Pedro V. Oliveira

Peat as a natural solid-phase for copper preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry.

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 molL(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 microgL(-1), with a detection limit estimated as 3 microgL(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n=20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111% range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level.

Determination of chlorine, bromine and iodine in milk samples by ICP-OES

A procedure coupling acid decomposition and precipitation, using inductively coupled plasma optical emission spectrometry (ICP- OES) is proposed for the determination of Cl, Br and I in milk samples. During the mineralization process in closed and open vessels (microwave ovens), anions are precipitated as salts of low solubility products (AgCl, AgBr and AgI). After separation from digestate solution, precipitates are dissolved with ammonia resulting in a 20% v/v solution. The final solution was directly introduced into the ICP-OES without any damage to the sample introduction system and with no severe spectral interference. Three biological reference materials were used to validate the methodology: Non-Fat Milk Powder SRM 1549 from NIST, Skim Milk Powder RM-151 from BCR and Whole Egg Powder RM 8415, also from NIST. The limits of detection (3σb/s) for Cl, Br and I in the solid sample were 30, 40 and 280 µg g−1 for the closed vessel microwave oven, and 15, 20 and 40 µg g−1 for the open vessel microwave oven, respectively. Relative standard deviations, considering five replicates of sample submitted to the proposed methodology, were 1% for Cl and Br, and 2% for I, when a closed vessel microwave was used. The results for Cl were in good agreement with the certified values (90% confidence level). For Br, recoveries ranged from 87 to 104% for closed vessel microwave oven and from 90 to 102% for open vessel microwave oven. As for I, recoveries ranged from 85 to 98% with a closed vessel microwave oven. Accurate results for determinations in certified materials and good recoveries demonstrated the efficiency of the procedure.

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.

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.

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.

Determination of lead in blood by tungsten coil electrothermal atomic absorption spectrometry

Abstract A method for the determination of lead in blood using a tungsten coil atomizer is described. A 100 μl volume of the whole blood sample is transferred to a sampler cup containing 100 μl of water plus 300 μl of 0.25% v/v Triton X-100. After lysis of blood cells, 500 μl of 10% w/v trichloroacetic acid is added for protein precipitation and 10 μl of the supernatant solution is automatically delivered into the tungsten coil. The furnace heating program is implemented in 41 s. It is shown by the paired t -test that there is no significant difference at the 5% probability level between results obtained by the proposed method and by using a transversely heated graphite atomizer with a longitudinal Zeeman background correction. Accuracy is also assessed by employing reference materials. The proposed tungsten coil procedure presents a characteristic mass of 15 pg Pb and a detection limit of 1.9 μg Pb dl −1 .

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.

Surface and gas phase temperatures of a tungsten coil atomizer

Abstract The electrothermal atomization of elements is critically affected by the volatility of the analyte and its compounds, the matrix constituents, the atomizer material and the surface and gas phase temperatures. There are scarce temperature data about the tungsten coil atomizer (TCA). This paper involves measurements of surface and gas phase temperatures of a TCA (Osram 150 W). Three strategies were adopted to assess the surface temperature: electric current measurements in each applied voltage to calculate resistivity and correlation of this latter parameter with temperature; melting points of organic and inorganic compounds in the 120–800 °C range, and optical pyrometer measurements in the 1000–3000 °C range. The first two methods led to at least estimate values and more accurate results were attained with the optical pyrometer. The gas phase temperature was estimated based on the two-line absorption method using tin as thermometric element. The data showed a pronounced difference between surface and gas phase temperatures that can reach values higher than 1000 °C depending on the applied voltage and observation height. Data are discussed considering thermochemical processes in a double layer tungsten coiled filament.

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.

Cu, Fe, Mn and Zn distribution in protein fractions of Brazil-nut, cupuassu seed and coconut pulp by solid-liquid extraction and electrothermal atomic absorption spectrometry

In this work Cu, Fe, Mn and Zn were determined in extracts of Brazil-nut (Bertholletia excelsa), cupuassu (Theobroma grandiflorum) seeds and coconut (Cocos nucifera) pulp, using solid-liquid extraction and electrothermal atomic absorption spectrometry. Different extractant solutions (mixture of methanol and chloroform 1:2 v/v, water, 0.5 mol L-1 NaCl, 70% v/v ethanol, and 0.5 mol L-1 NaOH) were used for extracting lipids, albumins, globulins, prolamins and glutelins, respectively. The protein concentrations determined in Brazil-nut are higher than those observed for cupuassu and coconut pulp. The analysis of lipid fractions reveals high concentations of Fe in Brazil-nut and cupuassu seed and Zn in coconut pulp. For Brazil-nut, these elements are mainly associated to albumin, globulin and glutelin fractions. The same behaviour was not observed for cupuassu seed and coconut pulp. The element concentrations changed in each protein fraction. In general, high concentrations of proteins were determined in NaOH extractants. On the other hand, low concentration of Cu, Fe, Mn and Zn were found in this fraction.