Investigation of the analytical performance of gliding spark source mass spectrometry (GSSMS) for the trace analysis of nonconducting materials

A radiofrequency (rf) spark discharge in vacuum developing across the surface of dielectrics – a so-called gliding spark – has been applied to the direct mass spectrometric trace analysis of nonconducting materials. The special configuration of the electrodes strengthened the electric field over the surface of a nonconducting sample and created optimum conditions for the sputtering and ionization of the sample material. Mass spectrometric investigations of the charge composition of atomic ion and molecular ion formation in radiofrequency gliding spark plasma showed a significant difference to that of the original rf spark discharge between two conducting electrodes. The analytical figures of merit (reproducibility, relative sensitivity factors and detection limits of chemical elements) of gliding spark source mass spectrometry have been studied by using the glass standard reference materials NIST SRM 610 and 611 for the determination of trace elements in glass matrix. Received: 31 March 1999 / Revised: 10 May 1999 / Accepted: 13 May 1999     

Classification of the distribution of trace impurities by spark source mass spectrometry analysis

Spark source mass spectrometry in combination with principal component analysis and clustering analysis was used to investigate the trace element distributions in metallic samples. The analysis of Zn and Cu samples and a comparison with direct imaging secondary ion microscopy demonstrated the consistency of the approach.On leave from Department of Chemistry, Nanjing Normal University, Nanjing, People's Republic of China.     

Determination of trace impurities in cobalt by spark source mass spectrometry

An analytical method, SSMS, for the determination of trace impurities in cobalt is described. This element is used as raw material for the production of⁶⁰Co in Embalse Nuclear Power Station. Tin, aluminum, lead, silicon, molybdenum, calcium, vanadium, boron, chromium, zirconium, tungsten, nickel, magnesium, iron, zinc and copper were determined. Manganese, analyzed by AAS, was used as an internal standard. The measurements were semiquantitative. The accuracy of the results was compared with that of emission spectrography and atomic absorption spectrometry, the agreement was found to be satisfactory.     

Use of spark source mass spectrometry for the analysis of copper cathodes

Summary More than 50% of the copper production is used as electrorefined material of high electrical conductivity in the field of electrical engineering. A lot of the normal copper impurities has a decreasing influence on the electrical conductivity so that an electrorefining process is necessary. The use of Periodic Current Reversal (PCR) leads to higher practical current densities producing cathodes of good quality. Some laboratory tests were made by the switching cycles. The contents of the impurities of the cathodes produced were analyzed by SSMS. Using a standard sample 4 photoplates were exposed and a sensitivity factor was determined for each element. Then the cathodes produced by the PCR-electrorefining process were analyzed. The analytical data were corrected by the sensitivity factors.

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Einsatz der Funkenmassenspektrometrie bei der Analyse von Kupferkathoden

Zusammenfassung Mehr als 50% der Weltkupferproduktion wird als elektroraffiniertes Cu in der Elektroindustrie eingesetzt. In beträchtlicher Weise beeinflussen Anzahl und Gehalt der Verunreinigungselemente die elektrische Leitfähigkeit. Ihre Entfernung erfolgt durch Raffinationselektrolyse; eine Elektrolyse mit periodischer Stromumkehr erlaubt höhere Stromdichten bei gleich guter physikalischer Qualität. Einige Untersuchungen wurden unter Anwendung der reversiblen Stromumkehr mit unterschiedlichen Stromdichten und Umschaltzeiten an Cu-Kathoden vorgenommen und deren Verunreinigungsgehalte mittels Funkenmassenspektrometrie bestimmt. Unter Verwendung eines Standards wurden 4 Photoplatten exponiert, und für jedes Element wurde ein Empfindlichkeitsfaktor ermittelt. Danach wurden die mittels Stromumkehrraffinationselektrolyse hergestellten Cu-Proben untersucht. Die Konzentrationswerte wurden mit Hilfe der Empfindlichkeitsfaktoren korrigiert.

     

Chemical analysis and distribution investigation of trace elements in indium matrix by spark source mass spectrometry

Summary High-purity indium was analysed by spark source mass spectrometry, using electrical and photoplate detection. For the calibration of the differences in elemental sensitivity, a standard sample was prepared in which 10 impurities were determined by graphite furnace atomic absorption spectrometry. In this way accuracies of less than 40% were obtained for relatively homogeneous elements at ppm and sub-ppm level. About 40 elements could be determined with detection limits of 10 to 30 ppb. Two pattern recognition methods, principal component analysis and clustering analysis, were applied to obtain information on trace element distribution, which indicated that a number of elements were strongly spatially correlated in the analysed sample.

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Chemische Analyse und Verteilungsbestimmung von Spurenelementen in Indium-Matrix durch Funkenquellen-Massenspektrometrie

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On leave from: Department of Chemistry, Nanjing Normal University, Nanjing, People's Republic of China     

Part I. Principles of spark source mass spectrometry (SSMS)

Summary A general survey of spark source mass spectrometry is given, comprising apparatus (ion source, analyzer, ion detector, spectral information), working techniques (sample preparation, evaluation methods) and a brief outline of application possibilities.

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Prinzipien der Funken-Massenspektrometrie

Zusammenfassung Ein grundlegender Überblick über die Funken-Massenspektrometrie wird gegeben, der die Apparatur (Ionenquelle, Analysator, Ionendetektor, Spektreninformation) sowie das Arbeitsverfahren (Probenvorbereitung, Auswertungsmethoden) und eine zusammenfassende Übersicht über die Anwendungsmöglichkeiten umfaßt.

     

Determination of trace constituents in high purity germanium tetrachloride by spark source mass spectrometry

Summary A procedure was developed for the determination of trace constituents at sub-ppm levels in high purity germanium tetrachloride (GeCl₄) by spark source mass spectrometry using the photoplate detection system. Experiments were conducted to study the loss of various elements present in the chloride form in GeCl₄ by using energy dispersive X-ray fluorescence. Relative sensitivity factors for various elements were determined using synthetically prepared samples. Blanks were determined for graphite powder and for quartz bi-distilled water. Intensities of the doubly charged ions for a number of elements were also determined and used for confirming the semi-quantitative results. The paper presents typical results obtained in the analysis of high purity GeCl₄ obtained from a commercial source. For a number of elements results were compared with those obtained with graphite furnace atomic absorption spectrometry.

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Bestimmung von Spurenbestandteilen in hochreinem Germaniumtetrachlorid mit Hilfe der Funkenionen-Massenspektrometrie

Zusammenfassung Ein Verfahren zur Bestimmung von Spurenbestandteilen in hochreinem GeCl₄ im sub-ppm-Bereich mit Hilfe der Funkenionen-MS mit Photoplattendetektion wurde ausgearbeitet. Untersuchungen über den Verlust verschiedener Elemente als Chloride wurden mit energiedispersiver Röntgenfluorescenz durchgeführt. Relative Empfindlichkeitsfaktoren wurden anhand synthetischer Proben bestimmt. Für Graphitpulver und bidestilliertes Wasser wurden Blindwerte bestimmt. IntensitÄten für zweifach geladene Ionen verschiedener Elemente wurden gemessen und zur BestÄtigung halbquantitativer Ergebnisse herangezogen. Typische Resultate für eine handelsübliche Probe werden angegeben. In einigen FÄllen wurden Vergleiche mit den Ergebnissen aus der Graphitofen-AAS angestellt.

     

Determination of trace impurities in zircaloy-2 and tellurium by spark source mass spectrometry

Determination of trace impurities in zircaloy-2 and tellurium by Spark Source Mass Spectrometry (SSMS) is reported. The advantage of SSMS lies in the fact that along with metallic trace constituents even the nonmetallic impurities and gases including hydrogen can also be determined.     

Influence of spark generator parameters in the analysis of graphite electrodes by spark source mass spectrometry

Spark source mass spectrometric analyses of doped carbon samples were performed at different pulse lengths, pulse frequencies and breakdown voltages. The pulse length and pulse frequencies had no influence on the analysis. The relation between breakdown voltage, spark gap and sample matrix was determined. With increasing breakdown voltage, the abundance of the multiply charged ions was found to decrease, whereas the abundance of the cluster ions increased. The breakdown voltage was also found to affect the absolute and relative intensities of different elements in different manners. Interpretation of these results led to some new considerations on the phenomena in a spark discharge.     

Analysis of tellurium by spark source mass spectrometry

Summary Three tellurium standards were analyzed by both spark source mass spectrometry (SSMS) and graphite furnace atomic absorption spectrophotometry (GFAAS). From these results relative sensitivity coefficients (RSC) for spark source mass spectrometry were derived for 24 elements.With these RSC's SSMS results within a factor 1.5 from the GFAAS values could be obtained for the determination of various impurities in tellurium. A comparison is made between SSMS, GFAAS and glow discharge mass spectrometry (GDMS) for the analysis of 4–6 N tellurium samples.

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Analyse von Tellurium mit Hilfe der Funkenionisations-Massenspektrometrie

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Dedicated to Prof, Dr. G. Tölg on the occasion of his 60th birthday     

Part IV. Review and evaluation of spark source mass spectrometry as an analytical method

Summary The analytical features and most important fields of application of spark source mass spectrometry are described with respect to the trace analysis of highpurity materials and the multielement analysis of technical alloys, geochemical and cosmochemical, biological and radioactive materials, as well as in environmental analysis. Comparisons are made to other analytical methods. The distribution of the method as well as opportunities for contract analysis are indicated and developmental tendencies discussed.

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Überblick und Bewertung der Funken-Massenspektrometrie als Analysenmethode

Zusammenfassung Die Analyseneigenschaften und wichtigsten Einsatzgebiete der Funken-Massenspektrometrie zur Spurenanalyse an hochreinen Materialien und zur Multielementanalyse an technischen Legierungen, geo- und kosmochemischen, biologischen und radioaktiven Materialien sowie in der Umweltanalytik werden beschrieben. Vergleiche zu anderen Analysenverfahren werden gegeben. Die Verbreitung der Methode sowie Möglichkeiten der Auftragsanalytik werden angegeben und Entwicklungstendenzen diskutiert.

     

A new spark source mass spectrometric technique for the analysis of sub-ng amounts of trace elements

Summary Spark source mass spectrometric tip-top-technique (TTT) is a new method for the analysis of sub-ng amounts of chemically separated trace elements in geological material. Besides its application to dissolved samples, TTT differs from conventional spark source mass spectrometry in reduction of measuring time (few minutes), photoplate background, and interferences by isobars and cluster-ions, resulting in enhanced sensitivities. Detection limits range from about 5 to 20 pg for the rare earth elements, U and Th, and from about 10 to 100 pg for noble metals. Precisions and accuracies of 1 to 5% are gained for trace elements abundances about 1 ng.A potential and especially useful application of TTT is the analysis of rocks available only in very small sample sizes and/or with very low concentration levels of trace elements. An additional application is the determination of osmium isotopes in geological material.

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Neues funkenmassenspektrometrisches Verfahren für die Analyse von sub-ng-Mengen von Spurenelementen

     

Matrix effects and analysis of biological material by spark source mass spectrometry

Summary Spark-source mass spectrometric analyses of synthetic simulated biological samples were performed to determine the importance of matrix effects. A correlation between the variation of the relative sensitivity coefficients (RSC's) and the spark plasma composition, hence plasma temperature, was found. The determined RSC's were used in the analysis of four biological standard reference materials. An accuracy of 10–13% and detection limits between 0.005 and 0.5 ppm were obtained during analysis under normal conditions.

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Matrixeffekte und Analyse von biologischem Material mit Hilfe der Funkenionen-Massenspektrometrie

Zusammenfassung Um die Bedeutung von Matrixeffekten zu untersuchen, wurden Analysen von synthetischem biologischem Material mit der Funkenquellen-Massenspektrometrie durchgeführt. Dabei wurde eine Beziehung zwischen der Veränderung der relativen Empfindlichkeitskoeffizienten und der Zusammensetzung des Funkenplasmas (und damit der Plasmatemperatur) festgestellt. Die bestimmten Empfindlichkeitskoeffizienten wurden zur Analyse von vier biologischen Standardreferenzmaterialien eingesetzt. Unter normalen Bedingungen wurde eine Genauigkeit von 10–13% und Nachweisgrenzen zwischen 0,005 und 0,5 ppm erreicht.

     

Computer aided mathematical analysis of interferences in spark source mass spectrometry spectra

Summary When analysing sulphide ores by spark source mass spectrometry different interferences on some mass-to-charge ratios, such as 60–62 (Ni) and 193–197 (Ir,Pt,Au), have been observed. These lines should be used in the estimation of element concentrations. Our program (SM13) gives hints to possible molecular ions derived from the matrix of the sample by using the theory of combination.The validity of this theory was checked by analysing the ASK III standard [3] and mixtures of sulphides and oxides. The formation of interfering molecular ions such as SiS⁺ and AgFeS⁺ was checked.

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Computergestützte mathematische Auswertung von Interferenzen in Funken-Massenspektren

Zusammenfassung Bei der Analyse sulfidischer Erze wurden in der Funken-Massenspektrometrie für die Masse-zu-Ladungs-Verhältnisse 60–62 (Ni) sowie 193–197 (Ir,Pt,Au), die für die Elementbestimmungen verwendet werden sollten, Interferenzen beobachtet. Hierzu wurden mit Hilfe eines Auswertungsprogramms (SM13) durch mathematische Kombinatorik Hinweise auf Interferenzen durch mögliche Molekülionen aus der Matrixzusammensetzung abgeleitet.Die Anwendbarkeit des mathematischen Modells wurde am ASK III Standard [3] sowie an Mischungen von Sulfiden und Oxiden erprobt. Die Bildung der interferierenden Molekülionen des Typs SiS⁺ und AgFeS⁺ konnte nachgewiesen werden.

     

Analysis of radioactive metals by spark source mass spectrometry

A spark source mass spectrograph with photographic plate recording has been adapted for the analysis of plutonium and americium metals. Over seventy elements can be determined simultaneously in these metals. A comparison has been made between results obtained by mass spectrography and by conventional methods for impurity elements. The operations involved in handling radioactive materials in the mass spectrograph are also discussed.     

Analysis of geothermal waters by spark source mass spectrometry

Summary Although the analysis of thermal water by spark-source mass spectrometry (SSMS) is rather timeconsuming, it allows the detection of about 20 elements of geochemical interest down to the ppb-level. A physical preconcentration is proposed in order to collect elements having quite different chemical properties, e.g. alkalis, transition elements, and elements occurring in anionic form. The relative sensitivity factors appear to be rather independent of the salt content of the graphite electrodes. Contrary to neutron activation analysis, SSMS has a quite uniform elemental sensitivity, and allows to determine elements for which neutron activation is not suitable, e.g. Sn and Pb. The precision of SSMS is however by a factor of about 2 worse than that obtained for neutron activation.

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Analyse von geothermalen Wässern mittels Funken-Massenspektrometrie

Zusammenfassung Die Analyse von Thermalwasser mittels Funken-Massenspektrometrie ist zwar zeitraubend, sie gestattet aber die Bestimmung von etwa 20 geochemisch interessanten Spurenelementen im ppb-Bereich. Es wird eine physikalische Anreicherung vorgeschlagen, um Elemente mit ganz verschiedenen chemischen Eigenschaften erfassen zu können, z. B. die Alkaligruppe, die Elemente der Übergangsreihe und anionische Verbindungen. Die relativen Empfindlichkeitsfaktoren sind vom Salzgehalt in den Graphitelektroden ziemlich unabhängig. Wegen ihrer gleichmäßigen Elementempfindlichkeit liefert die Funken-Massenspektrometrie Auskunft über den Gehalt von Elementen, die mit Neutronenaktivierung nicht erfaßt werden können, wie z. B. Sn und Pb. Ihre Reproduzierbarkeit ist aber etwa zweimal schlechter.

     

Applications of mass spectrometry in the trace element analysis of biological materials

The importance of mass spectrometry for the analysis of biological material is illustrated by reviewing the different mass spectrometric methods applied and describing some typical applications published recently. Though atomic absorption spectrometry is used in the majority of analyses of biological material, most mass spectrometric methods have been used to some extent for trace element determination in biomedical research. The relative importance of the different methods is estimated by reviewing recent research papers. It is striking that especially inductively coupled plasma mass spectrometry is increasingly being applied, partly because the method can be used on-line after chromatographic separation, in speciation studies. Mass spectrometric methods prove to offer unique possibilities in stable isotope tracer studies and for this purpose also experimentally demanding methods such as thermal ionization mass spectrometry and accelerator mass spectrometry are frequently used.     

Quantitative multielement analysis of geochemical and cosmochemical samples using spark source mass spectrometry

Summary Spark source mass spectrometry is a useful method for the chemical analysis of geochemical and cosmochemical samples. The technique is highly sensitive (limit of detection between 0.001 ppm and 0.1 ppm) and allows the simultaneous determination of about 70 major, minor and trace elements. With the help of electrical ion detection and multielement isotope dilution on solid and dissolved samples, a precision of better than ±5 % is obtained for many elements. The measured concentrations are in good agreement with literature data.

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Quantitative Multielementanalyse von geo- und kosmochemischen Proben unter Verwendung der Funken-Massenspektrometrie

Zusammenfassung Die Funken-Massenspektrometrie ist eine nützliche Methode für die chemische Analyse von geochemischen und kosmochemischen Proben. Diese Technik ist sehr empfindlich (die Nachweisgrenze liegt zwischen 0,001 ppm und 0,1 ppm) und ermöglicht die gleichzeitige Bestimmung von ungefähr 70 Haupt-, Neben- und Spurenelementen. Mit Hilfe des elektrischen Ionennachweises und der Multielement-Isotopenverdünnungsmethode an festen und gelösten Proben wird eine Genauigkeit von besser als ±5% für viele Elemente erreicht. Die ermittelten Konzentrationen stimmen gut mit Literaturdaten überein.