TY - CONF A1 - Abad Andrade, Carlos Enrique A1 - Florek, S. A1 - Becker-Ross, H. A1 - Huang, M.-D. A1 - Muench, S. A1 - Okruss, M. A1 - Mao, X. A1 - Zorba, V. A1 - Recknagel, Sebastian A1 - Tatzel, Michael A1 - Vogl, Jochen A1 - Jakubowski, Norbert A1 - Panne, Ulrich T1 - A comparative analysis of optical spectrometry methods and MC-ICP-MS for stable isotope analysis of magnesium in geological samples N2 - Society for Applied Spectroscopy (SAS) Atomic Section Student Award. Magnesium is a major element in the hydrosphere and biosphere and plays important roles in (bio-) geochemical and physiological cycles. Mg has three stable isotopes, 24Mg, 25Mg and 26Mg. It is due to their relatively large mass difference (~8% between) that isotope fractionation leads to slight variations of isotope amount ratios in biological, environmental and geological samples. Traditionally, isotope ratios are measured by mass spectrometric methods. Their drawbacks include the high costs for instruments and their operation, experienced operators and elaborate time-consuming chromatographic sample preparation. Recently, optical spectrometric methods have been proposed as faster and low-cost alternative for the analysis of isotope ratios of selected elements by means of high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS), and laser ablation molecular isotopic spectrometry (LAMIS). For the determination of Mg isotope ratios in selected rock reference materials, the molecular spectrum of the in-situ generated MgF and MgO molecules were studied and their results compared with MC-ICP-MS. By HR-CS-MAS, samples were dissolved by acid digestion and Mg isotopes analyzed with and without matrix. The absorption spectrum was recorded for MgF for the electronic transitions X 2Σ → A 2 Πi, and X 2Σ → B 2Σ+. In the case of LAMIS, we investigated the MgF molecule for the electronic transition A 2Πi → X 2Σ, as well as direct analysis by the MgO molecule for the electronic transition A 1Π+ → X 1Σ. The MgF and MgO spectra are described as the linear combination of their isotopic components or isotopologues: 24MgF, 25MgF, and 26MgF for the MgF and 24MgO, 25MgO, and 26MgO for the MgO. The isotope analysis was done by deconvolution of the MgF spectrum by partial least square regression (PLS) calibrated with enriched isotope spikes. Results were accurate with precisions ranging between 0.2 ‰ and 0.8 ‰ (2 SD, n= 10) for HR-CS-GFMAS. No statistically significant differences were observed for samples w/o matrix extraction. On the other hand, LAMIS allows the direct analysis of solid samples with the extended possibility of direct analysis, however the precision is lower due the lack of solid isotopic calibration standards. T2 - SciX 2019. 46th Annual North American Meeting of the Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) CY - Palm Springs, CA, USA DA - 13.10.2019 KW - Isotope analysis KW - Diatomic molecule KW - Magnesium KW - MC-ICP-MS KW - HR-CS-MAS KW - LIBS PY - 2019 AN - OPUS4-49883 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - von der Au, Marcus A1 - Meermann, Björn T1 - A fast and simple extraction method for the determination of PFASs in soil samples - HR-CS-GFMAS a new screening tool N2 - Here, we describe a fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) utilizing extractable organic fluorine (EOF) sum parameter analysis and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) in soil samples. After extraction and separation of inorganic and organic fluorinated compounds, organically bound fluorinated compounds were indirectly determined via the molecular absorption of gallium mono-fluoride at 211.248 nm. The implementation of the decisions of the “Stockholm Convention on persistent organic pollutants” as well as the “Protocol on Persistent Organic Pollutants of the Convention on Long-Range Transboundary Air Pollution” of the UNECE include the reduction respectively the elimination of PFASs in the environment. Currently, regulations aim to target single compounds (mostly C8-PFAS). But the PFAS group includes over 4700 substances, which are potentially persistent and toxic, thus target analytical approaches are not suitable for a holistic approach investigating the PFAS pollutant situation. Furthermore, forbidden PFASs are substituted by short-chain PFASs, thus the number of unknow substances is steadily increasing. For this reason, sum parameter approaches are more suitable to investigate and assess the pollution situation as well as derive exposure limits. Our developed analytical method was successfully applied to determine PFASs in soil samples from a polluted site. In view of steadily increasing numbers of PFAS substances, our method will make an important contribution in assessing the pollution situation as well as support policy makers in deriving exposure limits for PFAS in the future. T2 - ENSOr - International Workshop on Emerging policy challenges on new soil contaminants CY - Online Meeting DA - 06.05.2021 KW - PFAS KW - HR-CS-GFMAS KW - Soil KW - Sediment PY - 2021 AN - OPUS4-52608 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - Meermann, Björn T1 - A fast and simple PFAS extraction method for soil sample analysis using HR-CS-GFMAS N2 - Per- and polyfluorinated alkyl substances (PFASs) are a substance class of over 4730 individual compounds. Several PFASs are extremely persistent, bioaccumulative and toxic. The analysis of PFASs is challenging because of their different chemical and physical properties as well as the high number of target substances. Target-based approaches (e.g., LC-MS/MS) are limited to the availability of analytical grade standards and are not suitable for the analysis of new/unknown PFASs and transformation products. Therefore, PFAS sum parameter methods become increasingly important to indicate a realistic PFAS pollution level. PFAS sum parameters compromise the proportion of organically bound fluorine that can either be extracted (EOF) or adsorbed to activated carbon (AOF). For the instrumental analysis of such sum parameters, a fluorine selective detector is needed. High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) is a sensitive and highly selective tool for indirect fluorine determination. The method is based on the in situ formation of diatomic gallium-mono fluoride (GaF) in a graphite furnace at a temperature of 1550°C. The molecular absorption of GaF can be detected at its most sensitive wavelength at 211.248 nm providing limits of quantification of c(F) 2.7 µg/L. Here, we describe a fast and simple extraction method for the determination of the EOF using HR-CS-GFMAS in soil samples. Common approaches for the EOF determination use solid phase extraction (SPE). To omit the bias of this time consuming and expensive step we optimized a fast and simple SPE-free extraction method. The developed extraction method consists of a liquid-solid extraction using acidified methanol. Comparison of the method with and without an SPE clean-up step revealed a drastic underestimation of EOF concentrations using SPE. In the next step, the applicability of our method was tested for other solid matrices. In view of steadily increasing numbers of PFASs, our method will make an important contribution in assessing the pollution situation as well as support policy makers in deriving exposure limits for PFASs in the future. T2 - Analytica conference CY - München, Germany DA - 21.06.2022 KW - PFAS KW - HR-CS-GFMAS KW - Soil KW - Fluorine KW - SPE PY - 2022 AN - OPUS4-55124 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - von der Au, Marcus A1 - Meermann, Björn T1 - A fast and simple PFAS extraction method for soil samples utilizing HR-CS-GFMAS N2 - Here, we describe a fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) utilizing extractable organic fluorine (EOF) sum parameter analysis and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) in soil samples. After extraction and separation of inorganic and organic fluorinated compounds, organically bound fluorinated compounds were indirectly determined via the molecular absorption of gallium mono-fluoride at 211.248 nm. The implementation of the decisions of the “Stockholm Convention on persistent organic pollutants” as well as the “Protocol on Persistent Organic Pollutants of the Convention on Long-Range Transboundary Air Pollution” of the UNECE include the reduction respectively the elimination of PFASs in the environment. Currently, regulations aim to target single compounds (mostly C8-PFAS). But the PFAS group includes over 4700 substances, which are potentially persistent and toxic, thus target analytical approaches are not suitable for a holistic approach investigating the PFAS pollutant situation. Furthermore, forbidden PFASs are substituted by short-chain PFASs, thus the number of unknow substances is steadily increasing. For this reason, sum parameter approaches are more suitable to investigate and assess the pollution situation as well as derive exposure limits. Our developed analytical method was successfully applied to determine PFASs in soil samples from a polluted site. In view of steadily increasing numbers of PFAS substances, our method will make an important contribution in assessing the pollution situation as well as support policy makers in deriving exposure limits for PFAS in the future. T2 - SALSA Make and Measure ... and Machines CY - Online meeting DA - 16.09.2021 KW - PFAS KW - HR-CS-GFMAS KW - IC KW - EOF KW - Soil PY - 2021 AN - OPUS4-53302 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF 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 N2 - For the first time polyethylene (PE) frits were used to quantify sulphur in copper metal and its alloys by isotope dilution combined with LA-ICP-MS: an alternative approach for sample preparation. The properties of the PE frit meet the requirements for isotope dilution LA-ICPMS which are porous material, thermal and chemical resistance and high absorption efficiency. The breakthrough, however, as a support material, is the low sulphur blank, which is only two times of the gas flow blank (2.3-4.0 x 10⁴ cps). Additionally, the porosity of the frit was considered, as it directly affects the absorption efficiency for the sample solution, which is present in the cavities of the frit. The absorption efficiency was studied by loading sulphur standards with varying sulphur amounts (0 - 80 µg S) onto the frits. The remaining sulphur which was not absorbed by the frit was rinsed off and was measured by ICP-MS. This indirect method shows that more than 99.5 % of the loaded sulphur was absorbed by the frit. The so prepared frits with increasing sulphur amount were measured by LA-ICP-MS showing a good linearity between 0 µg S and 40 µg S with a coefficient of determination, r2 of 0.9987 and a sensitivity of 3.4x10⁴ cps µgˉ¹ for 32S. Three copper reference materials produced by BAM (BAM-M376a, BAM-228 and BAM-227) were selected to develop and validate the LA-ICP-IDMS procedure. The IDMS technique was applied to these samples as follows: the samples were spiked, dissolved, digested and then the digested solution was absorbed on the frits. The dried frit samples were then analyzed by LA-ICP-IDMS and it could be demonstrated that the sample solution dispersed on the frits did not influence the 32S/34S ratio significantly even though the sulphur intensities were fluctuating along the scan lines. Relative standard deviations of the isotope ratios were below 5 % in average between 3 lines (except for the pure spike solution and procedure blank). The measurement results were validated by comparing them with the results obtained by conventional ICP-IDMS. Plotting the mass fraction of sulphur in copper obtained by LA-ICP-IDMS versus those obtained by ICP-IDMS yields a linear curve with a correlation coefficient of 0.9999 showing a strong agreement between both techniques. The metrological traceability to the SI for the mass fraction of sulphur in copper is 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 the final mass fraction in the samples obtained by LA-ICP-IDMS is illustrated in this presentation. T2 - ESAS & CANAS 2018 CY - Berlin, Germany DA - 20.03.2018 KW - Laser ablation KW - Isotope dilution mass spectrometry KW - SI traceability KW - Measurement uncertainty PY - 2018 AN - OPUS4-44641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Oelze, Marcus A1 - Vogl, Jochen T1 - A second anchor Fe isotope reference material based on high purity Fe metal for the exhausted IRMM-014 N2 - Iron isotopes are used in a variety of fields from e.g., geologic question to medical applications. Measurements of iron isotopes are usually performed as delta measurements to an artificial based delta zero standard. In the case of Fe isotopes is that delta zero standard IRMM-014, a pure Fe metal. Unfortunately, that conventional delta zero reference material defining the 56/54Fe scale is out of stock and therefore unavailable. To overcome that situation and fulfill the need for laboratories that measure Fe isotope on a regular basis we will provide a set of solutions with IRMM-014 and a second anchor point for Fe isotope ratio measurements that is based on a pure Fe metal. This new second anchor point, a high purity Fe from BAM, will be calibrated against IRMM-014 and can be used as bracketing standard or as reference value for stable Fe isotope measurements. We are in the good situation that BAM ordered a large stock of IRMM-014 several years ago. That stock of IRMM-014 Fe cubes and IRMM-014 Fe wires will be dissolved in 6M HCl in a large quantity. The new anchor point, the high purity Fe metal, that is commercially available at BAM, is a pure Fe metal with only trace amounts of impurities. The high purity BAM material will also be dissolved in 6M HCl in large quantity. Several aliquots of both solutions will be measured on the Neptune Plus MC-ICP-MS to define this second anchor point with a low uncertainty. Further will we send several aliquots of both solutions to different laboratories to also measure this second anchor point of high purity Fe on the 56/54Fe scale. We will report the values of that study on BAM high purity Fe and will provide a guide for scale conversion to the IRMM-014 scale and for uncertainty calculation to use that new anchor point instead of the exhausted IRMM-014. T2 - EWCPS CY - Ljubljana, Slovenia DA - 30.01.2023 KW - Iron isotopes KW - Reference material PY - 2023 AN - OPUS4-58012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen A1 - Noordmann, J. A1 - Rosner, M. A1 - Goenaga-Infante, H. A1 - Štrok, M. A1 - Pramann, A. A1 - Vanhaecke, F. A1 - Meisel, T. A1 - Pröfrock, D. A1 - Prohaska, T. A1 - Vocke, R.D. A1 - Richter, S. T1 - Absolute Isotope Ratios N2 - Measurement results and scientific models leading to important decisions in forensics, food fraud or climatology are based on isotope ratio data. Molar masses of multi-isotopic elements are as well based on isotope ratio data. Thus, in the case of Si, isotope ratios directly impact the redefinition of the SI base units kilogram and mole. Therefore, new strategies are required leading to new primary isotope reference materials, whose isotope ratios are traceable to the SI. This in turn will ensure the comparability of isotope ratio data and will render the traceability exception requested by the CCQM superfluous. Such new procedures will be developed for the key elements S, Si, Ca, Sr and Nd at relative uncertainty levels of ≤ 0.01 %. T2 - EURAMET TC-MC Meeting CY - Vienna, Austria DA - 05.02.2018 KW - Metrology in chemistry KW - Isotope amount ratio KW - SI traceability KW - Atomic weight KW - Molar mass KW - Synthetic isotope mixtures PY - 2018 AN - OPUS4-44644 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogl, Jochen T1 - Absolute isotope ratios - a proposed research topic N2 - An introduction into absolute isotope ratios is given, with application fields ranging from fundamental science to geochronology and forensics. This is followed by a proposal for developing new calibration approaches for obtaining absolute isotope ratios at unrivaled uncertainty levels. This new developments will set the basis for improvements in all scientific fields. T2 - EURAMET TC-MC Workshop on Isotope Ratio Analysis CY - Bern, Switzerland DA - 05.02.2020 KW - Absolute isotope ratio KW - Isotope fractionation KW - Metrology KW - Fundamental science PY - 2020 AN - OPUS4-50346 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Junge, Florian A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Gehrenkemper, Lennart A1 - Zoister, Christian A1 - Nickl, Philip A1 - Koch, Matthias A1 - Meermann, Björn A1 - Haag, Rainer T1 - Adsorber Charge Dominates over Hydrophobic or Fluorophilic Functionalization in Influencing Adsorption of PFCA onto Polystyrene Resins JF - Advanced Materials Interfaces N2 - A systematic series of industrial-relevant polystyrene-based anion exchange resins that are functionalized with hydro- or fluorocarbon chains are compared regarding their adsorption behavior toward perfluorocarboxylic acids (PFCA) in respect to their charge, chain length, and type of chain. The results clearly show the dominance of electrostatic interactions in the adsorption process as uncharged adsorber materials showed no adsorption at all. In contrast, the charged adsorber materials showed in general a PFCA removal of 80% to 30% over the experiment depending on effluent fraction. Unexpectedly, for perfluorobutanoic acid (PFBA) the highest removal rate is found with consistently >90%. Despite observing significant benefits in the adsorption of PFCA for fluoroalkylated adsorbers in comparison to their non-fluorinated counterparts, this effect of fluoroalkylation is comparatively small and can not be clearly attributed to fluorophilic interactions between the fluoroalkyl chains. These findings help clarifying that the introduction of fluorocarbon moieties in adsorber materials is not necessary in order to remove fluorocarbon molecules from the environment. KW - PFAS KW - Remediation KW - Adsorption KW - Fluorophilic interactions PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601883 DO - https://doi.org/10.1002/admi.202400199 SP - 1 EP - 10 PB - John Wiley & Sons CY - Hoboken, New Jersey, USA AN - OPUS4-60188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Phukphatthanachai, Pranee A1 - Vogl, Jochen A1 - Traub, Heike A1 - Jakubwoski, Norbert A1 - Panne, Ulrich T1 - An alternative approach of using pe frits for the quantification of sulfur in copper metals and its alloys by isotope dilution LA-ICP-MS N2 - This is the first time that PE frits were used to quantify sulfur in copper and its alloys by isotope dilution combined with LA-ICP-MS: an alternative approach for sample preparation. The following properties of the PE frit meet the requirements for isotope dilution LA-ICPMS:: porous material, thermo plastic (melting point >100oC), chemical resistance (nitric acid >70%) and high adsorption efficiency. The breakthrough, however, as a support material, especially when comparing the PE frit with other materials such gelatin or sodium silicate is the low blank, which is only two times of the gas flow blank (2.3-4.0 x 104 cps). Additionally, the porosity of the frit was considered, as it directly affects the adsorption efficiency for the sample solution, which is present in the cavities of the frit. Adsorption efficiency was studied by depositing sulfur standards with varying sulfur amounts (0, 2, 5, 10, 20, 40 and 80 µg S) on the frits. The remaining sulfur which was not absorbed by the frit was rinsed off and was measured by ICP-MS. This indirect method shows that more than 99.5 % of the loaded sulfur was absorbed by the frit. Such high absorption efficiency is completely sufficient for a support material to be used in LA-ICP-IDMS. The so prepared frits whith increasing sulfur amount were measured by LA-ICP-MS showing a good linearity between 0 µg S and 40 µg S whit a correlation coefficient r2 of 0.9987 and sensitivy of 3.4x104 cpsµg-1 for 32S. Three copper reference materials produced by BAM were selected to develop and validate the LA-ICP-IDMS procedure. The IDMS technique was applied to these samples as follows: the samples were spiked, dissolved, digested and then the digest was adsorbed on the frits. T2 - Winter Conference on Plasma Spectrochemistry CY - Amelia Island, FL, USA DA - 08.01.2018 KW - Laser ablation KW - Isotope dilution mass spectrometry KW - SI traceability KW - Measurement uncertainty PY - 2018 AN - OPUS4-44642 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -