Evaluation of ammonia as diluent for serum sample preparation and determination of selenium by graphite furnace atomic absorption spectrometry

A method for the determination of total selenium in serum samples by graphite furnace atomic absorption spectrometry was evaluated. The method involved direct introduction of 1:5 diluted serum samples (1% v/v NH₄OH+0.05% w/v Triton X-100^®) into transversely heated graphite tubes, and the use of 10 μg Pd+3 μg Mg(NO₃)₂ as chemical modifier. Optimization of the modifier mass and the atomization temperature was conducted by simultaneously varying such parameters and evaluating both the integrated absorbance and the peak height/peak area ratio. The latter allowed the selection of compromise conditions rendering good sensitivity and adequate analyte peak profiles. A characteristic mass of 49 pg and a detection limit (3s) of 6 μg 1⁻¹ Se, corresponding to 30 μg l⁻¹ Se in the serum sample, were obtained. The analyte addition technique was used for calibration. The accuracy was assessed by the determination of total selenium in Seronorm™ Trace Elements Serum Batch 116 (Nycomed Pharma AS). The method was applied for the determination of total selenium in ten serum samples taken from individuals with no known physical affection. The selenium concentration ranged between 79 and 147 μg l⁻¹, with a mean value of 114±22 μg l⁻¹.     

Pigment identification in artwork using graphite furnace atomic absorption spectrometry

The use of a sampling technique is described for the identification of metals from inorganic pigments in paint. The sampling technique involves gently contacting a cotton swab with the painted surface to physically remove a minute quantity (∼1-2 μg) of pigment. The amount of material removed from the painted surface is invisible to the unaided eye and does not cause any visible effect to the painted surface. The cotton swab was then placed in a 1.5 ml polystyrene beaker containing HNO₃ to extract pigment metals prior to analysis using graphite furnace atomic absorption spectrometry (GFAAS). GFAAS is well suited for identifying pigment metals since it requires small samples and many pigments consist of main group elements (e.g. Al) as well as transition metals (e.g. Zn, Fe and Cd). Using Cd (cadmium red) as the test element, the reproducibility of sampling a paint surface with the cotton swab was approximately 13% in either a water or oil medium. To test the feasibility of cotton sampling for pigment identification, samples were obtained from paintings (watercolour and oil) of a local collection. Raman spectra provided complementary information to the GFAAS, which together are essential for positive identification of some pigments. For example, GFAAS indicated the presence of Cu, but the Raman spectra positively identified the modern copper pigment phthalocyanine green (Cu(C₃₂Cl₁₆N₈). Both Raman spectroscopy and GFAAS were useful for identifying ZnO as a white pigment.     

Solid sample graphite furnace atomic absorption spectroscopy for supporting arsenic determination in sediments following a sequential extraction procedure

Solid sample graphite furnace atomic absorption spectroscopy (SS-GFAAS) has been proposed since its appearance as a good alternative to wet methods of analysis in many matrices. Here, we examine the use of SS-GFAAS for total and leachable arsenic determination in sediments from distinct origins.Our direct analysis of seven selected sediments was not always free of spectral matrix interference, but the spectroscopic technique gave very good results for (a) direct arsenic measurement in solid residues from a range of leaching processes, (b) total arsenic determination (HNO₃ leaching test) and (c) the evaluation of its potential remobilisation (modified BCR three-step sequential extraction scheme). For the optimised instrumental conditions, the analysis limit was 0.44 mg kg⁻¹ and long-term reproducibility was between 10-15%.The sum of leachable arsenic in HNO₃ 65% and the residual fraction, gave recoveries from 72 to 118% of total arsenic content. These results are a good alternative to other cumbersome wet methods involving HF.     

Separation and speciation of selenium in food and water samples by the combination of magnesium hydroxide coprecipitation-graphite furnace atomic absorption spectrometric determination

A simple and economic separation and speciation procedure for selenium in food and water samples have been presented prior to its graphite furnace atomic absorption spectrometry (GFAAS). Magnesium hydroxide coprecipitation system for selenium(IV) was applied to the separation and speciation of selenium ions. The influences of the various analytical parameters for the quantitative recoveries of selenium ions like pH, amounts of magnesium ions as carrier elements, etc. on were examined. The effects of the alkaline and earth alkaline metals, some transition metals and some anions on the recoveries of selenium(IV) were also investigated. The recoveries of analytes were found greater than 95%. No appreciable matrix effects were observed. The detection limit, defined as three times the blank standard deviation (3σ), was 0.030 μg l⁻¹. The preconcentration factor for the presented system was 25. The proposed method was applied to the speciation of selenium(IV), selenium(VI) and determination of total selenium in natural waters and microwave digested various food samples with satisfactory results. The procedure was validated with certified reference materials. The relative errors and relative standard deviations were below 6% and 10%, respectively.     

微波消解-GFAAS测定浅水湖泊底泥中重金属元素

探讨了采用微波消解作为底泥样品的前处理方法,运用石墨炉原子吸收法测定浅水湖泊底泥中Cu,Pb,Zn,Cd,Cr含量的实验条件.方法的RSD为2.0％～4.1％,平均回收率为97.4％～101.5％,Cu,Pb,Zn,Cd,Cr的检出限分别为0.4,5,2.8,0.25,2.5ng.该法适合于浅水湖泊底泥中重金属含量的测定.     

石墨炉原子吸收法测定石脑油中微量砷

试样用四氢呋喃（THF）有机溶剂稀释,以硝酸镍为基体改进剂,研究采用石墨炉原子吸收法直接进样测定石脑油中的砷量。研究表明,砷量在0～50μg／L范围内线性关系良好,回收率93％～104％。     

Effectiveness of linearization of calibration curves in Zeeman graphite furnace atomic absorption spectrometry

A theoretical analysis is made of the effect of analytical line broadening and of non-absorbable radiation in the light source on the shape of concentration curves in Zeeman graphite furnace atomic absorption spectrometry. These results have been used in a systematic study of the effect of spectrometer slit width and hollow-cathode lamp (HCL) current on linearization of calibration graphs for 11 elements: Ag, Au, Bi, Cd, Co, Cu, Fe, Mn, Ni, Pb, and Sb. The effectiveness of linearization throughout the analytical range covered was estimated experimentally on series of 25–30 solutions. Three solutions in each series were used as standards for constructing the calibration graph, the others serving to evaluate the linearization effectiveness. Increasing the slit width and decreasing the HCL current compared to the standard measurement conditions have permitted us to reach a sufficiently high effectiveness of linearization for all the elements studied, with the exception of Ni. The maximum deviation of experimental points from the linear graph under optimum conditions does not exceed 6%. The effect of the Δ parameter used in the computational algorithm on linearization effectiveness is investigated.     

Monitoring of selenium in water samples using dispersive liquid-liquid microextraction followed by iridium-modified tube graphite furnace atomic absorption spectrometry

A simple and powerful microextraction technique was used for determination of selenium in water samples using dispersive liquid-liquid microextraction (DLLME) followed by graphite furnace atomic absorption spectrometry (GF AAS). DLLME and simultaneous complex formation was performed with rapid injection of a mixture containing ethanol (disperser solvent), carbon tetrachloride (extraction solvent) and ammonium pyrrolidine dithiocarbamate (APDC, chelating agent) into water sample spiked with selenium. After centrifuging, fine droplets of carbon tetrachloride, which were dispersed among the solution and extracted Se-APDC complex, sediment at the bottom of the conical test tube. The concentration of enriched analyte in the sedimented phase was determined by iridium-modified pyrolitic tube graphite furnace atomic absorption spectrometry. The concentration of selenate was obtained as the difference between the concentration of selenite after and before pre-reduction of selenate to selenite. Some effective parameters on extraction and complex formation, such as extraction and disperser solvent type and their volume, extraction time, salt effect, pH and concentration of chelating agent were optimized. Under the optimum conditions, the enrichment factor of 70 was obtained from only 5.00 mL of water sample. The calibration graph was linear in the range of 0.1-3 μg L^− 1 with detection limit of 0.05 μg L^− 1. The relative standard deviation (RSDs) for ten replicate measurements of 2.00 μg L^− 1 of selenium was 4.5%. The relative recoveries of selenium in tap, river and sea water samples at spiking level of 2.00 μg L^− 1 were 106, 96 and 98%, respectively.     

Surfactant/oil/water system for the determination of selenium in eggs by graphite furnace atomic absorption spectrometry

An oil-in-water formulation has been optimized to determine trace levels of selenium in whole hen eggs by graphite furnace atomic absorption spectrometry. This method is simpler and requires fewer reagents when compared with other sample pre-treatment procedures. Graphite furnace atomic absorption spectrometric (GF AAS) measurement was carried out using standard addition calibration and Pd as a modifier. The precision, expressed as relative standard deviation, was better than 5% and the limit of detection was 1 µg L^− 1. The validation of the method was performed against a standard reference material Whole Egg Powder (RM 8415), and the measured Se corresponded to 95.2% of the certified value. The method was used for the determination of the Se level in eggs from hens treated with Se dietary supplements. Inorganic and organic Se sources were added to hen feed. The Se content of eggs was higher when hens were fed with organic Se compared to the other treatments. The proposed method, including sample emulsification for subsequent Se determination by GF AAS has proved to be sensitive, reproducible, simple and economical.     

石墨炉原子吸收光谱法测定茶叶中的铅

采用石墨炉原子吸收光谱法测定茶叶中铅,以NH4H2PO4作为基体改进剂,提高了测定的灰化温度,消除了基体干扰.方法简便,快速,准确度高.通过对标准物质的多次测定,结果均在其保证值范围内,相对标准偏差为2.8%.对样品进行加标回收试验,回收率为96%～105%,方法检出限为0.12μg/L.     

石墨炉原子吸收法测定3-苯基丙烯酸酯类化合物中微量钯

利用高灵敏的石墨炉原子吸收法,在V(HCl):V(HNO3):V(H2O)＝5:1:94混合酸介质中测定苯基丙烯酸酯类化合物中的钯量.已纯化样品钯量的平均值是6.76 μg/g,标准相对偏差是4.8%,平均回收率为99.3%;未纯化样品钯量的平均值是121.2 μg/g,平均相对偏差是5.4%.还讨论酸介质对测定钯吸光度的影响,通过比较找到了合适的酸介质组成.     

Comparison of modifiers for determination of arsenic, antimony and selenium by atomic absorption spectrometry with atomization in graphite tube or hydride generation and in-situ preconcentration in graphite tube

The study was performed to compare the effect of magnesium modifier (magnesium nitrate) with that of other modifiers (palladium nitrate and nickel nitrate) in determination of arsenic, antimony and selenium by atomic absorption spectroscopy with atomization in a graphite tube, with generation of hydrides and in situ preconcentration in a graphite tube. The assumed criterion of a modifier performance was the magnitude of the analytical signal. It was found that in determinations with atomization in a graphite furnace the effects of all these modifiers were comparable, while in those with hydride generation and in situ preconcentration in a graphite tube the magnesium modifier showed poorer performance (25% decrease of the analytical signal). In determinations of arsenic and selenium the analytical signal obtained with magnesium salt as a modifier was comparable with those obtained in the presence of all other modifiers.     

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(NO₃)₂/Mg(NO₃)₂ was used as chemical modifier. All samples and reference solutions were automatically spiked with 500 μg l⁻¹ As and 0.2% (v/v) HNO₃ by the autosampler, eliminating the need for manual dilutions. For 10 μl 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 3.0 μg l⁻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%.     

Comparison of direct sampling and emulsion analysis using a filter furnace for the determination of lead in crude oil by graphite furnace atomic absorption spectrometry

The determination of trace elements in crude oil is difficult due to the complex nature of the sample and the various different chemical forms in which the metals can occur. The advantage of graphite furnace atomic absorption spectrometry is that only a minimum of sample pretreatment is required. In this work two techniques have been compared to establish a fast and reliable method for lead determination in crude oil. In the first one the crude oil samples were weighed directly onto solid sampling (SS) platforms and introduced into the graphite tube for analysis. In the second one the samples were prepared as oil-in-water emulsions and analyzed in a filter furnace (FF). Twenty μL of a mixture of 0.5 mg L^− 1 Pd + 0.3 mg L^− 1 Mg + Triton X-100 has been used as the modifier, and calibration against aqueous solutions has been used for both methods. The sensitivity obtained with the FF was more than a factor of two better than that with SS; however, as a larger sample mass could be introduced in the latter case, so that the limits of detection for both techniques were 0.004 mg kg^− 1. Seven crude oil samples were analyzed using the two procedures, and all results were in agreement at a 95% confidence level using a paired Student's t-test. For validation purposes, three crude oil samples have been mineralized using an open-vessel acid digestion, and the results were in agreement with those found with direct sampling and with emulsion sampling using FF according to ANOVA test. Both methods are simple, fast and reliable, being appropriated for routine analysis; however, the direct method using SS technology should be preferred because of its simplicity, speed and commercial availability.     

Dispersive liquid-liquid microextraction preconcentration of palladium in water samples and determination by graphite furnace atomic absorption spectrometry

A new method for the determination of palladium was developed by dispersive liquid-liquid microextraction preconcentration and graphite furnace atomic absorption spectrometry detection. In the proposed approach, diethyldithiocarbamate (DDTC) was used as a chelating agent, and carbon tetrachloride and ethanol were selected as extraction and dispersive solvent. Some factors influencing the extraction efficiency of palladium and its subsequent determination, including extraction and dispersive solvent type and volume, pH of sample solution, concentration of the chelating agent and extraction time, were studied and optimized. Under the optimum conditions, the enrichment factor of this method for palladium reached at 156. The detection limit for palladium was 2.4 ng L⁻¹ (3σ), and the relative standard deviation (R.S.D.) was 4.3% (n = 7, c = 1.0 ng mL⁻¹). The method was successfully applied to the determination of trace amount of palladium in water samples.     

石墨炉原子吸收法测定钢中铅的干扰抑制

研究了石墨炉原子化法测定钢铁中痕量铅的干扰情况，并进行了干扰抑制实验。提出了抑制干扰的方法。     

Solid sampling-graphite furnace atomic absorption spectrometry for the direct determination of boron in plant tissues

In this work, the potential of graphite furnace atomic absorption spectrometry for the direct determination of B in plant tissues has been investigated. Three certified reference materials (NIST SRM 1570a spinach leaves, NIST SRM 1573a tomato leaves and BCR CRM 679 white cabbage) were selected for this study, the goal always being to develop a fast procedure that could be robust enough to provide a satisfactory performance for all of them, without any modifications in the conditions applied.The use of a suitable chemical modifier was found to be essential for obtaining a reproducible and sufficiently sensitive signal for boron solutions. In this regard, the performance of the combination of citric acid plus W (added as a permanent modifier) was noteworthy, resulting in well-defined signal profiles, a remarkable analyte stabilization during the pyrolysis step (up to 2100 °C) and minimal memory effects. This mixture of modifiers provided a good performance for the direct analysis of solid samples as well, but only if a suitable temperature program, favoring the interaction between the analyte and the modifiers, was used. Thus, such a temperature program, with two pyrolysis steps and the addition of NH₄NO₃ in order to carry out the in situ sample microdigestion, was optimized. Under these conditions, the peak areas obtained for both solid samples and aqueous standards were comparable.Finally, the analysis of the samples was carried out. In all cases, a good agreement with the certified values was obtained, while R.S.D. values ranged between 6 and 10%. It can be concluded that the method proposed shows significant advantages for the determination of this complicated element in solid samples such as the use of aqueous standards for calibration, a high sample throughput (20 min per sample), a suitable limit of detection (0.3 μg g⁻¹) and reduced risk of analyte losses and contamination.     

Direct determination of germanium in botanical samples by graphite furnace atomic absorption spectrometry with palladium-zirconium as chemical modifier

A method has been described for the direct determination of trace levels of germanium by graphite furnace atomic absorption spectrometry (GFAAS) using chemical matrix modification technique. The stabilization and the pyrolysis temperatures for germanium were investigated with various chemical modifiers including palladium, palladium–magnesium, palladium–strontium and palladium–zirconium. The highest pyrolysis temperature and highest integrated absorbance were obtained using palladium–zirconium modifier, and the severe matrix interference from sulfate can be eliminated. The characteristic mass and absolute detection limit (3σ) of germanium were found to be 16 and 12 pg, respectively. The proposed method was applied to the determination of trace levels of germanium in botanical samples with a recovery range of 92–106%. The hydride generation atomic fluorescence spectrometric (HGAFS) method was employed to analyze the samples and the results agree well with those obtained by GFAAS. The contents of germanium in standard reference materials were determined and the results were in good agreement with the reference values.     

Automated on-line separation preconcentration system for palladium determination by graphite furnace atomic absorption spectrometry and its application to palladium determination in environmental and food samples

A flow injection (FI) system was used to develop an efficient on-line sorbent extraction preconcentration system for palladium by graphite furnace atomic absorption spectrometry (GFAAS). The investigated metal was preconcentrated on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). The palladium is eluted with 40 μl of HCl 4 M and directly introduced into the graphite furnace. The detection limit for palladium under the optimum conditions was 0.4 ng ml⁻¹. This procedure was employed to determine palladium in different samples.     

石墨炉原子吸收法测定肼类推进剂中九种金属杂质

建立了石墨炉原子吸收法测定肼类推进剂中锌、铁、铬、锰、铅、镍、铝、铜、钛等金属含量的检测方法 ,无需样品预处理过程 ,灵敏度高且快速、准确。各元素测定方法的精密度小于 1 0 % ,回收率在 82 %～ 1 1 6%之间。