TY - RPRT A1 - Vogl, Jochen A1 - Yim, Y.-H. A1 - Lee, K.-S. A1 - Goenaga-Infante, H. A1 - Malinovskiy, D. A1 - Vocke, R. D. A1 - Murphy, K. A1 - Nonose, N. A1 - Rienitz, O. A1 - Noordmann, J. A1 - Näykki, T. A1 - Sara-Aho, T. A1 - Ari, B. A1 - Cankur, O. T1 - CCQM-P134 Pb isotope amount ratios and delta-values in bronze N2 - Isotope amount ratios (hereafter referred to as simply isotope ratios) are proving useful in an ever increasing array of applications that range from studies unravelling transport processes, to pinpointing the provenance of specific samples as well as trace element quantification by using isotope dilution mass spectrometry (IDMS). These expanding applications encompass fields as diverse as archaeology, food chemistry, forensic science, geochemistry, medicine and metrology. However, to be effective tools, the isotope ratio data must be reliable and traceable to enable the comparability of measurement. The importance of traceability and comparability in isotope ratio analysis has already been recognized by the Inorganic Analysis Working Group (IAWG) within the CCQM. Three pilot studies have focused on the quality of isotope ratio determinations (P48 “U isotope ratios in urine”, P75 “stable isotopes in Methionine”, P105 “87Sr/86Sr in wine”). Moreover, isotope ratio measurements are fundamental to IDMS amount of substance determinations. For example, when Pb quantification using IDMS is undertaken, this requires the measurements of Pb isotope ratios. While the requirements for isotope ratio accuracy and precision in the case of of IDMS are generally quite modest, “absolute” Pb isotope ratio measurements for geochemical age dating and source rock characterization as well as forensic provenance and fingerprinting studies require Pb isotope ratio measurements of the highest quality. To support present and future CMCs on isotope ratio determinations, a Key Comparison was urgently needed. Therefore, it was decided at the IAWG meeting in Paris in April 2011 that a Key Comparison on the determination of Pb isotope ratios in a pure Pb solution and in a bronze sample should be organized and accompanied by a pilot study. Measuring Pb isotope amount ratios in a pure Pb solution, while seemingly straight forward, rigorously tests the ability of analyst to correct for any instrumental effects (such as mass discrimination and blank correction) on the measured ratios. Pb, present in trace amounts in a metal matrix sample (e.g. Pb in bronze), provides a real world test of the whole chemical and instrumental procedure, from chemical separation and sample purification to analysis and subsequent correction of appropriate instrumental effects on the separated samples. A suitable bronze material with a Pb mass fraction between 10 and 100 mg·kg-1 was available at BAM. A high purity solution of Pb with a mass fraction of approximately 100 mg·kg-1 was also available. By comparing the Pb isotope ratio results obtained for the bronze sample with the Pb isotope ratio results from the Pb solution, potential biases arising from the processing of the bronze sample could be effectively identified and separated from the instrumental effects arising from the measurement and data processing protocol. KW - Isotope ratio KW - Delta value KW - Molar mass KW - Measurement uncertainty KW - Traceability PY - 2017 UR - https://www.bipm.org/wg/CCQM/IAWG/Allowed/IAWG_Pilot_Studies/CCQM-P134.pdf SP - 1 EP - 42 PB - BIPM (Bureau International des Poids et Mesures) CY - Paris AN - OPUS4-47709 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Pritzkow, W. T1 - Bericht zur Herstellung und Zertifizierung eines Cadmium-Isotopenreferenzmaterials - Zertifiziertes Referenzmaterial BAM-I012 N2 - Dieser Bericht beschreibt die Herstellung und Zertifizierung einer Cadmiumlösung mit natürlicher Isotopenzusammensetzung. Für das Isotopen-Referenzmaterial sind sowohl die Isotopenverhältnisse als auch Isotopenhäufigkeiten und die molare Masse von Cadmium zertifiziert. Die Unsicherheiten sind erweiterte Messunsicherheiten U = k.uc mit k = 2. Der Cadmium-Massenanteil in der Lösung wird als indikativer Wert angegeben mit einer erweiterten Messunsicherheit U = k.uc mit k = 4,5. KW - Absolute Isotopenverhältnisse KW - Primäres Isotopenreferenzmaterial KW - Cadmium PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355845 SP - 1 EP - 15 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-35584 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Ostermann, Markus A1 - Becker, Dorit A1 - Janisch, N. T1 - Zertifiziertes Referenzmaterial ERM-AE104 bzw. BAM-I004 N2 - Dieser Bericht beschreibt die Zertifizierung einer synthetischen Isotopenmischung aus natürlicher und angereicherter Borsäure. Dieses Isotopen-ZRM liegt als konzentrierte, wässerige Borsäure-Lösung vor und ist bezüglich ihrer Isotopenzusammensetzung zertifiziert. Der Bor-Gesamtgehalt ist als Richtwert angegeben. Die Unsicherheiten sind erweiterte Messunsicherheiten mit k=2. Sie sind in Klammern angegeben und beziehen sich auf die letzten beiden Stellen. Das vorliegende Isotopen-ZRM ist bezüglich der Isotopenzusammensetzung mit erweiterten relativen Messunsicherheiten kleiner 0,08% zertifiziert. Die absolute, kombinierte Standardmessunsicherheit des prozentualen Stoffmengenanteils der Isotope (Isotopenhäufigkeit) liegt bei 0,014. In diesem Zertifizierungsbericht wird nur auf die Kapitel eingegangen, die abweichend vom bestehenden Zertifizierungsreport für die Referenzmaterialien BAM I001 bis BAM I003 sind und Einfluss auf die Endergebnisse haben. Dabei handelt es sich um die Kapitel 3.3, 3.4, 4, 6, 7 und 8, Die Kapitel 1, 2, 3, 3.1, 3.2, 5, 9 und 10 des alten Zertifizierungsberichts für die Referenzmaterialien BAM I001 bis BAM I003 behalten unverändert ihre Gültigkeit und sind nicht noch einmal aufgeführt worden. KW - Isotope KW - Kernkraftwerk KW - Bor PY - 2009 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355786 SP - 1 EP - 9 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-35578 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Klingbeil, P. A1 - Pritzkow, W. A1 - Riebe, Gundel A1 - Wermann, G. A1 - Turner, P. A1 - Wortel, N. A1 - Woittiez, J. T1 - HIIRM final report N2 - Accurate analytical results have become more and more an absolute essential tool for further progresses in technology and science. Precision however, often used in this context as a quality criterion for analytical methods, is not a replacement for accuracy in any way. Therefore, analytical procedures are necessary, which will generate reliable and accurate results and can be used for evaluation of other analytical procedures and certification of reference materials (RM). Especially the certification of reference materials for the amount content of trace elements requires highly accurate results with a small combined uncertainty. The best example for an analytical procedure having this capability is undoubtedly Isotope Dilution Mass Spectrometry, for inorganic as well as for organic applications. Applied on Thermal Ionization Mass Spectrometry (TIMS) isotope dilution provides results of highest quality and proven high accuracy especially in the field of RM certifications for more than 30 years. The major drawback of this approach often is the necessity for a complex chemical separation step. A major advantage of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is the potential to cope with a simplified or an on-line-carried-out sample preparation. A key requirement of isotope dilution analysis however is the accurate and precise determination of isotope ratios, because of its limiting factor for the accuracy and the total uncertainty of the result. Very precise isotope ratios can be determined in combination with a detection system that is capable of simultaneous detection of different isotopes, a so-called multi-collector system. The objective of the presented project is to evaluate the advantages of such a multi-collector ICP-MS for the application of IDMS in the field of trace elemental analysis in reference materials. The focus is on the development of simple and fast procedures for isotope ratio measurements in general and IDMS analysis in particular. Furthermore, it is an objective to develop and evaluate on-line spiking procedures. One of the first conclusions, which had a severe impact on the HIIRM project, arose during the early days of the project. Currently most certification experiments are accomplished by certification campaign based on a variety of participants’ results. The sample preparation, sending, analyzing and data evaluation however require lot of resources and the process may take a long time. An alternative way is given by using fewer participants with methods of higher metrological quality. For elemental amount contents such a method undoubtedly is isotope dilution analysis and multi-collector ICP-MS offers the necessary precision and matrix robustness and ruggedness as said above. Therefore, a multiple collector ICP-MS was manufactured as part of the project instead of the originally planned high-resolution instrument. Due to the novelty of the multicollector ICP-MS instrument, a lot of additional fundamental research became necessary. Especially interferences needed further attention. Fortunately, the IsoProbe is additionally equipped with a high-resolution option and with a brand new collison cell. The high-resolution option however can only be used to identify interferences but cannot be used to quantify them. On the other hand, the use of the collision cell proved to be a vital tool to overcome interferences. This is especially true because high resolution would have reduced the available sensitivity by a factor of ~100. Applying the collision cell technology the high sensitivity was maintained whilst most interferences were eliminated. However finding the right parameters of operation for the collision cell became a huge part of the method development process. A variety of gases like argon, helium, hydrogen, deuterium, nitrogen, krypton and xenon were tested for their suitability. Especially the tests accomplished for iron determinations revealed that carefully selected parameters have an incredible influence on the quality of the final results. Nonetheless collision cell technology will undoubtedly be widely used for newer ICP-MS instrumentation and contribute to eliminate wrong analytical values caused by interferences. The enhanced sensitivity of the instrument revealed also problems not detectable by other means. The control of contaminations seems to be one of the major analytical challenges in the future. Sector field based ICP-MS will give the user an opportunity to trace sources of contamination back to their origin and eliminate them. Even lower limits of detection will be the result as well as an enhanced reliability for analysts dealing with higher amount contents. The analyst will also benefit in controlling blank levels when the method of isotopically spiked procedure blanks is used as demonstrated in this project. Another main part of the project was the validation of the developed procedures. The first validation step was successfully accomplished by applying these procedures on the standard solutions provided by NRG. The main part of this validation however consisted of the evaluation of the fundamental parameters of the isotope dilution process and related measurements. This approach turned out to be superior compaired to the first step as a highly reliable uncertainty calculation can be easily performed. The best reputation and acceptance of the methods can however only be accomplished by participating in certification campaigns or in interlaboratory comparisons on highest metrological level. The results of the participations in general were brilliant. Not only the results but also the obtained realistic uncertainties were of superior quality. Direct comparisons at BAM with the results obtained by a multicollector TIMS applying the same calculation schemes showed the benefits of using multicollector ICP-MS. The main benefits of ICP-MS were identified, of which the first one is the enhanced precision of the isotope ratio measurement. For a variety of elements the values obtained by multicollector ICP-MS are even more precise than the ones obtainable by multicollector TIMS. The second important advantage identified was the simplified sample preparation. The laborious and time consuming analyte-matrix-separation step as necessary for TIMS measurements can either be omitted or at least be drastically reduced. Therefore, the advantages regarding time and enhanced sample throughput will result in further spread of ICP-MS in general and multicollector ICP-MS in particular. The third major part in terms of the method development process was mainly focused on developing an online isotope dilution system. The volumetric instead of the gravimetric IDMS approach proved difficult, if the high demands necessary for RM definition measurements are to be fulfilled. The major obstacle in this case is the missing stability and precision in terms of mass flow. Consequently, the initial development failed as the system made up of two piezoelectric droplet injectors was unable to reach the required stability as well as precision. The thereupon-created system consisting of two HPLC pumps proved to be far more valuable regarding automation and particularly the quantification of transient signals. Nevertheless, such a system will probably be rarely used in certification campaigns, as the gain of time is too small compared to the loss of reliability. However, this system proved most valuable in terms of species-specific elemental analysis as preliminary investigations showed. In this context this system will be suitable for certification measurements, as the major uncertainty contributions derive from sampling, sample treatment and species distribution and as moreover all availabel methods demonstrate far beyond. During the whole project, one of the main concerns regarding the multicollector ICP-MS instrument were software issues caused by the early development state of the original control programs. A lot of effort was necessary to accomplish the necessary data manipulations externally. The development of a new software suite by Micromass for the HIIRM project has solved this issue almost completely. With the new software suite and the validated parameters of measurement a step forward for institutes dealing with reference material certifications was achieved. Future certifications campaigns for minor elemental contents in different matrices should be performed by a small number of participants from highly qualified institutes. These institutes should apply very reliable methods of measurement like the ones developed in the HIIRM project. Many resources may be saved that way while the outcome of the certifications may easily be improved. ICP-MC-MS has the potential to be an important method in this context. Stable isotope dilution analysis in combination with a multi-detector ICP-MS, equipped with a hexapole collision cell for the suppression of important spectral interferences and for enhanced sensitivity, proved to be an advanced method of elemental analysis with a high potential for matrix independent measurements. Since ICP mass spectrometers of this type have only recently been introduced, no systematic evaluation of the capabilities of this specific application of the ICP-IDMS method has yet been made. KW - interferences KW - collision cell KW - ICPMS KW - IDMS PY - 2002 SP - 1 EP - 166 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-35579 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Becker, Dorit A1 - Koenig, Maren A1 - Yim, Y.-H. A1 - Lee, K.-S. A1 - Goenaga-Infante, H. A1 - Malinowskiy, D. A1 - Hill, S. A1 - Ren, T. A1 - Wang, J. A1 - Vocke, R. D. A1 - Murphy, K. A1 - Nonose, N. A1 - Rienitz, O. A1 - Noordmann, J. T1 - Certification Report for the Isotopic Reference Materials ERM-AE142 and ERM-EB400 N2 - Lead (Pb) isotope amount ratios are commonly used in applications ranging from archaeology and forensic sciences to terrestrial and extra-terrestrial geochemistry. Despite their utility and frequency of use, only three certified isotope amount ratio reference materials are currently available for Pb: NIST SRMs 981, 982 and 983. Because SRM 981 has a natural Pb isotopic composition, it is mainly used for correcting instrumental mass discrimination or fractionation. This means that, at present, there are no other certified isotope reference materials with natural Pb isotopic composition that could be used for validating or verifying an analytical procedure involving the measurement of Pb isotope amount ratios. To fill this gap, two new reference materials, both certified for their Pb isotopic composition, have been produced together with a complete uncertainty assessment. These new reference materials offer SI traceability and an independent means of validating or verifying analytical procedures used to produce Pb isotope amount ratio measurements. ERM-EB400 is a bronze material containing a nominal Pb mass fraction of 45 mg/kg. ERM-AE142 is a high purity solution of Pb with a nominal mass fraction of 100 mg/kg. Both materials have been specifically produced to assist analysts in verifying or validating their analytical procedures. Note that while one of these reference materials requires the chemical separation of Pb from its matrix (ERM-EB400), the other does not (ERM-AE142). Details on the certification of these isotope reference materials are provided in this report. KW - Lead isotopic composition KW - Isotope ratio KW - Reference material KW - Mass spectrometry PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-392060 SP - 1 EP - 16 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-39206 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Becker, Dorit A1 - Koenig, Maren A1 - Rosner, M. T1 - Certification report for the reference materials ERM-AE102a, -AE104a, -AE120, -AE121 and -AE122 N2 - Isotope reference materials are essential to enable reliable and comparable isotope data. Besides the correction of mass fractionation or mass discrimination isotope reference materials are indispensible for validation and quality control of analytical procedures. This article describes the production and certification of a set of five isotope reference materials ERM-AE102a, 104a, AE120, 121 and 122, for boron isotope analysis. The isotopic composition of all materials has been adjusted by mixing boron mother solutions enriched in 10B or 11B with a boron mother solution having natural-like isotopic composition under full gravimetric control. All mother solutions have been analysed for their boron mass fraction as well as their boron isotopic composition by TIMS using IDMS as calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agrees very well with the isotopic composition obtained from different TIMS techniques. Performed stability and homogeneity studies show no significant influence on the isotopic composition as well as on the related uncertainties. The certified isotope abundances for 10B are 0.29995 (27) for ERM-AE102a and 0.31488 (28) for ERM-AE104a. The certified δ11B values are -20.2 (6) ‰ for ERM-AE120, 19.9(6) ‰ for ERM-AE121 and 39.7 (6) ‰ for ERM-AE122. Together with the formerly certified ERM-AE101 and -AE103 a unique set of seven certified reference materials (CRM) for boron isotope analysis is now available from BAM. KW - Boron KW - Delta value KW - Isotope ratio KW - ICPMS KW - TIMS PY - 2010 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355813 SP - 1 EP - 24 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-35581 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Becker, Dorit A1 - Koenig, Maren A1 - Rienitz, O. A1 - Noordmann, J. T1 - Certification report for the reference materials ERM-AE140 and ERM-AE141 - Pd and Pt single spikes certified for their Pd and Pt mass fraction and isotopic composition N2 - Isotope dilution mass spectrometry often is applied for the quantification of platinum group elements in environmental and geological samples. In most cases, however, certified spike solutions offering complete uncertainty statements and SI-traceability are missing. This report describes the production and certification of two isotope reference materials, ERM-AE140 and ERM-AE141, serving as calibrated spike solutions for IDMS based quantification of Pd and Pt, respectively. Both materials were produced by dissolving highly enriched isotopes 106Pd and 194Pt and determining the mass fraction of 106Pd and 194Pt in the final solution by reverse IDMS. Two independent back-spikes were produced for each material from high purity Pd and Pt. Characterization measurements were carried out by MC-ICPMS. For ERM-AE140 the certified mass fractions are w(106Pd) = 20.24(5) mg/kg and w(Pd) = 20.54(5) mg/kg. For ERM-AE141 the certified mass fractions are w(194Pt) = 18.18(11) mg/kg and w(Pt) = 19.90(12) mg/kg. These values are traceable to the International System of Units (SI) in the shortest possible way. KW - Palladium KW - Enriched isotope KW - Platinum KW - Spike KW - IDMS PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355833 SP - 1 EP - 25 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-35583 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Becker, Dorit A1 - Koenig, Maren T1 - Certification report for the reference materials ERM-AE123 and ERM-AE124 - Certified for their boron isotope composition N2 - Isotope reference materials are essential to enable reliable and comparable isotope data. Besides the correction of mass fractionation or mass discrimination, isotope reference materials are indispensible for validation and quality control of analytical procedures. This report describes the production and certification of two isotope reference materials, ERM-AE123 and ERM-AE124, for boron isotope analysis. The isotopic composition of ERM-AE123 is the unaltered natural-like isotopic composition of the base material. The isotopic composition of ERM-AE124 has been adjusted by mixing two boron stock solutions enriched in 10B and 11B respectively under full gravimetric control. All stock solutions have been prepared fully under gravimetrical control. The corresponding boron isotopic composition has been analysed by TIMS. For both reference materials the isotopic composition obtained on the basis of the gravimetric data agrees very well with the isotopic composition obtained by TIMS. The certified isotope abundances for 10B are 0.19832 (21) for ERM-AE123 and 0.96006 (6) for ERM-AE124. Together with the formerly certified ERM-AE101, -AE102a, -AE103, -AE104a, -AE120, -AE121 and AE122, a unique set of nine certified reference materials (CRM) for boron isotope analysis is now available from BAM covering a range for the 10B isotope amount fraction from 0.2 to 0.96 and for the δ11B value from -20 ‰ to +40 ‰. KW - boron KW - isotope ratio KW - enriched isotope KW - ICPMS KW - TIMs PY - 2013 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355826 SP - 1 EP - 17 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-35582 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Vogl, Jochen A1 - Becker, Dorit A1 - Janisch, N. A1 - Klingbeil, P. A1 - Ludwig, H. P. A1 - Riebe, G. A1 - Pritzkow, W. A1 - Wermann, G. T1 - Zertifizierungsbericht für ERM-AE101 (auch BAM-I001), ERM-AE102 (auch BAM-I002) und ERM-AE103 (auch BAM-I003) N2 - Dieser Bericht beschreibt die Zertifizierung von 3 synthetischen Isotopenmischungen aus natürlicher und angereicherter Borsäure. Diese Isotopen-ZRM liegen als konzentrierte, wäs-serige Borsäure-Lösungen vor und sind bezüglich ihrer Isotopenzusammensetzung zertifi¬ziert. Der Bor-Gesamtgehalt ist als Richtwert angegeben. Die Unsicherheiten sind erweiterte Messunsicherheiten mit k=2. Sie sind in Klammern angegeben und beziehen sich auf die letzten beiden Stellen. Die vorliegenden Isotopen-ZRM sind bezüglich ihrer Isotopenzu¬sam-mensetzung mit erweiterten relativen Messunsicherheiten kleiner 0,12% zertifiziert. Die ab-solute, kombinierte Standardunsicherheit des prozentualen Stoffmengenanteils der Isotope (Isotopenhäufigkeit) liegt zwischen 0.012 und 0.017. KW - Isotope KW - Bor KW - Kernkraftwerke PY - 2009 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355777 SP - 1 EP - 21 CY - Berlin AN - OPUS4-35577 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Ecker, K. H. A1 - Wätjen, U. A1 - Berger, Achim A1 - Grötzschel, R. A1 - Persson, L. A1 - Pritzkow, W. A1 - Radtke, Martin A1 - Riebe, Gundel A1 - Riesemeier, Heinrich A1 - Vogl, Jochen T1 - Certification of antimony implanted in silicon wafer with a silicon dioxide diffusion barrier - IRMM-302 and BAM-L001 T2 - IRMM and BAM Information Reference Materials N2 - This Report describes the certification of the reference material antimony implanted in Si/SiO2 intended to be used for calibration of surface and near surface analytical methods. It describes the preparation, homogeneity measurements and the analytical work performed for the certification of both Areal density of antimony Atoms (retained dose) and the isotope amount Ratio as well as giving considerations on the stability of the material. KW - Isotope ratio KW - Areal density KW - Surface analysis PY - 2002 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-355752 SP - 1 EP - 40 PB - Institute for Reference Materials and Measurements CY - Geel, Belgium AN - OPUS4-35575 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -