石墨炉原子吸收法快速测定血液中铅和镉

建立了快速测定血液中铅和镉的石墨炉原子吸收光谱法。使用5%硝酸溶液对样品进行脱蛋白处理,然后在旋涡混合器上振摇,离心后取上清液上石墨炉原子吸收进行测定。 结果表明,Pb、Cd工作曲线线性关系良好,相关系数均大于0.9994;方法检出限分别为4.32μg/L和0.27μg/L;Pb的回收率为91.60%～97.31%,镉的回收率为97.04%～98.86%;Pb测定的RSD（n=7）为2.35%,Cd测定的RSD（n=7）为1.53%。冻干牛血铅、镉标准物质GBW09139k和GBW09140k的测定值与参考值吻合。该方法快速准确,精密度、准确度、检出限等测定结果令人满意。可以作为日常血铅、血镉的检测的方法。     

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.     

Hollow-fiber liquid-liquid-solid micro-extraction of lead in soft drinks and determination by graphite furnace atomic absorption spectrometry

A novel hollow-fiber liquid-liquid-solid micro-extraction technique based on simultaneous liquid-liquid micro-extraction and solid phase micro-extraction using a polypropylene microporous membrane has been developed. The applicability of the proposed procedure was evaluated by extraction of Pb(II) from aqueous solutions and soft drinks. The parameters affecting the extraction efficiency were optimized using multivariate methodology, and the analytical features were established. Under optimized conditions, Pb(II) was concentrated for 20 min on three microporous membrane hollow fibers of 6 mm of length each, placed into 20 mL of sample containing 60 μL of toluene and ammonium O,O-diethyl dithiophosphate. The fibers were introduced directly into the graphite furnace as a solid sample, and the analyte was thermally desorbed from the fiber and atomized using ruthenium as a permanent modifier. A detection limit of 7 ng L⁻¹ Pb was obtained for soft drink samples and good repeatability was found for all samples. The enrichment factor varied between 22 and 66, depending if only one or all three hollow fibers were used for the determination of lead. The results suggest that the proposed procedure represents a simple and low-cost micro-extraction alternative rendering adequate limits of quantification for the determination of Pb(II) in soft drink samples.     

Separation and preconcentration of ultratrace lead in biological organisms and its determination by graphite furnace atomic absorption spectrometry

A biological organism (chitosan) was utilized to preconcentrate lead ions from tap water. This preconcentration was achieved by mixing 0.8 ml of chitosan slurry with 10-50 ml of lead-containing solution and subsequently separating by centrifugation. The chitosan paste was then dissolved in 1 ml of 0.2% nitric acid and analysed by graphite furnace atomic absorption spectrometry. The extraction efficiency can approach 100% in the pH range 4-10. The amount of chitosan used was not critical. The effect of some impurities was also investigated. If six samples were prepared simultaneously, the time needed to preconcentrate each sample was less than 3 min. Two different modes of standard addition (the standard lead solutions being added before and after preconcentration) were used for analysis of tap water samples, and the results obtained by the two modes were found to be quite consistent.     

Determination of lead in geological and biological materials by graphite furnace atomic absorption spectrometry

Summary Serious systematic errors inherent in the determination of lead in geological and biological samples by flameless atomic-absorption spectrometry are demonstrated. The reduced absorption of lead is due to partial interaction with alkaline, alkaline-earth and iron chlorides during the atomization stage. Incomplete dissociation of the volatile monochloride of lead in the gaseous phase reduces the absorption signal. An addition of 20% hydrogen to nitrogen (purge gas) diminishes signal suppression by removing the chlorine in form of volatile HCl. The detection limit is about 0.6 ppm in rocks and about 0.3 ppm in plant materials. Depending on the content in the samples the relative standard deviation is between 1 and 12%. The accuracy of the method was tested on 39 international standard reference samples.

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Bestimmung von Blei in geologischen und biologischen Materialien durch AAS mit der Graphitrohrküvette

Zusammenfassung Schwerwiegende systematische Fehler bei der Bestimmung von Blei in geologischen und biologischen Materialien mit der Graphitrohrküvette werden aufgezeigt. Die Reaktion von Blei mit Alkali-, Erdalkali- und Eisenchloriden während der Atomisierungsphase führt zur Bildung von Bleimonochlorid, das nur unvollständig dissoziiert und eine Signalunterdrückung zur Folge hat. Ein Zusatz von 20% Wasserstoff zu Stickstoff als Spülgas vermindert die Signalunterdrückung, indem überschüssiges Chlor als Chlorwasserstoff entfernt wird. Die Nachweisgrenze liegt bei ca. 0,6 ppm für Gesteine und bei ca. 0,3 ppm für Pflanzenmaterialien. Je nach der Konzentration beträgt die relative Standardabweichung 1–12%. Die Genauigkeit der Methode wurde an 39 internationalen Standardreferenzproben überprüft.

     

Determination of tin and lead in sediment slurries by graphite furnace atomic absorption spectrometry

Methods were determined for lead and tin determinations in river, marine and lake sediments by slurry sampling and graphite furnace atomic absorption spectrometry. The optimizations were carried out using River Sediment BCR 320 and Marine Sediment PACS-2 for Pb and Sn, respectively. For Pb determination, the parameters studied included inorganic acid mixture, stabilizing agent, sample mass and sonication time. The influence of diluents and the extraction to the liquid phase for two different matrices was evaluated for Sn. The Pb content in the slurry liquid phase was ca. 56%, and ranged from 75% to 100% for Sn. Representative masses of 34 and 45 mg, and effective masses of 12 and 48 μg for Pb and Sn, respectively, were obtained under optimized conditions. Detection and quantification limits of 0.2 and 0.7 μg g⁻¹ for Pb, and 1.5–2.6 and 4.5–7.6 μg g⁻¹ for Sn were obtained.

     

Preconcentration of lead in biological matrices for graphite furnace atomic absorption spectrometry

Lead was transferred by a two-step extraction procedure from complicated biological matrices into an aqueous solution. Thereafter, lead could be accurately determined in the aqueous solution without interference by graphite furnace atomic absorption spectrometry (GFAAS). Biological samples were digested sequentially by a mixture of sulphuric acid and nitric acids and a strong oxidant, potassium peroxodisulphate. Lead was extracted by dithiocarbamate in chloroform from the digest solution and subsequently back-extracted into a mercury(II) solution. Matrix materials such as chloride, phosphate and sulphate, which were known to cause serious interference in the determination of lead by GFAAS, could be eliminated in the preconcentration procedure. Close to 90% recovery of lead was achieved. The proposed procedure was applied for the analysis of several NBS biological standard reference materials containing lead in the mg kg^?1 range and satisfactory results were obtained.     

Direct determination of atmospheric lead by Zeeman solid sampling graphite furnace atomic absorption spectrometry (GFAAS)

Summary Atmospheric lead was collected by membrane filters using two low volume air samplers at Jülich, Stolberg, and Wetzlar, Federal Republic of Germany. Sampling times varied from 2 to 8 h. After sampling, each filter was subsampled in two cross-sections using a clean stainless steel punch (diameter 5 mm). The lead content of each subsample disc was determined directly by Zeeman GFAAS, calibrated with aqueous standard solutions and supported by solid reference materials. The distribution of lead between the subsamples was generally homogeneous, with standard deviations ranging from 11 to 37%, but typically <15% for samples with 8 h sampling time. The analysis of each filter usually took about 30 min. The differences in air quality between the three sampling locations, as measured by the lead concentrations, are discussed. In general, Stolberg appears to have the highest lead concentrations. The mass particle-size distribution of lead in the aerosol samples collected by membrane filters using a cascade impactor at Stolberg was also investigated with the same analytical technique. Using graphite platform boats as direct samplers, it is possible for the dry deposition flux of lead to be estimated. This provides a quick means of assessing the levels of lead pollution in the atmospheric environment. With lead concentrations measured in parallel, the dry deposition velocities of lead can be estimated under various meteorological conditions. Application of similar sampling and analytical techniques to other atmospheric trace metals may be possible.     

Chemical reactions in the determination of germanium by graphite furnace atomic absorption spectrometry

The chemical reactions of Ge in the graphite furnace are determined by atomic absorption measurements, X-ray diffraction, electron microscopy and molecular absorption. The sodium germanate formed after the drying cycle is reduced by the carbon of the tube to elemental Ge. Volatile GeO is formed during this reduction process at temperatures higher than 1100 K leads to losses of atomizable Ge. Excess of NaOH enhances the absorbance value of Ge by a factor of two. The reason for this effect is an additional reduction process of GeO to Ge by metallic sodium at temperatures higher than 1500 K. Impregnation of the tube surfaces by carbide forming elements also leads to an enhancement of absorbance.     

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。     

微波消解-石墨炉原子吸收光谱法测定纸质包装材料中铅含量

建立了微波消解-石墨炉原子吸收光谱法测定纸质包装材料中铅含量的方法.该方法具有良好线性关系,线性相关系数R~2为0.999 5,检出限为0.028μg/L,回收率为97%~102%,其相对标准偏差在3.14%~5.76%之间,优点为检出限低、精密度好、准确度高,能精确测定纸质包装材料中的铅含量.     

The determination of low lead levels in the bone of lead-depleted mice by graphite furnace atomic absorption spectrometry

Low lead levels in the femurs of mice fed with a lead-depleted diet have been determined by use of electrothermal atomic absorption spectrometry with Zeeman-effect background correction. The method is based on the use of Mg(NO₃)₂/Pd as matrix modifier which enables significant reduction of the spectral interferences prevalent if chemical modifiers based on NH₄H₂PO₄ with either Ca or Mg are used for samples rich in Ca₃(PO₄)₂ matrix. The method was developed and validated by use of the NIST standard reference material 1486 bone. Bones were decomposed in a pressurized microwave-heated system using 70% nitric acid. Forty-three mice femurs, with a mass of 74.62 ± 12.54 mg, were dissolved in concentrated nitric acid. The lead results found in SRM 1486 (1.25 ± 0.15 μg g^–1, n = 9) were in good agreement with the certificate (1.335 ± 0.014 μg g^–1). Recoveries of 200 ng lead added to the SRM before or after digestion were 99.0 ± 1.4% and 98.5 ± 1.6%, respectively. The lead detection limit in bone samples is 0.06 μg g^–1 dry mass. This method is, therefore, suitable for the determination of very low lead levels (0.06–0.20 μg Pb kg^–1 bone) in the femurs of mice fed a diet with lead level of < 20μg kg^–1.     

The determination of low lead levels in the bone of lead-depleted mice by graphite furnace atomic absorption spectrometry

Low lead levels in the femurs of mice fed with a lead-depleted diet have been determined by use of electrothermal atomic absorption spectrometry with Zeeman-effect background correction. The method is based on the use of Mg(NO3)2/Pd as matrix modifier which enables significant reduction of the spectral interferences prevalent if chemical modifiers based on NH4H2PO4 with either Ca or Mg are used for samples rich in Ca3(PO4)2 matrix. The method was developed and validated by use of the NIST standard reference material 1486 bone. Bones were decomposed in a pressurized microwave-heated system using 70% nitric acid. Forty-three mice femurs, with a mass of 74.62 +/- 12.54 mg, were dissolved in concentrated nitric acid. The lead results found in SRM 1486 (1.25 +/- 0.15 microg g(-1), n = 9) were in good agreement with the certificate (1.335 +/- 0.014 microg g(-1)). Recoveries of 200 ng lead added to the SRM before or after digestion were 99.0 +/- 1.4% and 98.5 +/- 1.6%, respectively. The lead detection limit in bone samples is 0.06 microg g(-1) dry mass. This method is, therefore, suitable for the determination of very low lead levels (0.06-0.20 microg Pb kg(-1) bone) in the femurs of mice fed a diet with lead level of < 20 microg kg(-1).     

Cloud point extraction for the determination of cadmium and lead in biological samples by graphite furnace atomic absorption spectrometry

The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of Cd and Pb from digested biological samples. After complexation with O,O-diethyldithiophosphate (DDTP) in hydrochloric acid medium, the analytes are quantitatively extracted to the phase rich in the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. Methanol acidified with 0.1 mol L⁻¹ HNO₃ was added to the surfactant-rich phase prior to its analysis by electrothermal atomic absorption spectrometry (ET AAS). The adopted concentrations for DDTP, Triton X-114 and hydrochloric acid were all optimized. Pyrolysis and atomization temperatures were optimized using the extracts and pyrolysis temperatures of 700 °C for both elements and atomization temperatures of 1400 and 1600 °C for cadmium and lead, respectively, were used without adding any modifier, which shows that considerable analyte stabilization is provided by the medium itself. A more detailed investigation was carried out to determine which components of the extract were responsible for the high thermal stability achieved and it revealed that the amount of DDTP added and the phosphorus content of the digested samples contributed significantly to this phenomenon. Detection limits (3σ_B) of 6 and 40 ng g⁻¹, along with enrichment factors of 129 and 18 for Cd and Pb, respectively, were achieved. The proposed procedure was applied to the analysis of five certified biological reference materials after microwave-assisted acid digestion in a mixture of H₂O₂ and HNO₃. Comparison with certified values was performed for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level. The high efficiency of cloud point extraction to carry out the determination of the studied analytes in complex matrices was, therefore, demonstrated.     

Determination of cadmium,copper and lead in mineral coal using solid sampling graphite furnace atomic absorption spectrometry

Solid sampling graphite furnace atomic absorption spectrometry (SS-GF AAS) was investigated as a potential technique for the routine determination of trace elements in mineral coal and cadmium, copper and lead were chosen as the model elements. Cadmium and lead could be determined at their main resonance lines at 228.8 nm and 283.3 nm, respectively, but an alternate, less sensitive line had to be used for the determination of copper because of the high copper content in coal. No modifier was necessary for the determination of copper and calibration against aqueous standards provided sufficient accuracy of the results. For the determination of cadmium and lead two different modifiers were investigated, palladium and magnesium nitrates in solution, added on top of each sample aliquot before introduction into the atomizer tube, and ruthenium as a ‘permanent’ modifier. Both approaches gave comparable results, and it is believed that this is the first report about the successful use of a permanent chemical modifier in SS-GF AAS. Calibration against solid standards had to be used for the determination of cadmium and lead in order to obtain accurate values. The agreement between the values found by the proposed procedure and the certificate values for a number of coal reference materials was more than acceptable for routine purposes. The detection limits calculated for 1 mg of coal sample using the ‘zero mass response’ were 0.003 and 0.007 μg g⁻¹ for cadmium with the permanent modifier and the modifier solution, respectively, approximately 0.04 μg g⁻¹ for lead, and 0.014 μg g⁻¹ for copper.     

原子吸收法间接测定乳制品中乳酸的研究

乳酸作为酸味剂是乳制品的重要成分之一。它是由淀粉接种乳酸菌发酵的产物[1,2],也是判断乳制品质量和新鲜度的重要指标之一。乳酸的测定方法比较常用的有滴定法[2]和液相色谱法[3,4]。平时工作中,乳制品里面存在的大量白色乳浊基体使滴定法难于进行,同时给液相色谱法带来冗长乏味的、复杂的操作步骤。由于共存基体对乳酸测定的严重干扰,用上述方法不能快速、及时地测定日益增加的乳制品的乳酸含量。原子吸收法是测定金属元素的简便、快速、准确的方法。用原子吸收法测定有机化合物已有不少研究[5～11],用原子吸收法测定乳酸的也有报道[…     

Determination of cadmium,copper and lead in alumina based catalysts by direct solid sampling graphite furnace atomic absorption spectrometry

Trace impurities of Cd, Cu and Pb were determined in alumina based catalysts using direct solid sampling graphite furnace atomic absorption spectrometry (DSS-GF AAS). The analyzed catalysts are widely used in petrochemical processes. The following analytical parameters were evaluated: pyrolysis and atomization temperatures, feasibility of calibration with aqueous solutions, the necessity for palladium as chemical modifier and the sample mass introduced into the atomizer. Test samples between 0.05 and 8.5 mg were used. Palladium was investigated as chemical modifier but no improvement in analytical performance was obtained and its use was considered unnecessary for all elements. The results obtained by DSS-GF AAS were compared with those of inductively coupled plasma optical emission spectrometry (ICP OES) and also with conventional solution analysis by GF AAS (Sol-GF AAS). Characteristic masses were 1.4, 9 and 20 pg, for Cd, Cu and Pb, respectively. Using DSS-GF AAS the relative standard deviation was always less than 10% and the results agreed with those obtained by Sol-GF AAS and ICP OES. Calibration using aqueous solutions showed good linearity within the working range (R² better than 0.99). Limits of detection (3σ, n = 10) for Cd, Cu and Pb using the proposed procedure were 0.2, 22, and 1.2 ng g^− 1, respectively.     

Possibilities of improving the determination of extremely low lead concentrations in marine fish by graphite furnace atomic absorption spectrometry

Summary With the aim to produce reliable analytical data on lead contents in marine fish a multi-stage analytical procedure was developed, in which graphite furnace atomic absorption spectrometry was combined with pre-instrumental chemical sample treatment. The latter consisted of sample decomposition with nitric acid in a closed system under normal pressure, followed by separation and enrichment of lead traces by solvent extraction. For analytical quality assurance purposes the material to be analysed was labelled with practically carrier-free Pb-203 (internal standard) and recovery was controlled by activity measurement. As contamination throughout the analytical procedure represents a main source of systematic error in ultra trace lead analysis, special precautions were taken to hold the size and variability of the analytical blank as small and reproducible as possible.The practically obtainable detection ability of the method was demonstrated in an exemplary study of some specimens of marine fish (cod and plaice) from the North Sea. Results obtained for muscle tissue (range 0.5–4.1 ng g^–1=2.4–20 nmol kg^–1 wet weight) were extremely low and considerably below the most data published up to now in the literature.

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Möglichkeiten zur Verbesserung der Bestimmung extrem niedriger Bleikonzentrationen in Seefischen durch Graphitrohrofen-Atomabsorptionsspektrometrie

Zusammenfassung Mit dem Ziel, zuverlässige analytische Daten über Bleigehalte von Seefischen zu ermitteln, wurde ein mehrstufiges Analysenverfahren entwickelt, in dem Graphitrohrofen-Atomabsorptionsspektrometrie mit vorgeschalteter Probenaufbereitung verbunden wurde. Letztere bestand aus Probenaufschluß mit Salpetersäure in einem geschlossenen System unter Normaldruck, dem sich Abtrennung und Anreicherung der Bleispuren durch Solvent-Extraktion anschlossen. Zum Zwecke der analytischen Qualitätssicherung wurde das Untersuchungsmaterial mit praktisch trägerfreiem Pb-203 markiert (interner Standard) und mittels Aktivitätsmessung die Ausbeute überprüft.Da Kontaminationen während der analytischen Prozedur eine Hauptursache für systematische Fehler bei der extremen Bleispurenanalytik darstellen, wurden besondere Maßnahmen getroffen, um Größe und Schwankungsbreite des Blindwertes so klein und reproduzierbar wie möglich zu halten.Das praktisch erreichbare Nachweisvermögen der Methode wurde beispielhaft an Hand der Untersuchung einiger Fische (Kabeljau und Scholle) aus der Nordsee gezeigt. Die ermittelten Gehalte für Muskelfleisch-Frischsubstanz (Schwankungsbreite 0,5–4,1 ng g^–1=2,4–20 nMol kg^–1) lagen extrem niedrig und erheblich unter den meisten bisher in der Literatur publizierten Daten.

     

Single drop microextraction combined with graphite furnace atomic absorption spectrometry for determination of lead in biological samples

Single drop microextraction combined with graphite furnace atomic absorption spectrometry is introduced for the determination of trace lead in water samples. A drop of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) dissolved in benzene was held at the tip of a microsyringe and immerged into the sample solution which was stirred, the solvent drop interacts with the sample solution, and the analyte was extracted into the drop and concentrated. After extracting for a period of time, the drop was retracted into the microsyringe and directly injected into graphite furnace for GFAAS determination of Pb. Several factors affecting the extraction efficiency, such as pH of sample solution, drop volume, stirring rate and extraction time, were optimized. Under the optimized conditions, an enhancement factor of 16 was achieved, and the detection limits for Pb were 25 ng L⁻¹. The relative standard deviation for seven replicate determination of 10 ng mL⁻¹ Pb was 6.1%. The method was applied to determine trace Pb in biological samples with satisfactory results. Correspondence: Pei Liang, Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China