TY - CONF A1 - Vogl, Jochen T1 - Metrology for boron isotope analysis T2 - Boron Isotope Workshop, Goldschmidt Conference 2013 CY - Florence, Italy DA - 2013-08-24 PY - 2013 AN - OPUS4-29083 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Production and certification of Pd and Pt single spikes T2 - Goldschmidt Conference 2013 CY - Florence, Italy DA - 2013-08-25 PY - 2013 AN - OPUS4-29084 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, Martin A1 - Pritzkow, Wolfgang T1 - The need for new isotope reference materials N2 - Isotope reference materials are needed to calibrate and validate analytical procedures used for the determination of isotope amount ratios, procedurally defined isotope ratios or so-called δ values. In contrast to the huge analytical progress in isotope ratio analytics, the production of isotope reference materials has not kept pace with the increasing needs of isotope analysts. Three representative isotope systems are used to explain the technical and non-technical difficulties and drawbacks, on one hand, and to demonstrate what can be achieved at its best, on the other hand. A clear statement is given that new isotope reference materials are needed to obtain traceable and thus comparable data, which is essential for all kinds of isotope research. The range of available isotope reference materials and δ reference materials should be increased and matrix reference materials certified for isotope compositions or δ values, which do not exist yet, should be provided. KW - Isotope reference materials KW - Delta reference materials KW - Synthetic isotope mixtures KW - Mass spectrometry KW - Comparability KW - Traceability KW - Measurement uncertainty PY - 2013 DO - https://doi.org/10.1007/s00216-012-6605-3 SN - 1618-2642 SN - 1618-2650 VL - 405 IS - 9 SP - 2763 EP - 2770 PB - Springer CY - Berlin AN - OPUS4-28169 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Paz, B. A1 - Koenig, Maren A1 - Pritzkow, Wolfgang T1 - A modified lead-matrix separation procedure shown for lead isotope analysis in Trojan silver artefacts as an example N2 - A modified Pb–matrix separation procedure using NH4HCO3 solution as eluent has been developed and validated for determination of Pb isotope amount ratios by thermal ionization mass spectrometry. The procedure is based on chromatographic separation using the Pb·Spec resin and an in-house-prepared NH4HCO3 solution serving as eluent. The advantages of this eluent are low Pb blanks (<40 pgmL-1) and the property that NH4HCO3 can be easily removed by use of a heating step (>60 °C). Pb recovery is >95 % for water samples. For archaeological silver samples, however, the Pb recovery is reduced to approximately 50 %, but causes no bias in the determination of Pb isotope amount ratios. The validated procedure was used to determine lead isotope amount ratios in Trojan silver artefacts with expanded uncertainties (k=2) <0.09 %. KW - Analyte-matrix separation KW - Mass spectrometry KW - Pb isotope ratio thermal ionization mass spectrometry KW - Archaeometry PY - 2013 DO - https://doi.org/10.1007/s00216-012-6323-x SN - 1618-2642 SN - 1618-2650 VL - 405 IS - 9 SP - 2995 EP - 3000 PB - Springer CY - Berlin AN - OPUS4-28170 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen T1 - Advances in isotope ratio mass spectrometry and required isotope reference materials N2 - The article gives a condensed version of the keynote lecture held at the International Mass Spectrometry Conference 2012 in Kyoto. Starting with some examples for isotope research the key requirements for metrologically valid procedures enabling traceable and comparable isotope data are discussed. Of course multi-collector mass spectrometers are required which offer sufficiently high isotope ratio precision for the intended research work. Following this, corrections for mass fractionation/discrimination, validation of the analytical procedure including chemical sample preparation and complete uncertainty budgets are the most important issues for obtaining a metrologically valid procedure for isotope ratio determination. Only the application of such metrologically valid procedures enables the generation of traceable and comparable isotope data. To realize this suitable isotope and/or δ-reference materials are required, which currently are not sufficiently available for most isotope systems. Boron is given as an example, for which the situation regarding isotope and δ-reference materials is excellent. Boron may therefore serve as prototype for other isotope systems. KW - Isotope reference materials KW - Delta reference materials KW - Traceability KW - Comparability KW - Measurement uncertainty KW - Synthetic isotope mixtures KW - Mass fractionation KW - Mass discrimination PY - 2013 DO - https://doi.org/10.5702/massspectrometry.S0020 SN - 2187-137X SN - 2186-5116 VL - 2 IS - 50020 SP - 1 EP - 7 AN - OPUS4-28562 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Reference Materials and Metrological Principles for Isotope Research T2 - 15th Beijing Conference and Exhibition on Instrumental Analysis (BCEIA 2013) CY - Beijing, China DA - 2013-10-23 PY - 2013 AN - OPUS4-29295 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - CCQM-K98/P134 - Pb isotope amount ratios in bronze T2 - CCQM IAWG Meeting CY - Pretoria, South Africa DA - 2013-11-05 PY - 2013 AN - OPUS4-29296 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riebe, Gundel A1 - Klingbeil, Patrick A1 - Pritzkow, Wolfgang A1 - Vogl, Jochen T1 - Erfahrungen mit mikrowelleninduzierten Aufschluss-Verfahren für die Elementspurenanalytik T2 - MLS-Tagesseminar CY - Berlin, Deutschland DA - 2001-03-19 PY - 2001 AN - OPUS4-1111 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Riebe, Gundel A1 - Ostermann, Markus A1 - Pritzkow, Wolfgang A1 - Vogl, Jochen T1 - Combination of sophisticated sample digestion methods and highly accurate determination procedures shown for Sulphur in oil and Cadmium and Lead in sediment T2 - Internationale Konferenz "Trends in Sample Preparation 2002" CY - Seggau, Austria DA - 2002-06-30 PY - 2002 AN - OPUS4-1398 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ostermann, Markus A1 - Janisch, Nadine A1 - Vogl, Jochen T1 - On the determination of the moisture content in different matrix materials T2 - Internationale Konferenz "Trends in Sample Preparation 2002" CY - Seggau, Austria DA - 2002-06-30 PY - 2002 AN - OPUS4-1399 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Paz, B. A1 - Meyer, H.-P. A1 - Varychev, A. A1 - Rosner, M. A1 - Vogl, Jochen A1 - Behrendt, S. ED - Treister, M. ED - Yablonsky, L. T1 - Археометрические исследования стеклянных сосудов из погребений ранних кочевников Южного Приуралья T1 - Archäometrische Untersuchungen an achaimenidischen Glasgefäßen aus den Gräbern der frühen Nomaden des südlichen Urals N2 - Die untersuchten Gläser lassen sich in drei Gruppen einteilen. Die beiden Fragmente aus der Nekropole von Pjatimary deuten auf eine frühe Herstellungszeit hin und lassen sich mit eisenzeitlichen Fragmenten iranischer Herkunft vergleichen. Die Glasfunde aus der Nekropole Filippovka bestehen aus völlig unterschiedlichen Glasmaterialien und müssen einer späteren Herstellungszeit zugeordnet werden. Sowohl die unterschiedlichen Rezepturen als auch der definitive Hinweis auf verschiedene Rohstoffquellen zur Herstellung der untersuchten Gläser, lassen ein breitgefächertes Netz von weitreichenden Handelsbeziehungen erkennen. KW - Archäometrie KW - Isotopenverhältnisse Strontium und Blei KW - Elementanalyse KW - Massenspektrometrie KW - Herkunft PY - 2012 SN - 978-5-903011-85-8 VL - 1 SP - 262 EP - 267 PB - TAUS CY - Moskau AN - OPUS4-26899 LA - rus AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rienitz, O. A1 - Schiel, D. A1 - Görlitz, V. A1 - Jährling, R. A1 - Vogl, Jochen A1 - Lara-Manzano, J.V. A1 - Zon, A. A1 - Fung, W.-H. A1 - Buzoianu, M. A1 - De Sena, R.C. A1 - Dos Reis, L.A. A1 - Valiente, L. A1 - Yim, Y.-H. A1 - Hill, S. A1 - Champion, R. A1 - Fisicaro, P. A1 - Bing, W. A1 - Turk, G.C. A1 - Winchester, M. R. A1 - Saxby, D. A1 - Merrick, J. A1 - Hioki, A. A1 - Miura, T. A1 - Suzuki, T. A1 - Linsky, M. A1 - Barzev, A. A1 - Máriássy, M. A1 - Cankur, O. A1 - Ari, B. A1 - Tunc, M. A1 - Konopelko, L.A. A1 - Kustikov, Y.A. A1 - Bezruchko, M. T1 - Final report on CCQM-K87: Mono-elemental calibration solutions N2 - The aim of this comparison was to demonstrate the capability of national metrology institutes to measure elemental mass fractions at a level of w(E) ≈ 1 g/kg as found in almost all mono-elemental calibration solutions. These calibration solutions represent an important link in traceability systems in inorganic analysis. Virtually all traceable routine measurements are linked to the SI through these calibration solutions. Every participant was provided with three solutions of each of the three selected elements chromium, cobalt and lead. This comparison was a joint activity of the Inorganic Analysis Working Group (IAWG) and the Electrochemical Analysis Working Group (EAWG) of the CCQM and was piloted by the Physikalisch-Technische Bundesanstalt (PTB, Braunschweig, Germany) with the help of the Bundesanstalt für Materialforschung und -prüfung (BAM, Berlin, Germany), the Centro Nacional de Metrología (CENAM, Querétaro, Mexico) and the National Institute of Standards and Technology (NIST, Gaithersburg, USA). A small majority of participants applied inductively coupled plasma optical emission spectrometry (ICP OES) in combination with a variety of calibration strategies (one-point-calibration, bracketing, calibration curve, each with and without an internal standard). But also IDMS techniques were carried out on quadrupole, high resolution and multicollector ICP-MS machines as well as a TIMS machine. Several participants applied titrimetry. FAAS as well as ICP-MS combined with non-IDMS calibration strategies were used by at least one participant. The key comparison reference values (KCRV) were agreed upon during the IAWG/EAWG meeting in November 2011 held in Sydney as the added element content calculated from the gravimetric sample preparation. Accordingly the degrees of equivalence were calculated. Despite the large variety of methods applied no superior method could be identified. The relative deviation of the median of the participants' results from the gravimetric reference value was equal or smaller than 0.1% (with an average of 0.05%) in the case of all three elements. KW - CCQM KW - Metrology KW - IDMS PY - 2012 DO - https://doi.org/10.1088/0026-1394/49/1A/08010 SN - 0026-1394 SN - 1681-7575 VL - 49 IS - 08010, 1A (Technical Supplement 2012) SP - 1 EP - 104 PB - Inst. of Physics Publ. CY - Bristol AN - OPUS4-30458 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen A1 - Rosner, Martin T1 - Production and certification of a unique set of isotope and delta reference materials for Boron isotope determination in geochemical, environmental and industrial materials N2 - Isotopic reference materials are essential to enable reliable and comparable isotope data. In the case of boron only a very limited number of such materials is available, thus preventing adequate quality control of measurement results and validation of analytical procedures. To address this situation a unique set of two boron isotope reference materials (ERM-AE102a and -AE104a) and three offset δ11B reference materials (ERM-AE120, -AE121 and -AE122) were produced and certified. The present article describes the production and certification procedure in detail. The isotopic composition of all the materials was adjusted by mixing boron parent solutions enriched in 10B or 11B with a boron parent solution having a natural isotopic composition under full gravimetric control. All parent solutions were analysed for their boron concentration as well as their boron isotopic composition by thermal ionisation mass spectrometry (TIMS) using isotope dilution as the calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agreed very well with the isotopic composition obtained from different TIMS techniques. Stability and homogeneity studies that were performed showed no significant influence on the isotopic composition or on the related uncertainties. The three reference materials ERM-AE120, ERM-AE121 and ERM-AE122 are the first reference materials with natural δ11B values not equal to 0‰. The certified δ11B values are -20.2‰ for ERM-AE120, 19.9‰ for ERM-AE121 and 39.7‰ for ERM-AE122, each with an expanded uncertainty (k = 2) of 0.6‰. These materials were produced to cover about three-quarters of the known natural boron isotope variation. The 10B enriched isotope reference materials ERM-AE102a and ERM-AE104a were produced for industrial applications utilising 10B for neutron shielding purposes. The certified 10B isotope abundances are 0.29995 for ERM-AE102a and 0.31488 for ERM-AE104a with expanded uncertainties (k = 2) of 0.00027 and 0.00028, respectively. Together with the formerly certified ERM-AE101 and ERM-AE103 a unique set of four isotope reference materials and three offset δ11B reference materials for boron isotope determination are now available from European Reference Materials. KW - Boron isotope variations KW - Delta-scale KW - Stable isotopes KW - Isotope reference materials KW - Delta reference materials KW - Metrology in chemistry KW - Absolute isotope abundance PY - 2012 DO - https://doi.org/10.1111/j.1751-908X.2011.00136.x SN - 1639-4488 SN - 1751-908X VL - 36 IS - 2 SP - 161 EP - 175 PB - Blackwell CY - Oxford AN - OPUS4-26260 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Völling, E. A1 - Reifarth, N. A1 - Vogl, Jochen ED - Nosch, M.-L. ED - Laffineur, R. T1 - The intercultural context of treasure A in Troy - Jewellery and textiles N2 - At the end of May 1873, Heinrich Schliemann recovered Treasure A in Troy. He brought all the metal artifacts illegally to Athens and published his iscoveries one year later. Then he bequeathed the Trojan finds to Berlin where from 1881 onwards, Treasure A was exhibited in the Museum of Arts and Crafts (later Gropius Bau). Hubert. Schmidt inventoried and catalogued the Trojan remains in 1902 without the so-called “Dubletten” (duplicates). The transfer of the Treasure trove in 1945 to former Leningrad (St. Petersburg) and Moscow is well known, but there was a partial restoration of the looted art from the former Soviet Union back to the former GDR: eight out of eleven silver vessels of Treasure A came via Leipzig in 1979 finally back to Berlin’s Museum für Vor- und Frühgeschichte, Stiftung Preussischer Kulturbesitz in 1994. During its safe keeping in Leningrad and Leipzig, these silver jars remained ignored in the boxes in which they were transported, a Situation, which today permits them to be investigated almost in their condition of discovery. The study of the Originals allowed Information to be gleaned about their manufacture and offered opportunities for various analyses. After the gold jewellery came to light, technical data and an archaeological appraisal of the Trojan gold kept in the Pushkin Museum of Fine Arts in Moscow could be published in 1996. The considerable quantity of the outstanding gold artifacts of Treasure A was deposited inside the great silver vessel Sch 5873 and listed by Heinrich Schliemann. T2 - 13th International Aegean Conference CY - Copenhagen, Denmark DA - 21.04.2010 PY - 2012 SN - 978-90-429-2665-3 SP - 531 EP - 538 PB - Peeters Publishers CY - Liège, Belgium AN - OPUS4-26408 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogl, Jochen T1 - Measurement uncertainty in single, double and triple isotope dilution mass spectrometry N2 - Triple IDMS has been applied for the first time to the quantification of element concentrations. It has been compared with single and double IDMS obtained on the same sample set in order to evaluate the advantages and disadvantages of triple IDMS over single and double IDMS as an analytical reference procedure. The measurement results of single, double and triple IDMS are indistinguishable, considering rounding due to the individual measurement uncertainties. As expected, the relative expanded uncertainties (k = 2) achieved with double IDMS (0.08 %) are dramatically smaller than those obtained with single IDMS (1.4 %). Triple IDMS yields the smallest relative expanded uncertainties (k = 2, 0.077 %) unfortunately at the expense of a much higher workload. Nevertheless triple IDMS has the huge advantage that the isotope ratio of the spike does not need to be determined. Elements with high memory effects, highly enriched spikes or highest metrological requirements may be typical applications for triple IDMS. KW - Single IDMS KW - Double IDMS KW - Triple IDMS KW - Measurement uncertainty KW - Cd mass fraction PY - 2012 DO - https://doi.org/10.1002/rcm.5306 SN - 0951-4198 SN - 1097-0231 VL - 26 IS - 3 SP - 275 EP - 281 PB - Wiley CY - Chichester AN - OPUS4-25292 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Klingbeil, Patrick A1 - Vogl, Jochen A1 - Pritzkow, Wolfgang A1 - Riebe, Gundel A1 - Müller, J. T1 - Comparative studies on the certification of reference materials by ICPMS and TIMS using isotope dilution procedures N2 - A comparison of different isotope dilution mass spectrometric (IDMS) procedures using inductively coupled plasma mass spectrometry (ICPMS) and thermal ionization mass spectrometry (TIMS) was carried out to examine the degree of equivalence between the used procedures in terms of requirements for reference material certification. The comparison was based on the measurement results and their uncertainties. The sample used in this study is a pure zinc metal to be certified by the Bureau Communie de Référence (BCR) for amount contents of different trace elements. This study focuses on cadmium and thallium. The TIMS values contributed to the certified values. To guarantee identical conditions as far as possible for the procedures under investigation, the samples were split into subsamples after spiking and digestion took place. Thus, every IDMS procedure started with an identical set of samples. In total, four different IDMS procedures and one external calibration procedure using internal standardization as an example of routine analysis were applied. The IDMS procedures divide in a group with and a group without trace/matrix separation. Multicollector TIMS (TI-MC-MS) and multicollector ICPMS (ICP-MC-MS) were used in combination with trace/matrix separation, whereas quadrupole ICPMS (ICP-QMS) and ICP-MC-MS were also applied to nonseparated samples. All IDMS results agree well within their combined uncertainties, while some results from the external calibration procedure do not. IDMS results obtained by ICPMS without separation are comparable to those obtained by TI-MC-MS with separation regarding precision and accuracy. The smallest uncertainties were achieved using ICP-MC-MS in combination with trace/matrix separation. KW - ICP-MS KW - TIMS KW - IDMS KW - multi-collector KW - uncertainty budget KW - Certification KW - reference material PY - 2001 DO - https://doi.org/10.1021/ac001278c SN - 0003-2700 SN - 1520-6882 VL - 73 IS - 8 SP - 1881 EP - 1888 PB - American Chemical Society CY - Washington, DC AN - OPUS4-909 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - You, Zengchao A1 - Winckelmann, Alexander A1 - Vogl, Jochen A1 - Recknagel, Sebastian A1 - Abad Andrade, Carlos Enrique T1 - Determination of calcium, iron, and selenium in human serum by isotope dilution analysis using nitrogen microwave inductively coupled atmospheric pressure plasma mass spectrometry (MICAP-MS) N2 - In this study, we demonstrate the applicability of nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) for Ca, Fe, and Se quantification in human serum using isotope dilution (ID) analysis. The matrix tolerance of MICAP-MS in Na matrix was investigated, uncovering that high Na levels can suppress the signal intensity. This suppression is likely due to the plasma loading and the space charge effect. Moreover, 40Ca and 44Ca isotopic fractionation was noted at elevated Na concentration. Nine certified serum samples were analyzed using both external calibration and ID analysis. Overestimation of Cr, Zn, As, and Se was found in the results of external calibration, which might be resulted from C-induced polyatomic interference and signal enhancement, respectively. Further investigations performed with methanol showed a similar enhancement effect for Zn, As, and Se, potentially supporting this assumption. The mass concentrations determined with ID analysis show metrological compatibility with the reference values, indicating that MICAP-MS combined with ID analysis can be a promising method for precise Ca, Fe, and Se determination. Moreover, this combination reduces the influences of matrix effects, broadening the applicability of MICAP-MS for samples with complex matrix. KW - Selenium KW - Nitrogen microwave inductively coupled atmospheric pressure mass spectrometry KW - Isotope dilution KW - Human serum KW - Calcium KW - Iron PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598664 DO - https://doi.org/10.1007/s00216-024-05274-0 SN - 1618-2642 SP - 3117 EP - 3125 PB - Springer CY - Berlin AN - OPUS4-59866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Knobbe, N. A1 - Vogl, Jochen A1 - Pritzkow, Wolfgang A1 - Panne, Ulrich A1 - Fry, H. A1 - Lochotzke, H.M. A1 - Preiss-Weigert, A. T1 - C and N stable isotope variation in urine and milk of cattle depending on the diet N2 - The stable carbon and nitrogen isotopic composition of urine and milk samples from cattle under different feeding regimes were analysed over a period of six months. The isotope ratios were measured with isotope ratio mass spectrometry (IRMS). The δ13C values of milk and urine were dependent on different feeding regimes based on C3 or C4 plants. The δ13C values are more negative under grass feeding than under maize feeding. The δ13C values of milk are more negative compared to urine and independent of the feeding regime. Under grass feeding the analysed milk and urine samples are enriched in 13C relative to the feed, whereas under maize feeding the 13C/12C ratio of urine is in the same range and milk is depleted in 13C relative to the diet. The difference between the 15N/14N ratios for the two feeding regimes is less pronounced than the 13C/12C ratios. The δ15N values in urine require more time to reach the new equilibrium, whereas the milk samples show no significant differences between the two feeding regimes. KW - Cattle KW - Urine KW - Milk KW - Feeding regime KW - Stable isotope PY - 2006 DO - https://doi.org/10.1007/s00216-006-0644-6 SN - 1618-2642 SN - 1618-2650 VL - 386 IS - 1 SP - 104 EP - 108 PB - Springer CY - Berlin AN - OPUS4-12746 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Abad Andrade, Carlos Enrique A1 - Florek, S. A1 - Becker-Ross, H. A1 - Huang, M.-D. A1 - Heinrich, Hans-Joachim A1 - Recknagel, Sebastian A1 - Vogl, Jochen A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - Determination of boron isotope ratios by high-resolution continuum source molecular absorption spectrometry using graphite furnace vaporizers N2 - Boron isotope amount ratios n(10B)/n(11B) have been determined by monitoring the absorption spectrum of boron monohydride (BH) in a graphite furnace using high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS). Bands (0→0) and (1→1) for the electronic transition X1Σ+ → A1Π were evaluated around wavelengths 433.1 nm and 437.1 nm respectively. Clean and free of memory effect molecular spectra of BH were recorded. In order to eliminate the memory effect of boron, a combination of 2% (v/v) hydrogen gas in argon and 1% trifluoromethane in argon, an acid solution of calcium chloride and mannitol as chemical modifiers was used. Partial least square regression (PLS) for analysis of samples and reference materials were applied. For this, a spectral library with different isotopes ratios for PLS regression was built. Results obtained around the 433.1 nm and 437.1 nm spectral regions are metrologically compatible with those reported by mass spectrometric methods. Moreover, for the evaluated region of 437 nm, an accuracy of 0.15‰ is obtained as the average deviation from the isotope reference materials. Expanded uncertainties with a coverage factor of k = 2 range between 0.15 and 0.44‰. This accuracy and precision are compatible with those obtained by mass spectrometry for boron isotope ratio measurements. KW - Boron isotopes KW - Isotope ratios KW - Boron monohydride KW - Molecular absorption KW - High-resolution continuum source absorption spectrometry KW - Graphite furnace KW - Memory effect KW - HR-CS-MAS PY - 2017 UR - http://www.sciencedirect.com/science/article/pii/S0584854717302537 DO - https://doi.org/10.1016/j.sab.2017.08.012 SN - 0584-8547 VL - 136 SP - 116 EP - 122 PB - Elsevier CY - Amsterdam, The Netherlands AN - OPUS4-42071 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Panne, Ulrich A1 - Jakubowski, Norbert A1 - Vogl, Jochen T1 - SI-traceable quantification of sulphur in copper metal and its alloys by ICP-IDMS N2 - Previously applied methods for the quantification of sulphur in copper and other pure metals revealed a lack of SI-traceability and additionally showed inconsistent results, when different methods were compared. Therefore, a reference procedure is required which allows SI-traceable values accompanied by a Sound uncertainty budget. In this study a procedure was developed for the quantification of total sulphur in copper at low concentration levels using inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS). The major part of the copper matrix was separated by adding ammonia which forms a complex with the copper while releasing the sulphur followed by chromatographic separation using a weak cation resin. After that the sulphur fraction was further purified by chromatographic means using first an anion exchange method and second a chelating resin. The developed procedure shows high performance, especially concerning high efficiency in matrix removal (>99.999%) while keeping the recovery of sulphur above 80%. Procedure blanks are in the order of 3–53 ng resulting in LOD and LOQ values of 0.2 mg g1 and 0.54 mg g1, respectively. The procedure is sufficient to facilitate value assignment of the total sulphur mass fraction in reference materials. Additionally, relative measurement uncertainties were calculated to be below 1% and the measurement results were traceable to the SI. The procedure reported in this study is a new reference procedure for sulphur measurement in copper, being fit for two major purposes, certification of reference materials and assignment of reference values for inter-laboratory comparison. KW - Traceability KW - Measuremment uncertainty KW - Isotope dilution mass spectrometry KW - Reference measurements PY - 2018 DO - https://doi.org/10.1039/c7ja00338b SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 1 SP - 90 EP - 101 PB - Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-43614 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scharek, Vera M. A1 - Pfeifer, Jens A1 - Vogl, Jochen A1 - Traub, Heike A1 - Meermann, Björn T1 - Tin fractionation analysis in sediment samples via on-line ID ETV/ICP-MS N2 - We report a quantification approach for directly determining total tin and tin-based pollutants/species in sediments via electrothermal vaporization/inductively coupled plasma-mass spectrometry (ETV/ICP-MS) utilizing an on-line isotope dilution mass spectrometry (IDMS) approach. The method was developed and validated using an estuarine sediment reference material (BCR-277R), yielding a recovery of 106%. A relative standard deviation (RSD) of 14%, comparable to published data using a similar method, was obtained. A limit of quantification (LOQ) was estimated at 0.008 mg Sn kg−1 and sufficient for quantifying the total tin mass fraction of surface sediments along the tidal River Elbe course. Hereby, a decrease towards the river mouth, presumably due to dilution effects by less polluted marine sediment, was observed. Besides total tin, monitoring of organotin compounds (OTCs)/species is of interest in sediments due to their toxic effects on aquatic life. The method’s capability was extended by separating an OTC fraction in a sediment certified reference material (CRM) through the ETV temperature program. While spiking experiments with OTC standards confirmed the assignment, only a small fraction of the total certified OTC amount (3%), likely due to matrix effects, was recovered. However, applying the method to real-world samples, OTCs were detectable along the River Elbe course. By this, we demonstrated the potential of our method as a complementary fast-screening approach to species-specific analysis procedures. KW - ETV KW - Sn-Speciation KW - Sediment PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-640137 DO - https://doi.org/10.1007/s00216-025-06064-y SN - 1618-2642 SP - 1 EP - 10 PB - Springer Science and Business Media LLC AN - OPUS4-64013 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schannor, Mathias A1 - Oelze, Marcus A1 - Traub, Heike A1 - He, Yubei A1 - Schmidt, Robin A1 - Heidemann, Luisa A1 - Savic, Lynn Jeanette A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS N2 - Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an in situ method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 s) for inorganic reference materials and of better than 0.17 ‰ (2 s) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. In situ Cu isotope compositions between healthy (𝛿65/63NIST976(Cu) = −1.5 ‰ to 0.2 ‰) and tumorous (𝛿65/63NIST976(Cu) = 0.0 ‰ to 1.3 ‰) liver tissue show distinct differences in their isotope ratios. The observed isotopic dichotomy is consistent with previous solution-based MC-ICP-MS work, showing enrichment of heavy 65Cu in cancer biopsies relative to healthy tissue. KW - Biomarker KW - Laser Ablation KW - Reference Material PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626865 DO - https://doi.org/10.1021/acs.analchem.4c05626 SN - 1520-6882 VL - 97 IS - 8 SP - 4425 EP - 4432 PB - American Chemical Society (ACS) AN - OPUS4-62686 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen A1 - Traub, Heike A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - A new approach of using polyethylene frits for the quantification of sulphur in copper metals by isotope dilution LA-ICP-MS and comparison with conventional IDMS techniques N2 - Polyethylene (PE) frits were used to quantify sulphur in copper and its alloys by isotope dilution combined with LA-ICP-MS as an alternative approach to conventional sample preparation: the copper samples were spiked, the spiked samples were dissolved, the resulting solutions were absorbed in the PE frits and finally the PE frits were analysed by LA-ICP-MS. A prerequisite for such a support material is a low sulphur blank and thus PE was selected for this purpose. The absorption efficiency of the PE frits was studied for varying sulphur amounts ranging from 2 mg S to 80 mg S showing that more than 99.5% of the loaded sulphur was absorbed by the frit. The so prepared PE frits were measured by LA-ICP-MS and yielded a good linearity (R2 ¼ 0.999) for the sulphur ion intensities corresponding to sulphur amounts up to 40 mg S; the associated sensitivity is approximately 3.4 x 10⁴ cps μg⁻¹ for ³²S. For the validation of the developed procedure the reference materials BAM-M376a, BAM-228 and BAM-227 were applied such that 2 μg S, 5 μg S and 11 μg S were absorbed in the PE frits, respectively. These samples were pre-quantified for the adsorbed sulphur amount by external calibration LA-ICP-MS yielding sulphur amounts of 0.9 μg, 5.1 μg and 8.5 μg (quantified for ³²S only), respectively. Relative Standard deviations of the isotope ratios were below 5% in average (n ¼ 3 lines) in all cases (except for the pure spike solution). These samples were then analysed by LA-ICP-IDMS and the measurement results were validated by comparing them with the results obtained by conventional ICP-IDMS. The obtained relative expanded measurement uncertainties ranged between 10% and 26%. Pearson's coefficient was used to express the correlation between both techniques; the obtained value was 0.999 demonstrating a strong correlation. Contrary to most published LA-ICP-IDMS procedures, the developed procedure enables SI-traceability for the measurement results. The metrological traceability to the SI for the sulphur mass fractions in copper was established by an unbroken chain of comparisons, each accompanied by an uncertainty budget. Thus, the measurement results are considered reliable, acceptable and comparable within the stated measurement uncertainty. The metrological traceability chain from the kg down to mass fraction in the samples obtained by LA-ICP-IDMS is presented as well. KW - Laser ablation KW - IDMS KW - Traceability KW - Uncertainty KW - Purity PY - 2018 DO - https://doi.org/10.1039/c8ja00116b SN - 0267-9477 SN - 1364-5544 VL - 33 IS - 9 SP - 1506 EP - 1517 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-45899 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kazlagić, Anera A1 - Stephan, D. A1 - Ostermann, Markus A1 - Possolo, A. A1 - Vogl, Jochen T1 - Fingerprinting Portland cements by means of 87Sr/86Sr and 143Nd/144Nd isotope ratios and geochemical profiles N2 - This study uses conventional 87Sr/86Sr and 143Nd/144Nd isotope and interelement ratios of Ca, Sr, K, Mn, Mg and Ti as fingerprints for provenancing ordinary Portland cements (OPC). Herein, the first database of Sr and Nd isotope ratios investigated in OPCs, stemming from 29 cement plants located worldwide, was created. The results show that the Sr isotope ratios of OPCs are higher than those of seawater from the observed geological period. The spread of 143Nd/144Nd in OPCs is not as large as the spread for 87Sr/86Sr isotope ratios. However, the combination of both Sr and Nd isotope ratios provides the potential for distinguishing between cements of different production sites. Most of the OPCs investigated have measurable differences in their 87Sr/86Sr and 143Nd/144Nd isotope ratios, which can be employed as a valuable analytical fingerprinting tool. In the case of equivocal results, divisive hierarchical clustering was employed to help overcome this issue. The construction of geochemical profiles allowed the computing of suitably defined distances between cements and clustering them according to their chemical similarity. By applying this methodology, successful fingerprinting was achieved in 27 out of the 29 ordinary Portland cements that were analysed. KW - Elemental fingerprints KW - Geochemistry KW - Portland cement KW - Sr and Nd isotope analysis KW - Statistical analysis PY - 2023 DO - https://doi.org/10.1680/jadcr.23.00018 SN - 0951-7197 VL - 36 IS - 6 SP - 260 EP - 271 PB - Emerald Publishing Limited AN - OPUS4-57979 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -