On-line determination of manganese in solid seafood samples by flame atomic absorption spectrometry

Manganese is extracted on-line from solid seafood samples by a simple continuous ultrasound-assisted extraction system (CUES). This system is connected to an on-line manifold, which permits the flow-injection flame atomic absorption spectrometric determination of manganese. Optimisation of the continuous leaching procedure is performed by an experimental design. The proposed method allows the determination of manganese with a relative standard deviation of 0.9% for a sample containing 23.4 μg g⁻¹ manganese (dry mass). The detection limit is 0.4 μg g⁻¹ (dry mass) for 30 mg of sample and the sample throughput is ca. 60 samples per hour. Accurate results are obtained by measuring TORT-1 certified reference material. The procedure is finally applied to mussel, tuna, sardine and clams samples.     

Determination of copper and manganese in sea water by neutron activation analysis and atomic absorption spectrometry

Two methods are compared for the determination of copper and manganese in sea water; the methods have been developed independently at two laboratories. One method is based on the simultaneous isolation of the two elements from sea water by co-crystallization with 8-quinolinol. The crystals are irradiated with neutrons, and after simple purification steps radio-induced ⁶⁴Cu and ⁵⁶Mn are quantified by γ-ray spectrometry. The other method involves chloroform extraction of the diethyldithiocarbamates of copper and manganese and subsequent determination of the two elements by atomic-absorption spectrometry. Both methods provide reliable measurements of copper and manganese concentrations at natural levels in sea water.     

The determination of manganese in urine by atomic absorption spectrometry

Urine samples were digested with a mixture of nitric, sulfuric, and perchloric acids containing molybdate as catalyst. A two-point standard addition technique involved extracts of buffered, digested aliquots containing 10- and 20-p.p.b. manganese(II) in the aqueous phase. The extraction system was MIBK-cupferron. Of the substances tested only bismuth, antimony, and thallium interfered. From the same subject, five morning urine samples averaged 3.0 p.p.b. of manganese with a range of 2.0–4.2 p.p.b.; the average deviation was 0.6 p.p.b.     

Evolved-gas zeeman flame atomic absorption spectrometry for the determination of arsenic compounds

An evolved-gas separation/flame Zeeman atomic absorption spectrometric approach is demonstrated for the speciation and determination of arsenic in oyster tissue. No digestion is needed and separation of inorganic arsenic compounds having similar boiling points is achieved. A stoichiometric or air-rich acetylene/air flame for atomic absorption spectrometry is not generally suitable for arsenic determination because of severe ultraviolet absorption interference at 193.7 nm and low sensitivity; polarized flame Zeeman atomic absorption spectrophotometry with a fuel-rich flame is suitable for the detection of traces of arsenic. The evolved-gas separation/Zeeman atomic absorption approach is simple, based on commercially available instrumentation, and useful for the selective determination of major arsenic compounds. Data are given to demonstrate optimal conditions and to show application to oyster tissue.     

High performance flow flame atomic absorption spectrometry for interference-free trace determination

In High Performance Flow Atomic Spectrometry (HPF-AS), the aerosol is generated by injecting the sample solution into the gas mixing chamber with the aid of an HPLC pump (Hydraulic High Pressure Nebulization, HHPN, working pressure about 200 bar). Using an additional analytical HPLC column, between sample injection valve and nebulization nozzle, the elements under investigation can be separated from interfering elemental traces or major components (High Performance/Pressure Flow System, HPF). The elements to be determined and the interfering substances reach the flame at different times. This means, for example, that traces of Mg in solutions containing aluminum can be determined without interference. Compared to pneumatic nebulization, there is a 20 fold increase in the detection power when determining calcium in a saturated NaCl solution. HPF-AS is a rapid and sensitive method which allows separation of the calcium from the matrix with subsequent determination in less than 90 s.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

The determination of selenium in biological material by thermal neutron activation analysis and atomic absorption spectrometry

Neutron activation analysis and atomic absorption spectrometry (graphite furnace) methods for the analysis of selenium in human tissue are described. The sensitivity (10–30 ng/sample), accuracy and precision are of the same order for both techniques and the choice can only be made on grounds of urgency or convenience. AAS should be chosen for the analysis of wet tissue or the urgent analysis of small numbers of dry tissue. NAA should be chosen for the analysis of large numbers of dry tissue samples where time is not important. The selenium concentration of human liver is shown to be in the region of 1 to 2 ppm (dry weight). Selenium may be lost from tissue during freeze drying if the samples are not maintained at −35°C.     

火焰原子吸收光谱法间接测定药剂中的核黄素

本文利用高碘酸钠对相邻羟基氧化作用的专属性,在一定介质中,高碘酸钠与核黄素完全反应后,过量的高碘酸的钠与硝酸铅或者硝酸铜生成沉淀,通过测定Pb<'2+>或者Cu<'2+>,建立了间接测定核黄素含量的方法.铅体系和铜体系测定的相对标准偏差(RSD)分别为4.8%和5.2%,检出限分别为0.6μg.mL<'-1>和0.5μ...     

Indirect flow-injection determination of ascorbic acid by flame atomic absorption spectrometry

A continuous-flow procedure is proposed for the indirect determination of ascorbic acid, based on its reducing properties because of the oxidation of its 1,2-enediol group. Iron(III) was injected into a 1,10-phenanthroline stream, which was mixed with a sample carrier and then with a sodium picrate solution stream. In these conditions the iron(III) was reduced to iron(II) by the ascorbic acid. Thus, the iron(II) formed reacts with 1,10-phenanthroline to form a charged red complex, which with picrate ion forms a stable red-orange uncharged ion-association complex that is adsorbed on-line on a non-ionic polymeric adsorbent (Amberlite XAD-4), proportionally to the ascorbic acid in the sample. The unadsorbed iron was determined by flame atomic absorption spectrometry. The proposed method allows the determination of ascorbic acid in the range 0.5–25 g ml^–1 with a relative standard deviation of 2.9% at a rate of ca. 90 samples h^–1. This method has been applied to the determination of ascorbic acid in pharmaceutical preparations, fruit juices and sweets. The results obtained in the analysis are compared with those provided by the 2,6-dichloroindophenol method.     

Application of experimental design for investigating the determination of titanium in glass ceramics by flame atomic absorption spectrometry

Interferences of the matrix elements of glass ceramics (Al, Mg, Na and Si) on the titanium signal obtained by atomic absorption spectrometry with a nitrous oxide/acetylene flame were studied by means of experimental design. Quadratic polynomials were chosen as the model; full factorial designs with two, three and four variables at three levels were applied. As expected, aluminium increased the titanium signal, while magnesium reduced it. All the investigated elements interfered nonadditively with the titanium signal; the standard addition method therefore does not provide accurate results. Graphic evaluation of the empirical response surfaces was used to establish optimum conditions for titanium; these surfaces were compared with the polynomial surfaces to check the models. The results obtained on interactions in the system are used with some thermodynamic data to estimate the nature of the compounds formed in the flame. The strong interferences on the titanium signal requires fairly close matrix matching between the standard and sample solutions. The proposed method allows the determination of 3–6% Ti in glass ceramics with a relative standard deviation of 1%.     

On-line electrochemical preconcentration and flame atomic absorption spectrometric determination of manganese in urine samples

A sensitive and selective method was developed for the determination of traces of manganese in urine using on-line electrochemical preconcentration followed by flame atomic absorption spectrometry detection. A home made flow-through polypropylene cell (4.5 cm long × 0.8 cm diameter filled with glass marbles) with an effective inner volume of 0.5 ml containing a working and a counter electrode, both of glassy carbon and a Pt pseudo reference electrode was located in a flow injection manifold specially designed for the purpose of this work. The manganese was deposited from buffer solution of NH₃/NH₄Cl at pH 9.00 through an oxidizing process at a current of 400 mA during 7 min. A flow of HCl 0.1 mol l⁻¹ at 4 ml min⁻¹ through the cell, chemically dissolved the deposit. A small portion (15 μl) of the concentrate was introduced in a continuously flowing system by means of a timing device and was then carried to the detector for the manganese quantification. All electrochemical and spectroscopic variables as well as possible interferences in both systems were systematically studied. The relative standard deviations for ten consecutive measurements of manganese solutions of 2.0 and 20 μg l⁻¹ were of 2.3 and 1.5%, respectively, while for a sample processed five times was less then 5%. The accuracy of the developed procedure was evaluated by adding known amounts of manganese standard to urine samples and following the whole procedure. Recoveries within the range 97.2-102.8% were obtained. To further prove the accuracy, a Seronorm Trace Elements in Urine, Batch 403125 sample with a reported concentration of 13 μg Mn l⁻¹ was also analyzed. The experimental value obtained was of 12.7 ± 0.1 μg l⁻¹, which does not differ significantly from the reported amount (p < 0.05). A preconcentration factor of 40, a linear range between 0.015 and 60 μg l⁻¹ and a limit of detection of 15 ng l⁻¹ permitted the determination of manganese in real urine samples from non-exposed subjects in the range 0.5-2.8 μg l⁻¹.     

Direct determination of iron and manganese in wine using the reference element technique and fast sequential multi-element flame atomic absorption spectrometry

A procedure is proposed for the direct determination of manganese and iron in wine employing fast sequential flame atomic absorption spectrometry and the reference element technique to correct for matrix effects. Cobalt, silver, nickel and indium have been tested as reference elements. The results demonstrated that cobalt and indium at a concentration of 2 and 10mgL(-1) were efficient for quantification of manganese and iron, respectively. Under these conditions, manganese and iron could be determined with quantification limits of 27 and 40microg L(-1), respectively. The proposed method was applied to the determination of manganese and iron in 16 wine samples. The content of manganese varied from 0.78 to 2.89mgL(-1) and that of iron from 0.88 to 9.22mgL(-1). The analytical results were compared with those obtained by inductively coupled plasma optical emission spectrometry after complete mineralization using acid digestion. The statistical comparison by a t-test (95% confidence level) showed no significant difference between the results.     

Uncertainty of atomic absorption spectrometry: Application to the determination of lead in blood

The major sources of uncertainty of a method for determination of Pb in whole blood by atomic absorption spectrometry were identified. The combined uncertainty was compared to the experimentally determined variation and a satisfactory agreement was found, indicating that no significant sources of uncertainty have been overlooked and that the method is in a state of statistical control. The findings suggest that the major source of uncertainty at low concentrations are random fluctuations (noise) of the atomic signal. Therefore, if improvement of the method performance is needed, only actions directed towards enhancing the signal-to-noise ratio are suitable.     

Rapid and simple method for the determination of copper, manganese and zinc in rat liver by direct flame atomic absorption spectrometry.

An acidic homogenate method, which includes simple homogenization pre-treatment of tissue material and direct nebulization flame atomic absorption spectrometry (FAAS), is successfully applied to the simultaneous determination of copper, manganese and zinc in rat liver. The proposed method involves only a few steps for sample pre-treatment at room temperature, making the risk of systematic errors very small. Because recoveries of 101% for copper, 98% for manganese and 100% for zinc could be achieved using aqueous standards, matrix-matched standards were redundant. Favourable results obtained in biological media, including limits of detection of 0.04, 0.03 and 0.04 mg l-1 for Cu, Mn and Zn, respectively, together with accuracies of 0-3%, and relative standard deviations ranging from 2 to 10% are further evidence of the suitability of the method.     

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.     

The determination of lead in blood by atomic fluorescence flame spectrometry

The use of atomic flame fluorescence for the direct determination of lead in diluted blood is described. The method is sensitive enough to determine the lead concentration in 20× diluted blood accurately and with a precision of better than 4% at a lead concentration level of 0.20 μg ml^-1. A special design of hollow cathode lamp is used, with an argon-hydrogen-oxygen flame. Sodium interference is compensated by addition to standards, and light scatter effects are eliminated by a simple filter. Linear response to lead concentration is obtained in the range 0–40 μg ml^-1.     

微波消解火焰原子吸收光谱法连续测定金银花中铁、锌、铜和锰

采用微波消化技术,以氘灯背景校正方式,在HNO3介质中,直接用火焰原子吸收法在同一体系中连续测定了金银花中微量元素Fe、Zn、Cu、Mn,并优化了最佳实验条件.在选定条件下,检出限为Fe 0.0047 μg/mL,Zn 0.0032μg/mL,Cu 0.0052μg/mL,Mn 0.0028μg/mL,相对标准偏差为1.5%～3.2%,回收率为96.4%～103.4%.适用于金银花中微量Fe、Zn、Cu、Mn的测定.     

Problems in the determination of chromium in biological materials. Comparison of flameless atomic absorption spectrometry and neutron activation analysis

Summary The effects of sample preparation on the analysis of chromium in biological matter have been investigated using brewer's yeast as a test material. The apparent chromium content of the yeast as determined by flameless atomic absorption spectrometry was significantly higher after destruction of the organic matter with HNO₃ in a closed pressure vessel than after wet-ashing in open vessels and after direct introduction of the sample into the graphite furnace. The results obtained by neutron activation analysis without any sample preparation, which corresponded to the atomic absorption values after digestion in the pressure vessel, showed that considerable errors arise in the other methods of sample treatment. Chromium analyses of dried and ashed yeast suggest that losses of volatile organic chromium compounds may occur during heating.

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Probleme bei der Chrombestimmung in biologischem Material. Vergleich der Bestimmung durch flammenlose AAS und Neutronenaktivierung

Zusammenfassung Die Einflüsse der Probenvorbereitung auf die Analyse von Chrom in biologischen Materialien wurden am Beispiel der Bierhefe untersucht. Bei Anwendung der flammenlosen Atomabsorptionsspektrometrie wurden nach der Zerstörung der organischen Substanz mit HNO₃ in einem geschlossenen Druckgefäß signifikant höhere Chromkonzentrationen gefunden als nach der Naßveraschung in offenen Gefäßen und nach direkter Eingabe der Proben in die Graphitrohrküvette. Aus dem Vergleich mit den bei der Neutronenaktivierungsanalyse ohne Probenvorbehandlung erhaltenen Ergebnissen, die den Atomabsorptions-Werten nach der Naßveraschung im Druckgefäß entsprachen, ist ersichtlich, daß bei den anderen Methoden der Probenvorbereitung beträchtliche Fehler auftreten. Die Chromanalysen von getrockneten und veraschten Hefeproben lassen vermuten, daß beim Erhitzen Verluste durch leichtflüchtige organische Chromverbindungen entstehen.

     

Electrothermal atomic absorption spectrometry determination of molybdenum in whole blood

A method for the determination of molybdenum in whole blood by atomic absorption spectrometry with electrothermal atomization was developed and evaluated. Erbium (25 μg) was chosen from several potential chemical modifiers (Sm, Lu, Ho, Eu and Pd+Mg) as the most appropriate for the sensitive and reliable determination of molybdenum in such sample. The process used was direct dilution of the sample in a ratio 1:2 with a 0.1% (v/v) Triton X-100 solution. The injection of 20 μl of a solution of 15% (w/v) hydrogen peroxide and running the temperature program after 5 firings greatly reduced the effect of build-up of carbonaceous residues within the atomizer. The limit of detection and working ranges, respectively, were 0.6 and 2.0–100.0 μg l⁻¹, and the characteristic mass was 7.2 pg. The relative standard deviation varied from 0.8 to 1.5% for within and between batch determinations, respectively. The determination of molybdenum in Seronorm™ Trace Elements in Whole Blood with known added amounts of the analyte was performed to asses the accuracy. The optimized procedure has been applied to the determination of molybdenum in whole blood specimens of 20 subjects taken before and 10–12 h after receiving an over-supply of 1 mg of molybdenum. The molybdenum concentrations (±S.D.) were 10.9±0.4 μg Mo l⁻¹ (range 9.9–11.6 μg Mo l⁻¹) and 15.4±0.4 μg Mo l⁻¹ (range 13.1–16.9 μg Mo l⁻¹) for the individuals before and after the administration of molybdenum.     

Precipitation-dissolution system for silver preconcentration and determination by flow injection flame atomic absorption spectrometry

In this paper, flame atomic absorption spectrometry was used for the determination of silver in various materials. The proposed preconcentration method is based on the continuous precipitation of silver as p-dimethylaminobenzilidene-rhodanine (PDBR) complex and dissolution of the precipitate with potassium cyanide. EDTA was added to the sample solution to mask large concentrations of Fe(III), Ni(II), Cu(II), Zn(II), Pb(II), Co(II) and Al(III). An enhancement factor of 20 was obtained for a preconcentration time of 3 min, resulting in a sampling frequency of 16 h(-1). The detection limit (3sigma) in the sample solution was 5 ngml(-1). The relative standard deviation at 30 ngml(-1) level was 4.7%. Analytical results obtained for alloy, biological reference material and ore samples analyzed were in good agreement with the certified values and comparable to those obtained with other techniques.