenium) using five serum samples.

Use of the internal standardization for difficult sampling by graphite furnace atomic absorption spectrometry.

This work shows the potentiality of As as internal standard to compensate errors from sampling of sparkling drinking water samples in the determination of selenium by graphite furnace atomic absorption spectrometry. The mixture Pd(NO(3))(2)/Mg(NO(3))(2) was used as chemical modifier. All samples and reference solutions were automatically spiked with 500mugl(-1) As and 0.2% (v/v) HNO(3) by the autosampler, eliminating the need for manual dilutions. For 10mul dispensed sample into the graphite tube, a good correlation (r=0.9996) was obtained between the ratio of analyte absorbance by the internal standard absorbance and the analyte concentrations. The relative standard deviations (R.S.D.) of measurements varied from 0.05 to 2% and from 1.9 to 5% (n=12) with and without internal standardization, respectively. The limit of detection (LD) based on integrated absorbance was 3.0mugl(-1) Se. Recoveries in the 94-109% range for Se spiked samples were obtained. Internal standardization (IS) improved the repeatability of measurements and increased the lifetime of the graphite tube in ca. 15%.

Evaluation and application of bismuth as an internal standard for the determination of lead in wines by simultaneous electrothermal atomic absorption spectrometry.

A method for the direct determination of Pb in wines by simultaneous multi-element atomic absorption spectrometry (SIMAAS) using a transversely heated graphite atomizer, Zeeman-effect background corrector and internal standardization is proposed. Bismuth was used as an internal standard and Pd(NO3)2 plus Mg(NO3)2 as chemical modifier to stabilize both the analyte and the internal standard. The implementation of two pyrolysis steps avoided any build-up of carbonaceous residues on the graphite platform. All diluted samples (1 + 1 v/v) in 0.2% v/v HNO3 and reference solutions (5.0-50 microg l(-1) Pb in 0.2% v/v HNO3) were spiked with 25 microg l(-1) Bi. For a 20 microl aliquot dispensed into the graphite tube, a good correlation (r = 0.9997) was obtained between the ratio of the analyte signal to the internal standard signal and the analyte concentration of the reference solutions. The electrothermal behaviour of Pb and Bi in red, white and rosé wines were compared. In addition, absorbance variations due to changes in experimental conditions, such as atomizer temperature, integration time, injected sample volume, radiation beam intensity, graphite tube surface, dilution and sample composition, were minimized by using Bi as internal standard. Relative standard deviations of measurements based on integrated absorbance varied from 0.1 to 3.4% and from 0.5 to 7.3% (n = 12) with and without internal standard correction, respectively. Good recoveries (91-104%) for Pb spikes were obtained. The characteristic mass was 45 pg Pb and the limit of detection based on integrated absorbance was 0.9 microg l(-1) Pb. Internal standardization increased the lifetime of the tube by 25%. Direct determinations of Pb in wines with and without internal standardization approaches were in agreement at the 95% confidence level. The repeatability and the tube lifetime were improved when using Bi as internal standard. The improvement in accuracy using an internal standard was only observed when the analytical results were affected by errors.