Simultaneous determination of copper and lead by graphite-furnace atomic absorption spectrometry after liquid-liquid extraction of the ion pair with zephiramine

A procedure for the simultaneous determination of copper and lead by graphite-furnace atomic absorption spectrometry was investigated by means of a two-channel atomic absorption spectrometer. Both copper(II) and lead(II) are converted into their iodo complex anions and extracted quantitatively into diisobutyl ketone as their ion pairs with tetradecyldimethylbenzylammonium (zephiramine) in a 10-ml centrifuge tube. An aliquot of the organic extract is directly pipetted from the upper layer in the centrifuge tube and injected into the graphite furnace. The detection limits (S/N = 3) are 2.6 ng ml^?1 of copper and 1.0 ng ml^?1 of lead. The relative standard deviations for 10 replicate determinations are 2.9% for 20 ng ml^?1 of copper and 2.7% for 10 ng ml^?1 of lead. Results of analyses of some practical samples are given.     

Determination of silicon in fats and oils by electrothermal atomic absorption spectrometry with in-furnace air oxidation

A graphite-furnace atomic absorption spectrometric emthod is reported for determination of dimethylpolysiloxane (silicone) in edible fats and oils. It incorporates an air-oxidation step in the furnace program to reduce matrix interferences. The detection limit is 0.3 mg kg^?1 in soils, and short-term precision is about 6% at silicon concentrations of 1.7–2.0 mg kg^?1. The procedure was successfully applied to a variety of commercial frying fats and oils, to quantify silicone loss during polish filtration during oil manufacture, to quantify sorption of antifoam onto fried food, and to detect fugitive sources of silicone encountered in deep-fat frying operations.     

Determination of beryllium in urine by graphite-furnace atomic absorption spectrometry

A method has been developed for the determination of beryllium in urine by graphite-furnace atomic absorption spectrometry. Ammonium 12-molybdophosphate and ascorbic acid were employed as a matrix modifier. The tolerable charring temperature for beryllium in both aqueous solution and urine was raised to 1400 °C in the presence of a matrix modifier. The sensitivity for the determination of beryllium was also improved by a factor of 1.5 in comparison with that obtained by using magnesium nitrate as a matrix modifier. The mechanism of the enhancement effect of ammonium molybdophosphate was ascribed to the effectiveness of the formation of gaseous BeO, which is a precursor of free beryllium. Beryllium in urine can be determined simply by dilution with ascorbic acid solution. The relative standard deviation for seven replicate determinations of beryllium was 1.9% for a urine sample containing 0.029 μg ml^?1 of beryllium.     

The uses of 1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin on the solid phase extraction of traces heavy metal ions and their determinations by atomic absorption spectrometry

1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin was used as solid phase extractor of copper, nickel, cadmium, lead, chromium and cobalt ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The parameters including pH, sample volume, matrix effects were also investigated. The relative standard deviation (R.S.D.) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was between 0.21 and 1.4 μg l⁻¹. The results were used for preconcentration of analyte ions from natural water samples. The method was also applied to a stream sediment standard reference material (GBW7309) for the determination of Cu, Ni, Cd, Pb, Cr and Co.     

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.     

Determination of Metals in Olive Oil by Electrothermal Atomic Absorption Spectrometry: Validation and Uncertainty Measurements

The determination of trace metals in organic matrices is still highly demanding despite improvements in analytical instrumentation. The present study was undertaken in order to evaluate electrothermal atomic absorption spectrometry for the determination of cadmium, copper, iron, lead, and nickel in olive oil. A variety of approaches were used. The most suitable digestion procedure was heating the samples at 300°C for 24 hours and ashing in a muffle furnace at 450°C for 16 hours. The validation data were detection limits of 0.2–153 ng g^?1; mean trueness on certified reference materials of 81–94%; mean recovery on spikes of 90–120%; and repeatability of 12–53%. The combined relative uncertainty was 0.298–0.766. Oils processed by pressing had higher copper, iron, and lead concentrations than oils processed by centrifugation. The reported method provides an efficient way for monitoring trace metal content during olive oil production.     

Direct determination of lead in blood by electrothermal atomic absorption spectrometry with L'vov platform and matrix modification

An electrothermal atomic-absorption procedure with the L'vov platform and a simple five- or ten-fold sample dilution with a matrix-modifier solution containing diammonium hydrogenphosphate, Triton X-100 and nitric acid, is described for the direct determination of relatively low levels of lead in heparinized blood. The graphite-furnace parameters and matrix-modifier composition are optimized. Sensitivity, imprecision, accuracy and detection limit are reported. Results obtained by standard addition for ten human blood samples (30–400 μg l^?1 lead) were confirmed by an extraction/flame atomic-absorption reference method. Differences in mean lead values ranged from 2 to 31 μg l^?1 with 5.1% mean relative difference. The mean relative standard deviations for consecutive and between-day determinations were 4.6 and 9%, respectively. Accuracy was verified by analyzing six bovine-blood standards certified for lead in the range 70–1100 μg l^?1; deviations of found concentrations from expected values ranged from 0 to 44 μg l^?1 with 4.3% mean relative error. Recovery experiments done with human blood gave 104% (90–121%) of the added lead. The method offers several advantages for routine application in comparison with the extraction/flame atomic-absorption procedure.     

Determination of heavy metal ions in environmental samples employing preconcentration on novel resins of polyurethane foam linked with o-Aminophenol or o-Hydroxyphenylazonaphthol

o-Aminophenol (AP) and its azo derivative with ß-Naphthol(Naph) is bonded to polyurethane foam (BPUF) and used as solid phase extractor of nickel, cadmium and zinc ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The novel resins of polyurethane foam were characterised by density, elemental analysis, IR spectra and chemical stability. The parameters including pH, sample volume, matrix effects were investigated. The relative standard deviation (RSD) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was found between 0.06 and 0.22?µg?L^?1. The procedure was used for determination of analyte ions in natural water samples, apple leaves and fish liver.     

Determination of ultra-trace amounts of nickel in environmental samples by atomic absorption spectrometry with in-situ trapping of volatile species in an iridium–palladium coated graphite furnace

A sensitive and accurate method is described for the determination of ultra-trace nickel in environmental samples with in-situ trapping of volatile species in iridium-palladium coated graphite furnace atomic absorption spectrometry. The effects of the conditions for the generation and collection of volatile nickel species, such as medium acidity, potassium borohydride concentration, enhancement reagent concentration, reaction temperature, as well as graphite tube coating, carrier gas flow rate and trapping time were investigated. Phenanthroline was selected as the enhancement reagent due to its good enhancing effect, and iridium–palladium coating was used for the in-situ trapping of volatile nickel species at 300°C. Under the optimal conditions, the calibration curve was linear from 0.21 up to 30.0 ng mL^?1 with correlation coefficient of 0.9991, the detection limit (S/N = 3) was 0.21 ng mL^?1 for 4 mL sample volumes and the relative standard deviation for 11 determinations of Ni at 10 ng mL^?1 was 3.5%. The results found by the proposed methods are accordant with the certified values of water, soil and tea certified reference materials. The proposed methods have been applied for the determination of ultra-trace Ni in tap, river and wastewater, as well as rice and soil samples, with recoveries ranging from 97.3 to 100.5%.     

Determination of chromium,manganese and vanadium in sediments and soils by modifier—free slurry sampling electrothermal atomic absorption spectrometry

Slurried sediment and soil samples of the certified reference materials with a highly elevated level of the metals of interest (Mn, Cr and V) were analysed by electrothermal atomic absorption spectrometry (ETAAS) with Zeeman effect background correction. The method of slurry preparation and time-temperature programmes were optimized and, finally, the use of chemical modifiers was not necessary. The effect of alternate spectral lines and gas mini-flows on characteristic masses of analytes was studied. The homogeneity of samples and the influence of short sample grinding were also discussed. The simple, aqueous standard based calibration graphs (except Mn at the concentration > 1000 mg kg⁻¹) were applied for the quantification of results. The results of determinations obtained by slurry sampling agreed well with the cetified values, and the relative standard deviations (RSDs) for the over-all analytical procedure repeatability (at slurries concentration level about 2 mg/2 ml) were less than 9.5%, except manganese (10.4%).     

Anodic stripping voltammetry at a mercury film electrode: baseline concentrations of cadmium,lead, and copper in selected natural waters

A simple, rapid, and inexpensive anodic stripping voltammetric method with a mercury thin film electrode is reported for the establishment of baseline concentrations of cadmium, lead, and copper in natural waters. The procedure for routine surface preparation of wax-impregnated graphite mercury film electrodes requires about 30 min. Concentrations in the 0.006–6 μg l^-1 range are determined by linear d.c. voltage sweeps; the total time for a plating and stripping cycle is 6 min or less. The need for pressure-digesting samples for copper determinations is demonstrated. The a.s.v. results correlate well with corresponding analyses performed by graphite-furnace atomic absorption spectrometry.     

Flame atomic absorption spectrometric determination of trace amounts of nickel after extraction and preconcentration onto natural modified analcime zeolite loaded with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

Nickel is a moderately toxic element compared with other transition metals. However, inhalation of nickel and its compounds leads to serious problems, including cancer of the respiratory system and a skin disorder, nickel-eczema. Thus, attention has focused on the toxicity of nickel at low concentrations, and the development of reliable, analytical approaches for the determination of trace amounts of nickel is needed. This paper describes a simple, rapid, and sensitive flame atomic absorption spectrometric method for the determination of trace amounts of nickel in various samples after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex on a modified Analcime column in the pH range of 7.5-10.5. The retained analyte on the Analcime is recovered with 5.0 mL 2 M nitric acid and determined by flame atomic absorption spectrometry. The detection limit is 20 ng/mL, and the calibration curve is linear for analyte concentrations in the range of 0.1-8 microg/mL final solution, with a correlation coefficient of 0.9993. Eight replicate determinations of nickel at 2 microg/mL in the final solution gave an absorbance of 0.1222, with a relative standard deviation (RSD) of +/-1.2%. The interference of a large number of anions and cations was studied, and the proposed method was used for the determination of nickel in various standard reference samples. The accuracy of the proposed method was evaluated by analyzing standard reference samples, and the results were satisfactory (recoveries of >96%; RSD of <3.5%).     

Electrothermal atomic absorption spectrometric determination of arsenic in essential lavender and rose oils

Analytical procedures for electrothermal atomic absorption spectrometric (ETAAS) determination of arsenic in essential oils from lavender (Lavendula angustifolia) and rose (Rosa damascena) are described. For direct ETAAS analysis, oil samples are diluted with ethanol or i-propanol for lavender and rose oil, respectively. Leveling off responses of four different arsenic species (arsenite, arsenate, monomethylarsonate and dimethylarsinate) is achieved by using a composite chemical modifier: l-cysteine (0.05 g l⁻¹) in combination with palladium (2.5 μg) and citric acid (100 μg). Transverse-heated graphite atomizer (THGA) with longitudinal Zeeman-effect background correction and ‘end-capped’ graphite tubes with integrated pyrolytic graphite platforms, pre-treated with Zr-Ir for permanent modification are employed as most appropriate atomizer. Calibration with solvent-matched standard solutions of As(III) is used for four- and five-fold diluted samples of lavender and rose oil, respectively. Lower dilution factors required standard addition calibration by using aqueous (for lavender oil) or i-propanol (for rose oil) solutions of As(III). The limits of detection (LOD) for the whole analytical procedure are 4.4 and 4.7 ng g⁻¹ As in levender and rose oil, respectively. The relative standard deviation (R.S.D.) for As at 6-30 ng g⁻¹ levels is between 8 and 17% for both oils. As an alternative, procedure based on low temperature plasma ashing in oxygen with ETAAS, providing LODs of 2.5 and 2.7 ng g⁻¹ As in levender and rose oil, respectively, and R.S.D. within 8-12% for both oils has been elaborated. Results obtained by both procedures are in good agreement.     

Semi-automated method for the determination of bismuth in rocks

A rapid and accurate method for the determination of bismuth in rock samples is described. Automated equipment is used to generate bismuth hydride from solutions of rock samples prepared by digestion with a mixture of hydrofluoric and perchloric acids. The evolved hydride is carried to a heated quartz tube by a stream of argon, and the atomic absorption of bismuth recorded. Thiosemicarbazide and 1,10-phenanthroline are used as masking agents to minimize interferences from copper and nickel. As little as 20 ng Bi g^-1 can be determined; the average r.s.d. is 5.4%. Results obtained for six USGS standard rocks are in close agreement with the recommended values obtained by an isotope dilution technique.     

Column system using diaion HP-2MG for determination of some metal ions by flame atomic absorption spectrometry

A column solid-phase extraction method for the preconcentration and determination of cadmium(II), copper(II), cobalt(II), iron(III), lead(II), nickel(II) and zinc(II) dithizone chelates by atomic absorption spectrometry has been described. Diaion HP-2MG was used as adsorbent for column studies. The influences of the various analytical parameters including pH of the aqueous solutions, amounts of ligand and resin were investigated for the retentions of the analyte ions. The recovery values are ranged from 95 to 102%. The influences of alkaline and earth alkaline ions were also discussed. The preconcentration factor was 375, when the sample volume and final volume are 750 and 2 ml, respectively. The detection limits of the analyte ions (k=3, N=21) were varying 0.08 μg/l for cadmium to 0.25 μg/l for lead. The relative standard deviations of the determinations at the concentration range of 1.8×10⁻⁴ to 4.5×10⁻⁵ mmol for the investigated elements were found to be lower than 9%. The proposed solid-phase extraction procedure were applied to the flame atomic absorption spectrometric determinations of analyte ions in natural waters (sea, tap, river), microwave digested samples (milk, red wine and rice) and two different reference standard materials (SRM1515 apple leaves and NRCC-SLRS-4 riverine water).     

Direct determination of chromium in human urine by electrothermal atomic absorption spectrometry

A rapid, accurate and direct method for urinary chromium determinations by graphite-furnace atomic absorption spectrometry is described. Few reagents are used and very little sample preparation and manipulation are required, greatly reducing the incidence of sample contamination. The method of standard additions is used to compensate for changes in sensitivity as the furnace tube ages, and for the widely different matrices encountered in urine samples. Furnace parameters must be carefully controlled. The detection limit is in the order of 0.03 ng Cr ml^-1. Agreement with independent methods is evaluated.     

Determination of vanadium in petroleum crudes and fuel oils by gas chromatography

A method is described for determining levels of vanadium as low as 0.1 μg g^-1 in petroleum oils by gas chromatography with flame-ionization detection. The method involves decomposition of the oils, derivatization and solvent extraction of vanadium as the chelate, [2,2,2',2'-tetramethyl-5,5'-(ethane-1,2-diyldiimino)bis(hex-4-en-3-onato)-(2-)] oxovanadium(IV), followed by gas chromatography on a non-polar (SE-30) column. The procedure is applied to a variety of samples, including standard reference and fuel oils used in an interlaboratory study. The results are compared with those of emission spectrography and two standard methods. The new procedure can be extended to the selective, simultaneous detection of copper, nickel and vanadium in such samples.     

Determination of manganese in serum and urine by electrothermal atomic absorption spectrometry

Manganese is determined in serum and urine by graphite-furnace atomic absorption spectrometry after dilution (1 + 1) with distilled water. Simple aqueous standards are used for calibration. Background absorption from the matrix is decreased by attention to the heating programme, sample dilution and gas flow-rate during atomisation. Remaining background absorption is removed by a deuterium-arc background correction system. To obtain accurate results, great care is needed in collecting samples to avoid contamination. Blood is collected through a plastic cannula, because stainless steel needles introduce considerable contamination. The mean normal concentration of manganese in serum was found to be 0.58 μg l^?1 (it- = 9) which is in agreement with other literature values. For urine, the mean normal concentration found was 0.7 μg l^?1 (it- = 16). Patients on total parenteral nutrition with manganese supplements show elevated serum and urine manganese concentrations.     

Optimum phase-behavior formulation of surfactant/oil/water systems for the determination of chromium in heavy crude oil and in bitumen-in-water emulsion

An “oil in water” formulation was optimized to determine chromium in heavy crude oil (HCO) and bitumen-in-water emulsion (Orimulsion-400®) samples by transversally heated electrothermal atomic absorption spectrometry (TH-ET AAS) using Zeeman effect background correction. The optimum proportion of the oil-water mixture ratio was 7:3 v/v (70 ml of oil as the internal phase) with a non-ionic surfactant concentration (Intan-100) in the emulsion of 0.2% w/w. Chromium was determined in different crude oil samples after dilution of the emulsions 1:9 v/v with a 0.2% w/w solution of surfactant in order to further reduce the viscosity from 100 to 1.6 cP and at the same time to bring the concentration of chromium within the working range of the ET AAS technique. The calibration graph was linear from 1.7 to 100 μg Cr l⁻¹. The sensitivity was of 0.0069 s l μg⁻¹, the characteristic mass (m_o) was of 5.7 pg per 0.0044 s and the detection limit (3σ) was of 0.52 μg l⁻¹. The relative standard deviation of the method, evaluated by replicate analyses of three crude oil samples varied in all cases between 1.5 and 2.6%. Recovery studies were performed on four Venezuelan crude oils, and the average chromium recovery values varied between 95.9-104.8, 90.6-107.6, 95.6-104.0 and 98.8-103.9% for the Cerro Negro, Crudo Hamaca and Boscán crude oils and for the Orimulsión®-400, respectively. The results obtained in this work for the Cerro Negro, Crudo Hamaca and Boscán crude oils and for the Orimulsión®-400 following the proposed procedure were of 0.448±0.008, 0.338±0.004 0.524±0.021 and 0.174±0.008 mg Cr l⁻¹, respectively, which were in good agreement with the values obtained by a tedious recommended standard procedure (respectively: 0.470±0.05, 0.335±0.080, 0.570±0.021 and 0.173±0.009 mg Cr l⁻¹).     

Determination of cadmium by flow injection-chemical vapor generation-atomic absorption spectrometry

A method was developed for the generation of a “cold vapor” of cadmium by means of flow injection-chemical vapor generation from aqueous samples, the determination being conducted with an atomic absorption spectrometer (Pyrex glass T-cell). Several gas-liquid separator designs, atomizer designs, and the effect of several reagents previously reported as sensitivity enhancers (including cobalt, nickel, thiourea and didodecyl-dimethylammonium bromide) were investigated. The limit of detection, calculated as the concentration giving a signal equal to three times the standard deviation of the blank, was 16 ng L^–1, and the relative standard deviation was 1.4% for a concentration of 2 μg L^–1 and 3.8% for 0.1 μg L^–1. The addition of nickel and thiourea to the samples provided improved tolerance to the interference of coexisting ions. Two NIST certified reference materials, Montana Soil and Apple Leaves (respectively containing ¶41.7 ± 0.25 mg kg^–1 Cd and 0.013 ± 0.002 mg kg^–1 Cd) were accurately analyzed. The interference of lead was overcome by coprecipitation with barium sulfate, and the experimental values obtained were 41 ± 1 mg kg^–1 Cd and 0.013 ± 0.002 mg kg^–1 Cd, respectively.