Flow injection—atomic absorption spectrometry with organic solvents

A flow injection technique with an organic solvent carrier stream is recommended for the determination of trace elements by atomic absorption spectrometry. Carrier streams of methyl isobutyl ketone and especially n-butyl acetate are effective in enhancing sensitivity. The proposed method permits about 300 determinations per hour with a relative standard deviation of less than 5%.     

Determination of some heavy metals in sea water by atomic absorption spectrophotometry

Summary Direct determination of trace metals in sea water by flame atomic absorption technique suffers from serious interferences caused by the high salt content. Separation of the metals from the matrix has been effected by chelation and extraction with ammonium pyrrolidine dithiocarbamate and methyl-isobutyl-ketone. Besides a separation preconcentration and increased sensitivity is achieved with this extraction. Organic substances and metal-organic complexes are destroyed with UV-radiation before extraction is carried out. Flameless atomic absorption has been tried using the Heated Graphite Furnace combined with a) a selective volatilization procedure, b) removing of sodium from the samples using hydrated antimon pentoxide (HAP). Both methods were used to remove the interfering substances (mainly sodium salt). All the techniques have been compared by analysing the same sea water samples, some of which were also analysed by other laboratories.

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Bestimmung einiger Schwermetalle in Meereswasser durch Atomabsorptions-Spektralphotometrie

Zusammenfassung Die direkte Bestimmung der Spurenmetalle in Meereswasser durch Flammen-Atomabsorption wird durch den hohen Salzgehalt behindert. Die Abtrennung der Metalle von der Matrix wurde durch Komplexierung und Extraktion mit Ammoniumpyrrolidindithiocarbamat und Methylisobutylketon erreicht, wodurch außerdem eine Anreicherung und Steigerung der Empfindlichkeit erzielt wird. Organische Substanzen und metallorganische Komplexe können durch UV-Bestrahlung vor der Extraktion zerstört werden. Die flammenlose Technik mit Hilfe des erhitzten Graphitrohres wurde in Kombination mit a) einer selektiven Verdampfungsmethode und b) der Entfernung des Natriums mit hydratisiertem Antimonpentoxid eingesetzt. Alle Verfahren wurden an Hand der gleichen Wasserproben verglichen. Tests wurden auch von anderen Laboratorien durchgeführt.

This work was made possible by substantial grants from International Atomic Energy Agencies (IAEA) and from the Royal Norwegian Council for Scientific and Industrial Research.     

Determination of wear metals in lubricating oils by flame atomic absorption spectrophotometry

A simple, rapid and reliable method was developed for the determination of copper, nickel, iron and lead in fresh and used lubricating oil samples by flame atomic absorption spectrophotometry (FAAS). In the present study, a mixture of organic solvents containing propionic acid and iso-butylmethyl ketone (1: 1) was used to extract the metals from lubricating oil samples followed by FAAS analysis. Aqueous standard solutions can be easily employed with the proposed mixed solvent system instead of organometallic standards. The analytical results obtained by employing the proposed solvent extraction system were found to be in good agreement with the results for aqueous media obtained after the destruction of oil samples matrix. Percentage recovery studies showed 88–98% for Cu, 92–95% for Fe, 96–106% for Ni and 84–100% for Pb with relative standard deviation of 2–6%. The developed method was effectively applied to routine determination of Cu, Ni, Fe, and Pb in lubricating oil samples.     

Determination of heavy metals in seawater and marine organisms by flameless atomic absorption spectrophotometry

Summary For the determination of cadmium in culture water from toxicological experiments with marine organisms direct flameless atomic absorption spectrophotometry seems to be an appropriate method, because it is less complicated than any combination with an extraction method. Unfortunately, it cannot be applied in the g·l^–1-range without modifications, because matrix effects lead to unacceptable variations in the results. It was found that these difficulties can be overcome by the addition of ammonium peroxodisulphate and sulphuric acid. A routine method basing on this effect has been developed.

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Bestimmung von Schwermetallen im Meerwasser und in marinen Organismen durch flammenlose Atomabsorptions-Spektralphotometrie. VI. Cadmiumbestimmung in Kulturwässern von toxikologischen Experimenten mit Meeresorganismen

Zusammenfassung Zur Cadmiumbestimmung in Kulturwasser von toxikologischen Versuchen mit marinen Organismen scheint die direkte flammenlose Atomabsorptions-Spektralphotometrie besonders geeignet zu sein, denn sie ist weniger umständlich als jede Kombination mit einer Extraktionsmethode. Ohne Modifikationen kann die Direktbestimmung jedoch im g/l-Bereich nicht eingesetzt werden, denn Matrixeffekte bewirken allzu starke Streuungen der Meßergebnisse. Es wird gezeigt, daß ein Zusatz von Ammoniumperoxodisulfat und Schwefelsäure zur Probenlösung eine deutliche Verbesserung bewirkt. Eine Routinemethode wurde entwickelt, bei der von diesem Effekt Gebrauch gemacht wird.

     

Determination of nonmetals by atomic absorption spectrophotometry

Inorganic anions and organic compounds are determined using conventional atomic absorption apparatus. Several methods are studied in which the desired compound either limits or interferes with the determination or absorption of a metal. A direct relationship is obtained between the absorption by the metal and the amount of substance sought. Substances determined include orthophosphate, sulfate, iodide, sulfide, iodate, glucose, protein, 8-hydroxyquinoline, ethylenediaminetetraacetic acid, and ammonium pyrrolidine dithiocarbamate.     

Determination of vanadium by atomic absorption spectrophotometry

Methods for the determination of vanadium, in the range 0.5–100 mg/l, by atomic absorption spectroscopy in an oxy-acetylene as well as in a nitrous oxideacetylene flame are presented. For use with oxy-acetylene flames, vanadium is extracted as vanadium cupferrate into a mixture of methyl isobutyl ketone and oleic acid (78:22, v/v) and the organic phase is aspirated to the flame. The sensitivity is 0.7 mg/l of vanadium in the organic phase. For nitrous oxide-acetylene flames, an aqueous solution of vanadium is aspirated directly. The sensitivity is further improved by the use of methyl isobutyl ketone, the addition of Al³⁺ and diethylene glycol diethyl ether. Many potential interferences were examined and methods to overcome those found are given.     

Determination of thallium by atomic absorption spectrophotometry

Summary The determination of thallium by atomic-absorption Spectrophotometry is described. Many substances interfere with the direct analysis of thallium under the conditions chosen. However, these interferences can be overcome by adding a lithium, potassium, or sodium buffer (5000 ppm). In this way the deviations caused by foreign substances can be reduced to less than ten per cent. Under the same conditions the effect of organic solvents has been studied.

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Zusammenfassung Die Bestimmung von Thallium mit Hilfe der atomaren Absorptionsspektrophotometrie wird beschrieben. Die direkte Bestimmung von Thallium wird im allgemeinen durch viele Fremdionen in höheren Konzentrationen gestört. Durch Verwendung eines Li-, K-, oder Na-Puffers (5000 ppm) können die Störungen auf weniger als 10% herabgesetzt werden. Unter den gleichen experimentellen Bedingungen wird die Wirkung von organischen Lösungsmitteln untersucht.

     

消解方法对原子吸收分光光度法测定藜麦中铅含量的影响

采用原子吸收分光光度法测定藜麦中的痕量铅,研究了五种不同的前处理方式对藜麦中铅含量测定的影响。五种方法的加标回收率为95.4%~104.8%,分析标准物质的结果与推荐值一致,比较得出微波消解法具有操作简单、消解彻底、稳定性高和污染低等优点,在藜麦中铅含量的测定中具有很大的应用前景。     

Determination of heavy metals in seawater and in marine organisms by flameless atomic absorption spectrophotometry

Summary The appicability of flameless AAS to direct cadmium determinations in seawater samples is limited to a level of about 2g l^–1 [22]. Thus, for lower concentrations, a combination with an extraction method has been tested. It has been shown that the extraction can well be carried out with ammonium pyrrolidine dithiocarbamate (APDC). However, several modifications of the well known APDC/MIBK-Method were necessary. The key for the method presented was the choice of an appropriate solvent (CCl₄, C₂Cl₄) for the reagent as well as for its Cd-complex. Then a simple, sensitive and miniaturized method has been developed, which has then been applied to a few natural seawater samples.

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Bestimmung von Schwermetallen im Meerwasser und in marinen Organismen durch flammenlose AtomabsorptionsspektralphotometrieVII. Ein einfaches Extraktionsverfahren zur Bestimmung extrem niedriger Cadmiumgehalte in kleinen Seewasserproben

Zusammenfassung Die direkte Bestimmung von Cadmium im Meerwasser durch flammenlose AAS stößt unterhalb einer Konzentration von 2g l^–1 auf beträchtliche Schwierigkeiten [22]. Deshalb wurde eine kombinierte Methode erprobt, bei welcher das Metall zunächst extrahiert und dann mittels flammenloser AAS bestimmt wird. Es zeigte sich, daß die Extraktion gut mit Ammoniumpyrrolidindithiocarbamat (APDC) ausgeführt werden kann. Es wurden jedoch erhebliche Abwandlungen der wohlbekannten APDC-MIBK-Extraktionsmethode erforderlich. Erst als es gelang, ein geeignetes Solvens (CCl₄, C₂Cl₄) sowohl für das APDC als auch für seinen Cd-Komplex zu finden, konnte eine einfache, empfindliche und miniaturisierte Bestimmungsmethode entwickelt werden, mit deren Hilfe dann der Cd-Gehalt einiger Meerwasserproben bestimmt wurde.

     

Blood lead by furnace-Zeeman atomic absorption spectrophotometry

A quick, accurate graphite furnace-atomic absorption spectrophotometric method for blood lead in the range 5 to 50 μg/dl was evolved by adding a 0.100-ml blood sample to 0.400 ml of aqueous 0.2% (w/v) Triton X-100, followed by the addition of 0.500 ml of Type I water. After shaking, a 10-μl aliquot was inserted into a pyrolytically coated graphite furnace tube in a Zeeman atomic absorption spectrophotometer. The method was validated by the method of standard additions, by mixing bloods of known lead content in known ratios, by two independent methods of isotope dilution/mass spectrometry, and by two independent methods involving anodic stripping voltammetry. Mixing bloods of known lead content in defined ratios is an acceptable substitute for the standard additions method.     

The determination of selenium by atomic absorption spectrophotometry

The problems involved in the determination of selenium by atomic absorption spectrophotometry are discussed. A practical method is described for which the sensitivity is approximately 1 p.p.m. Such concentrations can be determined in organic samples, but with mineral samples the preliminary treatment renders the procedure unsuitable for concentrations lower than 50 p.p.m. in a sulphide ore.     

Determination of heavy metals in sea water and in marine organisms by flameless atomic absorption spectrophotometry

Summary An ultraquick light-beam oscillograph has been used to track the growing and destruction of the atomic cloud in a graphite tube atomizer. In view of the results obtained it was stated that the analytical signal is mainly determined by the stepwise growing of the atomic cloud and its simultaneous destruction by thermal expansion of the inert gas from the tube. Thermodiffusion and recondensation seem to be much slower processes. The dependence of the analytical signal on the settings of the atomizer or the presence of matrix components and on thermal ballast like the L'vov platform is discussed in view of the above thesis. Finally, some proposals are made to overcome the matrix effects by separating the atomization process from the heating and thermal expansion of the surrounding inert gas. For this purpose atomizers with two separate electric current circuits are recommended.

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Bestimmung von Schwermetallen im Meerwasser und in marinen Organismen durch flammenlose AtomabsorptionsspektralphotometrieXV. Matrixeffekte in Graphitrohr-Atomisatoren und Wege zu ihrer Überwindung

Zusammenfassung Ein schneller Lichtpunktschreiber wurde eingesetzt, um das Entstehen und den Abbau der Atomwolke in einem Graphitrohr-Atomisator zu verfolgen. Aufgrund der erhaltenen Ergebnisse wird geschlossen, daß das analytische Signal im wesentlichen durch das allmähliche Wachsen der Atomwolke und deren gleichzeitigen Abbau infolge thermischer Ausdehnung des Inertgases im Rohr bestimmt wird. Thermodiffusion und Rekondensation verlaufen offenbar langsamer. Die Abhängigkeit des analytischen Signals von den Geräteeinstellungen, von der Gegenwart bestimmter Matrixkomponenten und von thermischem Ballast wie der L'vov-Plattform wird im Lichte der o.a. These diskutiert. Schließlich werden einige Wege zur Behebung der Matrixabhängigkeit vorgeschlagen. Sie zielen auf eine möglichst weitgehende Trennung der eigentlichen Atomisierung vom Erhitzen und Sichausdehnen des umgebenen Inertgases. Hierzu werden Atomisatoren mit zwei getrennten elektrischen Heizkreisen vorgeschlagen.

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XIV. Mitt. Fresenius Z Anal Chem (1982) 310:254–256

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Presented at the Colloquium Spurenanalytik, Konstanz, 7.–9.4. 1981     

The determination of gold by atomic absorption spectrophotometry

Gold can be isolated from most other elements other than the platinum metals by the extraction of iron(II) 1,10-phenanthroline tetrabromoaurate in chloroform. After isolation gold can be determined in the organic solvent by atomic absorption spectroscopy or colorimetrically by decomposition of the complex and determination of the iron by bathophenanthroline.     

Determination of heavy metals in sea water and in marine organisms by flameless atomic absorption spectrophotometry

Summary This paper presents results of an intercalibration of cadmium determination by means of flameless AAS in biological materials from toxicological experiments. Furthermore, the philosophy of this kind of investigation is discussed in some detail. The goal and the result of this investigation was a correspondence of the measurement results within an acceptable range. Contamination during further handling has been identified as the main reason for severe deviations. The authors made measurements in the labs of several colleagues. The equipment itself did not produce individual variations. Repeated intercomparison after elimination of identified systematic errors showed sufficient correspondence of the results.Teil XII: Fresenius Z. Anal. Chem.301, 294–299 (1980)     

Determination of heavy metals in sea water and in marine organisms by flameless atomic absorption spectrophotometry

Summary This publication is a part of a series in which the author describes a set of methods for the determination of cadmium in environmental samples by means of flameless AAS. Common properties of these methods are their miniaturization and standardization. These have been attained by the utmost reduction of the number of steps and by their simplification. The method described in this publication consists of an acid digestion procedure followed by neutralization, extraction, and flameless AAS measurement. The main characteristics are: digestion takes place in small 1.5 ml tubes of quartz, polyvinyldifluoride or polypropylene. Neutralization is not performed by titration but only by an excess of saturated NaHCO₃ solution. Extraction results are independent of pH in the region to be expected. Extraction is carried out by a (stable) solution of APDC in CCl₄. The organic extract is also stable for at least 16h. Precision of the method lies in the range of 8.4%, at a concentration of 18.9 ng Cd g^–1; sensitivity is at least in the range of 1.2 ng Cd g^–1. The latter can be increased, if necessary, by a several-step extraction procedure.Teil VIII: Z. Lebensm.-Unters. Forsch. 168, 193-194 (1979)