TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Advances and Applications of Molecular Absorption Spectrometry: from Non-Metals to Isotope Analysis N2 - Wie kann Nicht-Messbares messbar gemacht werden? Die Antwort der Dissertation auf diese zentrale Frage der analytischen Chemie lautet: die Anwendung der hochauflösenden optischen Spektroskopie der diatomischen Moleküle. In der Arbeit wird in einem ersten Schritt in Grafitöfen, die wie Chemiereaktoren funktionieren, und durch die Anwendung verschiedener analytischer Methoden die diatomische Molekülbildung nachvollzogen. In einem zweiten Schritt werden die aufgedeckten Mechanismen auf die Bestimmung von Nichtmetallen und die Analyse von Isotopen angewendet. Die Isotopenanalytik ist das zukunftsweisendes Herzstück der Dissertation und von alltäglicher und politischer Relevanz: Mittels dieser Technik lässt sich die Herkunft von Lebensmitteln aber auch Chemiewaffen kostengünstiger und wesentlich schneller bestimmen als mit bisherigen Methoden der Massenspektrometrie. Möglich ist die Bestimmung, da alles um uns herum aus Atomen verschiedener Elemente besteht und die meisten Elemente mehrere Isotope haben. Isotope unterscheiden sich hinsichtlich ihres Gewichts, da sie über eine unterschiedliche Anzahl an Neutronen verfügen. Die Informationen über das Verhältnis von schweren und leichten Isotopen lässt sich nutzen, um zu bestimmen wo etwas entstanden ist. Jeder Ort auf unserem Planeten hat seinen persönlichen Element- und Isotopenanteil (Isotopenfingerabdruck). Das in der Arbeit angewandte Instrument misst das Verhältnis indirekt und nutzt hierzu die Interaktion zwischen Licht und Materie. Für das schwerere Isotop wird mehr Licht/Energie benötigt, um es in Bewegung zu bringen, als für das leichtere. Diese kleinen Unterschiede an Energie, die wir dafür aufwenden müssen, werden gemessen und ermöglichen die Herkunftsbestimmung. Damit leistet die Arbeit nicht nur einen wichtigen Beitrag zur Grundlagenforschung in der analytischen Chemie, sondern kann mit den aufgezeigten Ergebnissen auch Anwendung in den Bereichen Verbraucherschutz, Umweltforschung und Waffenkontrolle finden. N2 - The present work covers two main aspects of high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS), an analytical technique for elemental trace analysis. First, a comprehensive mechanistic study of molecule formation in graphite furnaces is presented, which is a key step into the recovery of analytical signals. For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in HR-CS-GFMAS. A zirconium coating catalyzes the CaF formation, and its structure was investigated. The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. Here a mechanism is proposed, where ZrO2 works as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. Second, analytical methods were developed by using HR-CS-MAS as detector for non-metals and isotope analysis. Therefore, the determination of organic absorbable chlorine in water, the quantification of fluorine in consume care products with declared perfluorinated ingredients, and the determination of sulfur content in crude oils were investigated. Finally, the high resolution of the instrumentation allows to measure isotopic shifts with high precision in some observed molecular spectra. Consequently, the molecular spectra of enriched isotopes of boron and magnesium were investigated, establishing so the potential of HR-CS-MAS for the accurate and precise determination of isotopic amount ratios. T2 - Applied Photonics Award 2020 CY - Jena, Germany DA - 22.09.2020 KW - Herkunftsbestimmung KW - Isotopenanalyse KW - Isotope KW - Optischer Spektroskopie PY - 2020 AN - OPUS4-51996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Abad Andrade, Carlos Enrique T1 - Isotopic analysis by high-resolution optical spectroscopy N2 - Isotope analysis can be used to determine the age and provenance of geological samples or to study dynamic systems like Li-ion batteries. Modern techniques in optical spectrometry allow us a fast and slow-cost isotope analysis. These techniques include high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS) and laser ablation molecular isotopic spectrometry. This seminar will discuss our recent work on precise and accurate isotope analysis of boron, magnesium, and lithium with geology, climate, and energy research applications. T2 - Recent Trends in Chemical Science and Technology, Christian College Chengannur, India CY - Online meeting DA - 29.09.2020 KW - Isotopes KW - Optical spectrometry KW - Machine learning PY - 2020 AN - OPUS4-51997 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Garde, Raul A1 - Abad Andrade, Carlos Enrique A1 - Recknagel, Sebastian A1 - Nakadi, F. A1 - Garcia-Ruiz, E. A1 - Resano, M. T1 - Simultaneous determination of halogens by high resolution absortion spectrometry N2 - The high ionization potentials and low wavelength emission lines of halogens difficult the analysis of their organohalogen compounds by ICP-based methods [1]. Other techniques, such as combustion ion chromatography (CIC) or ion-selective electrodes have proven to be more reliable to determine these elements. However, these techniques are more time-consuming and/or have lower precision and accuracy. High resolution continuum source graphite furnace molecular absorption spectrometry (HR CS GFMAS) allows the determination of solid and liquid samples by monitoring a molecule formed with the analyte and a molecule forming reagent. In the case of F, Cl and Br, several molecule forming agents have been studied for their determination. Among all of them, calcium can form a stable bond with the three elements and provides optimal analytical properties for trace analysis [2]. However, the spectral window of commercially available continuum source AAS instruments is not broad enough to cover the wavelength range necessary for a simultaneous determination. Thus, coupling it with a modular simultaneous echelle spectrograph (MOSES), which can register around 200 nm in a single measure, allows the simultaneous study of the three analytes [3]. This instrumentation is capable of register more than 200 nm of the spectra per measure keeping a high resolution. This spectral window is suitable for the monitorization of a variety of transitions of the three molecules. However, some of them are overlapped and the competitive mechanism of formation of the three molecules modify their sensitivity depending on the proportions in the sample. In this study, a compromise in the conditions and modifiers were selected in order to maximize the sensitivity and signal to noise ratio for the three molecules. The determination was carried out by standard addition of CaF and Cl and Br were obtained from the PLS model. References: [1] X. Bu, T. Wang, G. Hall, J. Anal. At. Spectrom., 18, 1443–1451 (2003) [2] M. Resano, E. García-Ruiz, M. Aramendía, M. A. Belarra, J. Anal. At. Spectrom., 34, 59–80 (2019) [3] S. Geisler, M. Okruss, H. Becker-Ross, M. Dong Huang, N. Esser, S. Florek, Spectrochimica Acta PartB, 107, 11–16 (2015) T2 - Adlershofer Forschungsforum CY - Berlin, Germany DA - 11.11.2019 KW - Halogens KW - Fluorine KW - Simultaneous determination KW - MOSES KW - Chemometry KW - Interferences PY - 2019 AN - OPUS4-51998 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 - Lopez-Linares, F. A1 - Poirier, L. A1 - Jakubowski, Norbert A1 - Recknagel, Sebastian A1 - Panne, Ulrich T1 - Shake, shut, and go – A fast screening of sulfur in heavy crude oils by highresolution continuum source graphite furnace molecular absorption spectrometry via GeS molecule detection N2 - A fast and simple method for sulfur quantification in crude oils was developed by using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). For this, heavy crude oil samples were prepared as microemulsion (shake) and injected into a graphite furnace (shut). Finally, the concentration of sulfur was determined by monitoring in situ the transient molecular spectrum of GeS at wavelength 295.205nm after adding a germanium solution as molecular forming agent (and go). Zirconium dioxide in the form of nanoparticles (45–55nm) was employed as a permanent modifier of the graphite furnace. Calibration was done with an aqueous solution standard of ammonium sulfate, and a characteristic mass (m0) of 7.5ng was achieved. The effectiveness of the proposed method was evaluated analizing, ten heavy crude oil samples with Sulfur amounts ranging between 0.3 and 4.5% as well as two NIST standard reference materials, 1620c and 1622e. Results were compared with those obtained by routine ICP-OES analysis, and no statistical relevant differences were found. KW - Heavy crude oil KW - Sulfur KW - HR-CS-MAS KW - Germanium sulfide KW - Microemulsion PY - 2019 DO - https://doi.org/10.1016/j.sab.2019.105671 SN - 0584-8547 VL - 160 SP - 105671 PB - Elsevier B.V. CY - Amsterdam, Netherlands AN - OPUS4-48747 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Richter, Silke A1 - Kipphardt, Heinrich A1 - Recknagel, Sebastian A1 - Pfeifer, Jens T1 - Characterisation of a high purity nickel material to be used as a primary standard for element determination N2 - A candidate material for the use as primary standard for nickel determination was characterized with respect to total purity. For element determination a pure material can serve as primary standard. However, real world materials are never absolutely pure, hence the total purity of such materials need to be determined experimentally. A reasonable target uncertainty for the purity statement is 10-4 relative. Usually, the purer the material, the easier it is to achieve this target uncertainty. There are two basic ways in order to be able to establish a total purity statement. One is to determine the main component of a high purity material by a direct method such as coulometry, gravimetry or titrimetry. However, these methods are not selective enough for one element and therefore require certain efforts to analyse the material with respect to impurities with interfering analytes. Moreover, to reach the defined target uncertainty is not easy or often impossible to achieve. The second approach is to determine the sum of all possible impurities (as mass fraction) and to subtract it from the ideal purity of 100 % (1 kg/kg). In principle all impurities (all elements not being the matrix element), metals and non-metals must be considered. In this work both approaches to determine the total purity of the nickel material were followed and compared. The primary (solid) standards are usually used to prepare primary calibration solutions to which secondary and lower order calibration solutions are linked. T2 - BERM-15 CY - Berlin, Germany DA - 23.09.2018 KW - Primary standard KW - High purity material KW - Nickel PY - 2018 AN - OPUS4-46216 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Röthke, A. A1 - Richter, Silke A1 - Görlitz, V. A1 - Pape, C. A1 - Schulz, U. A1 - Jährling, R. A1 - Meinhardt, R. A1 - Koenig, M. A1 - Becker, D. A1 - Charoud-Got, J. A1 - Weber, M. A1 - Rienitz, O. T1 - As good as or even better than ID-ICP-MS? High accuracy ICP OES determination of 1 g/kg mercury solutions N2 - To establish the SI traceability of the element content w(Hg) of a gravimetrically prepared 1 g/kg mercury solution, the latter was compared to a primary reference solution by means of high accuracy inductively coupled plasma optical emission spectrometry (ICP OES) measurements. For this purpose, the ICP OES bracketing method previously described [1] was improved to yield a relative expanded uncertainty of the mercury element content of Urel(w(Hg)) = 0.5 % (with k = 2) associated with the comparison of two monoelemental solutions. In case of mercury, such a small uncertainty was achieved for the first time. Before, in general, such small uncertainties were only reported applying isotope dilution methods performed with MC-ICP-MS. However, for mercury solutions at this concentration range, several dilution steps are necessary to prepare the samples for ID-MC-ICP-MS. The sum of the uncertainty contributions stemming from the dilution steps, as well as the intrinsic difficulties of measuring mercury at low concentrations, result in an overall uncertainty of the ICP-MS measurements, which is comparable to or even larger than those, achieved with the ICP OES method applied. We will present details of the sample preparation as well as of the dedicated ICP OES measurement approach, which were crucial to achieve such a small measurement uncertainty. The newly developed method was successfully applied in the context of the development and production of elemental solution chemical reference standards (CRS), which are distributed by the EDQM. The CRS are intended to support measurements required by the European Pharmacopoeia, which has recently incorporated a new international guideline for the control of elemental impurities in medicinal products. T2 - ICP-MS Anwendertreffen CY - Berlin, Germany DA - 03.09.2018 KW - Traceability KW - Mercury solution PY - 2018 AN - OPUS4-46218 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Richter, Silke T1 - Zertifizierung von Referenzmaterialien an der BAM N2 - Wege zur Zertifizierung von Referenzmaterialien an der BAM werden anhand des Leitfadens und praktischer Beispiele gegeben. T2 - Schulung zur Zertifizierung von RM CY - Berlin, Germany DA - 11.04.2018 KW - Referenzmaterialien KW - Zertifizierung PY - 2018 AN - OPUS4-46221 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Richter, Silke A1 - Pfeifer, Jens A1 - Recknagel, Sebastian T1 - The USE of GDMS in the certification procedure of reference materials N2 - Reference materials are essential, when the accuracy and reliability of measurement results need to be guaranteed in order to generate confidence in the analysis. These materials are frequently used for determining measurement uncertainty, for validation of methods, suitability testing and quality assurance. Especially direct solid sampling methods require reference materials for calibration. They guarantee that measurement results can be compared to recognized reference values. This presentation gives an overview about the use of GDMS in various certification procedures. Because it represents a fast, sensitive, multielement analyses technique without extensive sample preparation it plays a special role for the purity determination of high purity standards. Various calibration strategies and the preparation of traceable matrix matched calibration standards will be discussed. For the certification of analyte content in matrix materials mainly techniques with solvent sample preparation are used. Here GD-MS is used to identify possible loss or contamination with analytes during the sample preparation step. Typically used acids to dissolve matrices lead to interferences in the ICP- mass spectrometric detection of various analytes and their quantification. Here GD-MS as direct method can also add an important contribution in the certification process. T2 - 4th IGDSS CY - Berlin, Germany DA - 15.04.2018 KW - GDMS KW - Reference materials PY - 2018 AN - OPUS4-46222 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoffmann, V. A1 - Richter, Silke T1 - Progress at the calibration of light elements N2 - Analytical glow discharges with optical (GD-OES) and mass spectrometric (GD-MS) detection are able to obtain depth resolved information about the light elements hydrogen, carbon, nitrogen and oxygen in solid samples, where most of the other analytical techniques fail. However, the interpretation or even quantification of the measured signals is still very challenging. Problems arise due to physical effects (plasma processes such as the ‘Hydrogen effect’, the Doppler effect, self absorption or diffusion of hydrogen in the sample during sputtering) chemical effects(e.g. formation of compounds with argon or the matrix, poisoning of the sample or gettering) as well as instrumental difficulties (e.g. of the sensitivity, calibration and vacuum quality).. The GD techniques are direct solid sampling methods and require reference materials for calibration. Unfortunately the list of available certified reference materials (CRM) suited for calibration of light elements in different matrix is relatively short Therefore, sintered materials doped with the analytes H2, O2 and N2 were produced at IFW Dresden and applied as calibration standards for hydrogen, oxygen and nitrogen. Due to the high analyte concentration added, it is very likely that the real concentration agree well with the added amount of light elements in the corresponding phases. The validation of the determination of the light element concentration in the sintered samples was possible in some cases only due to the lack of suitable techniques. This fact proves the need for the development of a reliable quantification of light elements by GDS. A systematic dependence of the sputtering rate on the composition was found and can be explained by basic principles. Using mixtures of TiH2 and ZrH2 with Cu the ratio of hydrogen and Cu lines has a good correlation with the corresponding concentration ratio. The hydrogen emission yield however decreases over 0.3 m% hydrogen and finally the hydrogen intensity may even decrease. This behaviour can be explained by a very similar quenching of the hydrogen and copper intensity caused by the hydrogen effect. First experiments with GD-MS show no saturation of the hydrogen ion current and thus confirm the quenching of the emission yield in GD-OES. Sintered material for the oxygen calibration (Al2O3, CuO, Cu2O and MgO mixed with Cu, Al and Mg) confirmed the blue line shift effect at O I 130.22 nm, first time reported by Köster 2009 [1]. The effect is more pronounced at Mg than in Al and Cu, which due to line interference leads to a matrix dependent EY. This effect is negligible at O I 777.19 nm and the EY is matrix independent. Using GD-MS first promising results for the calibration of oxygen with these sintered samples could be obtained, when the sputtering rate was included in the evaluation. More recently also sintered material for nitrogen calibration (AlN mixed with Al and Si3N4 mixed with Cu) was produced and points to a matrix independent emission yield of nitrogen T2 - 04 IGDSS CY - Berlin, Germany DA - 15.04.2018 KW - Glow Discharge KW - Non metals PY - 2018 AN - OPUS4-46223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinrich, Hans-Joachim A1 - Richter, Silke A1 - Recknagel, Sebastian T1 - Certification of the mass fractions of trace elements in a medium purity graphite reference material N2 - The increasing application of graphite materials in various fields of technology and science enhances the demand for strictly controlled properties which are often directly correlated to the contents of trace element impurities. Therefore, the availability of powerful, rapid and reliable analytical methods for the determination of trace impurities is essential for process and quality control. Certified reference materials, indispensable for the development and validation of appropriate trace analytical methods for the characterization of special purity graphite materials are still lacking. Therefore, BAM in co-operation with the working group “Special Materials” of the committee of chemists of GDMB (Gesellschaft der Metallurgen und Bergleute e.V.) certified an industrially sourced graphite material with genuine elemental impurities. The candidate material was a commercial product (NBG 18) taken from the customary production line of the producer SGL CARBON, Chedde (France). The homogeneity of the powdered material was assessed by means of ETV-ICP OES and DC Arc-OES. Certification of the candidate reference material was based on an inter-laboratory comparison involving 17 expert laboratories from Germany, France, Slovenia, USA, South Africa. A variety of different mineralization, digestion, leaching, fusion and combustion techniques prior to ICP OES and photometry, methods without sample preparation (INAA, k0-INAA) as well as typical solid sampling methods (ETV-ICP OES, ETV-ICP-MS, SS-ET AAS, DC Arc-OES, MF-DC Arc-OES) were used to characterise the material. Certified mass fractions and their expanded uncertainties (k = 2) were assigned for 27 elements (Al, B, Ba, Be, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Ti, V, W, Y, Zn, Zr), ranging from (0.00050 ± 0.00027) mg/kg for Be to (41 ± 6) mg/kg for Si. Informative values are given for further parameters: trace element contents of Ag, As, Au, Bi, Cd, Cs, Dy, Eu, Ga, Gd, Hg, In, La, Nb, Rb, Re, Rh, Sb, Sc, Se, Sm, Sn, Ta, Tb, Te, Th, U; method specific values obtained by ETV-ICP OES (BETV and SiETV) and ash content. The new certified material is available as BAM Reference Material BAM-S009 Medium Purity Graphite Powder. T2 - BERM-15 CY - Berlin, Germany DA - 23.09.2018 KW - Certification KW - Graphite KW - Reference material KW - Trace elements PY - 2018 AN - OPUS4-46235 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -