TY - CONF A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - On-line species-specific isotopic analysis of sulfur by hyphenation of capillary electrophoresis with MC-ICP-MS N2 - In many scientific fields, isotopic analysis can offer valuable information. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. Whereas some works hyphenating GC and IC with MC-ICP-MS have already been reported, LC and CE hyphenations are still inadequately represented based on the capabilities of these separation techniques. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species using a multiple-injection approach for instrumental mass bias correction by standard-sample bracketing. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared to data from off-line analysis of the same samples to ensure accuracy. The precision of the results of the on-line measurements was promising regarding the differentiation of the river systems by the isotopic signature of river water sulfate. The great potential of this method is based on the versatility of the applied separation technique, not only in the environmental field but also for, e.g., biomolecules, as sulfur is the only covalently bound constituent of proteins that can be analyzed by MC-ICP-MS. T2 - Virtual Goldschmidt 2020 CY - Online meeting DA - 21.06.2020 KW - Isotopic analysis KW - Hyphenated techniques KW - Capillary electrophoresis KW - Multicollector-ICP-MS KW - Speciation analysis PY - 2020 AN - OPUS4-50922 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - Method development for on-line species-specific sulfur isotopic analysis by means of capillary electrophoresis/multicollector ICP-mass spectrometry JF - Analytical and Bioanalytical Chemistry N2 - In this work, a method for species-specific isotopic analysis of sulfur via capillary electrophoresis hyphenated on-line with multicollector ICP-MS (CE/MC-ICP-MS) was developed. Correction for the mass bias caused by instrumental mass discrimination was realized via external correction with multiple-injection sample-standard bracketing. By comparing the isotope ratio measurement results obtained using the newly developed on-line CE/MC-ICP-MS method with those obtained via traditional MC-ICP-MS measurement after analyte/matrix separation by anion exchange chromatography for isotopic reference materials and an in-house bracketing standard, the most suitable data evaluation method could be identified. The repeatability for the sulfate-δ34S value (calculated from 18 measurements of a standard conducted over seven measurement sessions) was 0.57‰ (2SD) and thereby only twice that obtained with off-line measurements (0.30‰, n = 68). As a proof of concept for analysis of samples with a real matrix, the determination of the sulfur isotopic composition of naturally present sulfate was performed for different river systems. The CE/MC-ICP-MS results thus obtained agreed with the corresponding off-line MC-ICP-MS results within the 2SD ranges, and the repeatability of consecutive δ34S measurements (n = 3) was between 0.3‰ and 1.3‰ (2SD). Finally, the isotopic analysis of two different S-species in a river water sample spiked with 2-pyridinesulfonic acid (PSA) was also accomplished. KW - River water sulfate KW - Environmental speciation KW - Sulfur isotopes KW - On-line CE/MC-ICP-MS KW - Multiple-injection sample-standard bracketing PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509549 DO - https://doi.org/10.1007/s00216-020-02781-8 SN - 1618-2642 VL - 412 IS - 23 SP - 5637 EP - 5646 PB - Springer CY - Berlin, Heidelberg AN - OPUS4-50954 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - On-line Species-specific Isotopic Analysis of Sulfur by Hyphenation of Capillary Electrophoresis with Multicollector-ICP-MS N2 - In many scientific fields, isotopic analysis can offer valuable information. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. Whereas some works hyphenating GC and IC with MC-ICP-MS have already been reported, LC and CE hyphenations are still inadequately represented based on the capabilities of these separation techniques. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species using a multiple-injection approach for instrumental mass bias correction by standard-sample bracketing. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared to data from off-line analysis of the same samples for validation. The repeatability of the results of the on-line measurements was promising regarding the differentiation of the river systems by the isotopic signature of river water sulfate. The great potential of this method is based on the versatility of the applied separation technique, not only in the environmental field but also for, e.g., biomolecules because sulfur is the only covalently bound constituent of proteins that can be analyzed by MC-ICP-MS. T2 - SciX 2020 CY - Online meeting DA - 12.10.2020 KW - Capillary electrophoresis KW - Hyphenated techniques KW - Isotopic analysis KW - Speciation analysis PY - 2020 AN - OPUS4-51402 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - On-line hyphenation of CE with multicollector-ICP-MS for species-specific isotopic analysis of sulfur N2 - In many scientific fields, isotopic analysis can offer valuable information, e.g., for tracing the origin of food products, environmental contaminants, forensic and archaeological samples (provenance determination), for age determination of minerals (geochronological dating) or for elucidating chemical processes. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared with data from off-line analysis of the same samples to ensure accuracy. The precision of the results of the on-line measurements was high enough to distinguish the rivers from one another by the isotopic signature of the river water sulfate. Next to environmental applications, a future field could be species-specific isotopic analysis of biomolecules, as sulfur is the only covalently bound constituent of proteins which can be analyzed by MC-ICP-MS. T2 - CE-Forum 2019 CY - Waldbronn, Germany DA - 11.12.2019 KW - Isotopic analysis KW - Multicollector-ICP-MS KW - Capillary electrophoresis KW - Hyphenated techniques KW - Speciation analysis PY - 2019 AN - OPUS4-50038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian A1 - Rodiouchkina, K. A1 - Vanhaecke, F. A1 - Meermann, Björn T1 - On-line hyphenation of CE with multicollector-ICP-MS for species-specific isotopic analysis of sulfur N2 - In many scientific fields, isotopic analysis can offer valuable information, e.g., for tracing the origin of food products, environmental contaminants, forensic and archaeological samples (provenance determination), for age determination of minerals (geochronological dating) or for elucidating chemical processes. Up to date, typically bulk analysis is aimed at measuring the isotopic composition of the entire elemental content of the sample. However, the analyte element is usually present under the form of different species. Thus, separating species of interest from one another and from matrix components prior to isotope ratio measurements can provide species-specific isotopic information, which could be used for tracing the origin of environmental pollutants and elucidation of (environmental) speciation. Using on-line hyphenations of separation techniques with multicollector-ICP-MS (MC-ICP-MS) can save time and effort and enables the analysis of different species during a single measurement. In this work, we developed an on-line hyphenation of CE with multicollector-ICP-MS (CE/MC-ICP-MS) for isotopic analysis of sulfur species. With this method, the isotopic composition of sulfur in sulfate originating from river water could be analyzed without sample preparation. The results were compared with data from off-line analysis of the same samples to ensure accuracy. The precision of the results of the on-line measurements was high enough to distinguish the rivers from one another by the isotopic signature of the river water sulfate. Next to environmental applications, a future field could be species-specific isotopic analysis of biomolecules, as sulfur is the only covalently bound constituent of proteins which can be analyzed by MC-ICP-MS. T2 - DGMS 2020 CY - Münster, Germany DA - 01.03.2020 KW - Capillary electrophoresis KW - Hyphenated techniques KW - Isotopic analysis KW - Multicollector-ICP-MS KW - Speciation analysis PY - 2020 AN - OPUS4-50501 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - Döring, A.-K. A1 - Meermann, Björn T1 - Development of complementary CE-MS methods for speciation analysis of pyrithione-based antifouling agents JF - Analytical and Bioanalytical Chemistry N2 - In the recent decade, metal pyrithione complexes have become important biocides for antifouling purposes in shipping. The analysis of metal pyrithione complexes and their degradation products/species in environmental samples is challenging because they exhibit fast UV degradation, transmetalation, and ligand substitution and are known to be prone to spontaneous species transformation within a chromatographic system. The environmental properties of the pyrithione species, e.g., toxicity to target and non-target organisms, are differing strongly, and it is therefore inevitable to identify as well as quantify all species separately. To cope with the separation of metal pyrithione species with minimum species transformation during analysis, a capillary electrophoresis (CE)–based method was developed. The hyphenation of CE with selective electrospray ionization- and inductively coupled plasma–mass spectrometry (ESI-, ICP-MS) provided complementary molecular and elemental information for the identification and quantification of pyrithione species. To study speciation of pyrithiones, a leaching experiment of several commercial antifouling paints containing zinc pyrithione in ultrapure and river water was conducted. Only the two species pyrithione (HPT) and dipyrithione ((PT)2) were found in the leaching media, in concentrations between 0.086 and 2.4 μM (HPT) and between 0.062 and 0.59 μM ((PT)2), depending on the paint and leaching medium. The limits of detection were 20 nM (HPT) and 10 nM ((PT)2). The results show that complementary CE-MS is a suitable tool for mechanistical studies concerning species transformation (e.g., degradation) and the identification of target species of metal pyrithione complexes in real surface water matrices, laying the ground for future environmental studies. KW - Complementary MS KW - Environmental speciation KW - Capillary electrophoresis-mass spectrometry KW - Antifouling biocides PY - 2019 DO - https://doi.org/10.1007/s00216-019-02094-5 SN - 1618-2642 VL - 411 IS - 27 SP - 7261 EP - 7272 PB - Springer CY - Berlin, Heidelberg AN - OPUS4-48962 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meermann, Björn A1 - Faßbender, Sebastian T1 - Antifoulingmittel im Wasser JF - Nachrichten aus der Chemie N2 - Für das Biozid Zink-Pyrithion, das in Schiffsanstrichen weit verbreitet ist, fehlten bisher die analytischen Methoden, um den Komplex und seine Abbauprodukte in der Umwelt nachzuweisen. Kapillarelektrophorese, gekoppelt mit komplementärer Massenspektrometrie könnte dieses Problem lösen. KW - Antifouling-Biozide KW - Kapillarelektrophorese-Massenspektrometrie KW - Komplementäre Massenspektrometrie KW - Umwelt-Speziation PY - 2019 DO - https://doi.org/10.1002/nadc.20194088793 SN - 1439-9598 SN - 1868-0054 VL - 67 IS - 12 SP - 56 EP - 58 PB - Wiley-VCH CY - Weinheim AN - OPUS4-49789 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Koenig, Maren A1 - Pelzer, J. A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS JF - Analytical and bioanalytical chemistry N2 - A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. KW - Methylmercury KW - Legacy pollution KW - Finow Canal KW - Isotope dilution KW - Mercury speciation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529967 DO - https://doi.org/10.1007/s00216-021-03497-z SN - 1618-2642 VL - 413 IS - 21 SP - 5279 EP - 5289 PB - Springer CY - Berlin AN - OPUS4-52996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Chronakis, Michail A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Size determination of nanoparticles by ICP-ToF-MS using isotope dilution in microdroplets JF - Journal of Analytical Atomic Spectrometry N2 - Within this work, the combination of a microdroplet generator and an ICP-ToF-MS for nanoparticle analysis is presented. For the size determination of platinum nanoparticles an on-line isotope dilution analysis approach was developed. The 194Pt/195Pt isotopic ratio was used for the characterization of the particles, while the 182W/183W isotopic ratio was monitored simultaneously for mass bias correction. The on-line ID-MDG-sp-ICP-ToF-MS approach was deployed for the size determination of three platinum nanoparticle samples (50 nm, 63 nm, 70 nm); for validation, complementary size characterization techniques (sp-ICP-ToF-MS and TEM) were used. The robustness of this technique was evidenced, by using sodium chloride concentrations up to 100 mg L−1 as a matrix component. Our new on-line ID MDG-sp-ICP-ToF-MS approach is a promising tool for the fast and reliable determination of nanoparticles' size in severe matrix concentrations, e.g., environmental samples. KW - ICP-ToF-MS KW - Nanoparticles KW - Isotope Dilution PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552727 DO - https://doi.org/10.1039/D2JA00072E SN - 0267-9477 VL - 37 IS - 6 SP - 1203 EP - 1207 PB - Royal Society of Chemistry AN - OPUS4-55272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Mercury speciation in sediments of a historic industrially used canal in Northern Germany using SSID GC-ICP-ToF-MS N2 - Sediments and soils can act as sinks of species of inorganic mercury (Hg2+), while they are simultaneously sources of volatile (Hg0) and organic species, such as monomethylmercury (MMHg). Although the fraction of MMHg in total Hg of sediments is suggested to be as low as 0.1 1%, MMHg is a serious threat for humans and wildlife due to its high potential for bioaccumulation and biomagnification and the ability to pass the blood-brain barrier. This is highlighted by exceptionally high MMHg concentrations found in fish and fish predators, as well as aquatic insects and birds living in close vicinity to Hg contaminated waterbodies. Humans are exposed to MMHg mainly by ingestion of (predatory) fish and rice. One example of a highly Hg contaminated waterbody is Finow Canal, the oldest artificial waterway still in operation in Germany, with Hg mass fractions of up to or even more than 100 µg/g found in the sediment, which are suggested to be attributable to a chemical plant producing (among other things) mercury-based seed dressings. Despite this high mass fraction of Hg, anaerobic conditions, high amounts of organic matter and iron, which are all favorable for Hg methylation, no investigations of Hg speciation have been conducted there up to now. We investigated Hg speciation in sediments of Finow Canal on length from before the known polluted sited into the confluence with another waterway using species-specific isotope dilution (SSID) GC-ICP-ToF-MS. Mass fraction of up to 41 ng/g MMHg were determined in samples taken from Finow Canal and elevated concentrations could also be found around 14 km downstream of the confluence of Finow Canal with another waterway. In addition to this, highly toxic monoethylmercury (EtHg) could be detected in most of the sediment samples. These results are the first evidence of the occurrence of MMHg in this region and show the need for further investigation of the whole regional ecosystem, as well as the consideration of possible measures of remediation. T2 - Virtual Goldschmidt 2021 CY - Online meeting DA - 04.07.2021 KW - Methylmercury KW - Finow Canal KW - Legacy pollution KW - Isotope dilution PY - 2021 AN - OPUS4-52945 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Retzmann, Anika A1 - Faßbender, Sebastian A1 - Rosner, M. A1 - von der Au, Marcus A1 - Vogl, Jochen T1 - Performance of second generation ICP-TOFMS for (multi-)isotope ratio analysis: a case study on B, Sr and Pb and their isotope fractionation behavior during the measurements JF - Journal of Analytical Atomic Spectrometry N2 - The performance of second generation ICP-TOFMS, equipped with a micro-channel plate (MCP) enabling multi-isotope detection, in terms of isotope ratio precision and instrumental isotopic fractionation (IIF) for (multi-)isotope ratio analysis was thoroughly assessed for B, Sr and Pb. Experimental isotope ratio precision of 0.14 % for 11B/10B intensity ratio, 0.15 % for 87Sr/86Sr intensity ratio and 0.07% for 208Pb/206Pb intensity ratio were obtained at high signal levels ($500 mg L−1) which is comparable to first generation ICP-TOFMS. The long-term stability of isotope ratios, measured over several hours and expressed as repeatability, is between 0.05 % and 1.8 % for B, Sr and Pb. The observed IIF per mass unit is negative for B (i.e., −11 % for 11B/10B) which is in accordance with measurements using sector field (MC) ICP-MS. But the observed IIF per mass unit is positive for Sr (i.e., 2 % for 87Sr/86Sr) and Pb (i.e., 4.5 % for 208Pb/206Pb) which is not in accordance with measurements using sector field (MC) ICP-MS. Furthermore, different IIFs per mass unit were observed for different isotope pairs of the same isotopic system (i.e., Sr, Pb) and adjacent isotopic systems (i.e., Pb vs. Tl). This and the observations from three-isotope plots for Sr and Pb show that ion formation, ion extraction, ion transmission, ion separation and ion detection in second generation ICP-TOFMS is subject to IIF that does not follow the known mass dependent fractionation laws and is possibly caused by mass independent fractionation and/or multiple (contradictory) fractionation processes with varying contributions. The non-mass dependent IIF behavior observed for second generation ICP TOFMS has profound consequences for the IIF correction of isotope raw data, including application of multi-isotope dilution mass spectrometry (IDMS) using ICP-TOFMS. Hence, only IIF correction models that correct also for mass independent fractionation are applicable to calculate reliable isotope ratios using second generation ICP-TOFMS. In the present study, reliable d11B values, and absolute B, Sr and Pb isotope ratios could be determined using the SSB approach in single-element solutions as well as in a mixture of B, Sr and Pb, where the isotopes were measured simultaneously. KW - ICP-TOFMS KW - Isotope delta value KW - Isotope amount ratio KW - Conventional isotope ratio KW - Instrumental isotope fractionation PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-582239 DO - https://doi.org/10.1039/d3ja00084b SN - 0267-9477 VL - 38 IS - 10 SP - 2144 EP - 2158 PB - Royal Society of Chemistry AN - OPUS4-58223 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Chronakis, Michail Ioannis A1 - von der Au, Marcus A1 - Faßbender, Sebastian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - MDG-ICP-ToF-MS: A Versatile Tool for Quantification in the field of Single Particle ICP-MS Using Isotope Dilution N2 - In the interest of exploring their potential in the field of single particle analysis, a Microdroplet Generator (MDG) was coupled to an ICP-ToF-MS. Isotopic Dilution Analysis was also incorporated for the size determination of three different Platinum nanoparticles samples (50, 63 and 70 nm). The performance of the technique was validated by comparison to traditional size characterization techniques (sp-ICP-ToF-MS, TEM), while the robustness of the technique was proven by incorporating NaCl in the samples’ matrix, up to 100 mg/L. T2 - European Winter Conference on Plasma Spectrochemistry CY - Ljubljana, Slovenia DA - 29.01.2023 KW - MDG KW - Single Particle KW - Isotope Dilution PY - 2023 AN - OPUS4-57643 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -