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 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 Törne, Wipert Jannik A1 - Steinhäuser, Lorin A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species N2 - The plant secondary metabolite families of coumarin and 4-hydroxy coumarin have a broad pharmacological spectrum ranging from antibacterial to anticancer properties. One prominent member of this substance class is the synthetic but naturally inspired anticoagulant drug and rodenticide warfarin (coumadin). A vast number of publications focus on the identification of warfarin and its major cytochrome P450-mediated phase I metabolites by liquid chromatography (LC) with mass spectrometry (MS) and tandem mass spectrometric (MS/MS) detection techniques. For the first time, electron ionization (EI) induced high-resolution quadrupole time-of-flight mass spectrometric (HR-qToF-MS) data of in-liner derivatized warfarin and selected hydroxylated species is provided in this study as an alternative to LC-MS/MS approaches. Furthermore, the characteristic fragments and fragmentation pathways of the analyzed methyl ethers are concluded. The obtained data of analytical standards, specific deuterated and 13C-labeled compounds prove inductive cleavage of the acyl or acetonyl side chain, methyl migration, and H-migration, along with consequential inductive cleavage as predominant fragmentation routes. Based on the HR-spectral data, commonalities and differences between the analyzed compounds and fragment groups were evaluated with future applicability in structure elucidation and spectra prediction of related compounds. KW - High-resolution mass spectrometry KW - Warfarin KW - Hydroxy warfarin KW - Fragmentation pathway PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596025 DO - https://doi.org/10.1016/j.ijms.2024.117220 SN - 1387-3806 VL - 499 SP - 1 EP - 7 PB - Elsevier B.V. AN - OPUS4-59602 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - von Törne, Wipert Jannik A1 - Klyk-Seitz, Urszula-Anna A1 - Piechotta, Christian T1 - Developing a GC-EI-MS/MS method for quantifying warfarin and five hydroxylated metabolites generated by the Fenton reaction N2 - AbstractSince the 1950s, Warfarin has been used globally as both a prescription drug and a rodenticide. Research has shown that warfarin and other rodenticides are present in the environment and food chain. However, emerging contaminants are subject to degradation by biotic and abiotic processes and advanced oxidation processes. In some cases, detecting the parent compound may not be possible due to the formation of structurally changed species. This approach aims to identify hydroxylated transformation products of warfarin in a laboratory setting, even after the parent compound has undergone degradation. Therefore, the Fenton reaction is utilized to insert hydroxylation into the parent compound, warfarin, by hydroxyl and hydroperoxyl radicals generated by Fe2+/Fe3+ redox reaction with hydrogen peroxide. Using multiple reaction monitoring, a GC–MS/MS method, incorporating isotopically labeled reference compounds, is used to quantify the expected derivatized species. The analytes are derivatized using trimethyl-3-trifluoromethyl phenyl ammonium hydroxide, and the derivatization yield of warfarin is determined by using isotopically labeled reference compounds. The method has a linear working range of 30 to 1800 ng/mL, with detection limits ranging from 18.7 to 67.0 ng/mL. The analytes are enriched using a C18-SPE step, and the recovery for each compound is calculated. The Fenton reaction generates all preselected hydroxylated transformation products of warfarin. The method successfully identifies that 4′-Me-O-WAR forms preferentially under the specified experimental conditions. By further optimizing the SPE clean-up procedures, this GC–MS-based method will be suitable for detecting transformation products in more complex matrices, such as environmental water samples. Overall, this study provides a better understanding of warfarin’s degradation and offers a robust analytical tool for investigating its transformation products. KW - Health, Toxicology and Mutagenesis KW - Pollution KW - Environmental Chemistry KW - General Medicine PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595737 DO - https://doi.org/10.1007/s11356-024-32133-3 SN - 0944-1344 VL - 31 SP - 16986 EP - 16994 PB - Springer Science and Business Media LLC AN - OPUS4-59573 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bilsel, M. A1 - Gökçen, T. A1 - Binici, B. A1 - Isleyen, A. A1 - Piechotta, Christian A1 - Kar-wai, A. A1 - Krylov, A. A1 - Miheeva, A. A1 - Beliakov, M. A1 - Palagina, M. A1 - chenko, Irina Tka A1 - Perkola, N. A1 - Lewin, M. A1 - Hua, T. T1 - High polarity analyte(s) in aqueous media: determination of L-PFOA and L-PFOS in ground water N2 - The CCQM-K156 comparison was coordinated by TUBITAK UME on behalf of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) for National Measurement Institutes (NMIs) and Designated Institutes (DIs) which provide measurement services in organic analysis under the 'Comité International des Poids et Mesures' Mutual Recognition Arrangement (CIPM MRA). Perfluoro alkyl substances (PFAS) such as PFOS and PFOA have been used in numerous industrial applications and products. Because of their high stability and resistance to biodegradation, atmospheric photooxidation, direct photolysis and hydrolysis, they are extremely persistent in the environment. The European Union (EU) Water Framework Directive lists PFOS as a priority hazardous substance that poses a significant risk to the aquatic environment. The use of PFOS-containing Aqueous Film-Forming Foams (AFFFs) has been banned since June 2011 in the EU. As relatively water-soluble, effectively non-degradable compounds, PFOS and PFOA migrate to ground water. They are not removed in the conventional drinking water treatment, and therefore cause health risks in polluted areas. The EU Drinking Water Directive and the European Commission has proposed a limit value of 100 ng/L for the sum of 20 PFAS, including PFOS and PFOA. This study provides the means for assessing measurement capabilities for determination of high polarity measurands in a procedure that requires extraction, clean-up, analytical separation and detection. Successful participation in CCQM-K156 demonstrates measurement capabilities in determining mass fraction of organic compounds, with a molecular mass of 200 g/mol to 700 g/mol, having high polarity pKow -2, in a mass fraction range from 0.5 ng/kg to 500 ng/kg in aqueous media. Nine NMIs and DIs participated in the CCQM-K156 key comparison. Seven institutes reported their results. SPE was applied in the sample pre-treatment and LC-MS was applied for detection. All participating laboratories applied isotope dilution mass spectrometry (IDMS) techniques for quantification. Participants established the metrological traceability of their results using certified reference materials (CRMs) from NMIs with stated traceability; where commercially available high purity materials were used the purity was determined in-house. The CCQM-K156 results for L-PFOA and L-PFOS range from 2.75 ng/kg to 5.50 ng/kg with a % RSD of 19.5 % for L-PFOA and from 2.04 ng/kg to 4.45 ng/kg with a % RSD of 21.3 % for L-PFOS. The KCRV was assigned using a Hierarchical Bayesian Random Effects Model (HB REM) estimator from the values reported by six of the participants. One participant result of L-PFOS and one result of L-PFOA were excluded from the KCRV for technical reasons. The KCRV was 4.9 ng/kg ± 0.4 ng/kg for L-PFOA and 3.8 ng/kg ± 0.4 ng/kg for L-PFOS. The six institutes that were included in the assignment of consensus KCRV all agreed within their standard uncertainties. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA). KW - PFAS KW - Surface water KW - ILC KW - CCQM PY - 2022 DO - https://doi.org/10.1088/0026-1394/59/1A/08016 VL - 59 IS - 1A SP - 1 EP - 3 PB - IOP Publishing AN - OPUS4-58941 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - EDC-WFD: A project to deliver reliable measurements for better monitoring survey and risks assessments. N2 - Monitoring programs should generate high-quality data on the concentrations of substances and other pollutants in the aquatic environment to enable reliable risk assessment. Furthermore, the need for comparability over space and time is critical for analysis of trends and evaluation of restoration of natural environment. Additionally, research work and exercises at the European level have highlighted that reliable measurements of estrogenic substances at the PNEC level are still challenging to achieve. The project EDC-WFD Metrology for monitoring endocrine disrupting compounds under the EU Water Framework Directive aims to develop traceable analytical methods for determining endocrine disrupting compounds and their effects, with a specific focus on three estrogens of the first watch list (17-beta-estradiol (17βE2), 17-alpha-ethinylestradiol (EE2), and estrone (E1)). Estrogens 17-alpha-estradiol (17E2) and estriol (E3) will be included to demonstrate the reliability of the developed methods and to support the requirements of Directive 2013/39/EC, Directive 2009/90/EC and Commission Implementation Decision (EU) 2018/840, hence improving the comparability and compatibility of measurement results within Europe. During the EDC-WFD project four selected effect-based methods (EBM) will be deeply investigated in order to improve their rationale use and their support in water quality assessment. In particular, the EBM sensitivity, specificity and accuracy on reference materials with single or mixture solutions of the five substances at a concentration of EQS values will be explored. This contribution will present the objectives and methods applied within the EDC-WFD project. T2 - EuChemS CY - Lisbon, Portugal DA - 29.08.2022 KW - WFD KW - Estrogens KW - Whole water samples KW - EQS PY - 2022 AN - OPUS4-57096 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - A method for monitoring estrogens in whole surface waters by GC-MS/MS N2 - Natural and synthetic estrogens are key endocrine-disrupting chemicals. Despite occurring at ultra-trace levels (below ng L-1), it is believed that they are contributing to an increase in feminized fish and other endocrine disruptive effects, and hence, their inclusion in the Watch list was not unexpected. One of the main sources ofestrogens to surface waters is wastewater effluent. Once in surface waters, they can partition into different compartments, i.e., water and suspended particulate matter. For this reason, there is an urgent need for a methodology to monitor estrogen levels below the environmental quality standards (EQS) set by the Water Framework Directive requirements. In this study, a precise and accurate gas chromatography-mass spectrometry method (GC-MS/MS) for the analysis of estrone (E1), 17β-estradiol (17β-E2), 17α-estradiol (17α- E2), 17-alpha-ethinylestradiol (EE2), and estriol (E3) in whole water samples with ng L-1 limit of quantification (LOQ) was developed and validated in accordance with CEN/TS 16800:2020 guidelines. T2 - IMSC 2022 CY - Maastricht, Netherlands DA - 27.08.2022 KW - EDC KW - WFD KW - GC-MS PY - 2022 AN - OPUS4-57097 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steinhäuser, Lorin A1 - Piechotta, Christian A1 - Westphalen, Tanja A1 - Kaminski, Katja T1 - Evaluation, comparison and combination of molecularly imprinted polymer solid phase extraction and classical solid phase extraction for the preconcentration of endocrine disrupting chemicals from representative whole water samples N2 - Estrogens are endocrine disrupting chemicals and of high concerns due to demonstrated harmful effects on the environment and low effect levels. For monitoring and risk assessment, several estrogens were included in the "watch list" of the EU Water Framework Directive which sets very low environmental quality standard (EQS) levels for Estrone (E1) and 17β-Estradiol (E2) of 0.4 ng L−1 and for 17α-Ethinylestradiol (EE2) of 0.035 ng L−1 requiring sensitive detection methods, as well as extensive sample preparation. A sensitive, derivatization-free, isotope dilution calibration HPLC-MS/MS method for a panel of 5 selected estrogens (including the 3 estrogens of the EU WFD watchlist), and a procedure for the reproducible preparation of a representative whole water matrix including mineral water, humic acids and solid particulate matter are presented. These are used in a diligent comparison of classical solid phase extraction (SPE) on hydrophilic-lipophilic balanced (HLB) phase to SPE on an estrogen-specific molecularly imprinted polymer phase (MISPE) for ultra-trace levels of the analytes (1–10 ng L−1). Additionally, a two-step procedure combining HLB SPE disks followed by MISPE is evaluated. The tow-step procedure provides superior enrichment, matrix removal and sample throughput while maintaining comparable recovery rates to simple cartridge SPE. Estimated method quantification limits (MQLs) range from 0.109–0.184 ng L−1 and thus meet EQS-levels for E1 and E2, but not EE2. The representative whole water matrix provides a reproducible comparison of sample preparation methods and lays the foundation for a certified reference material for estrogen analysis. The presented method will serve as the basis for an extended validation study to assess its use for estrogen monitoring in the environment. KW - Estrogens KW - Whole water samples KW - Molecular imprinted polymers KW - EU-WFD PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-563547 DO - https://doi.org/10.1016/j.talo.2022.100163 SN - 2666-8319 VL - 6 SP - 1 EP - 5 PB - Elsevier B.V. CY - Amsterdam, Niederlande AN - OPUS4-56354 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Neue Desinfektionsnebenprodukte und Metaboliten ausgewählter Inhaltsstoffe in Personal Care Products (PCP) am Beispiel von AHTN und HHCB N2 - Inhaltsstoffe von Personal Care Products können zunehmend in der aquatischen Umwelt nachgewiesen werden. Dabei handelt es sich um Inhaltsstoffe von Kosmetikartikeln, Medikamenten oder Reinigungsmitteln. Der Eintrag erfolgt größtenteils über kommunale Kläranlagen, die die Analyten nicht komplett zurückhalten können. Zu diesen Verbindungen zählen im Rahmen dieser Arbeit die Moschusdüfte 6-Acetyl-1,1,2,4,4,7-hexamethyltetraline (AHTN) und 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-y-2-benzopyran (HHCB). Diese Analyten können im μg/L- bzw. ng/L-Bereich im Oberflächenwasser nachgewiesen werden. Zur Desinfektion von Wasser für Schwimmbäder oder zur Gewinnung von Trinkwasser werden hypochlorithaltige Chemikalien oder Ozon eingesetzt, um Mikroorganismen zu vernichten, wobei unter anderem auch Desinfektionsnebenprodukte (DBP – Disinfection By-Products) von PCPs gebildet werden können. In dieser Arbeit werden erste neue DBPs präsentiert, die durch Ozonierung oder Chlorierung mittels Natriumhypochlorit aus den genannten Chemikalien in Modellreaktoren hervorgingen. Auch werden die dazu gehörigen Strategien zu deren Identifizerung und Charakterisierung vorgestellt. Hier kommen diverse chromatographische Verfahren, wie LC-MS/MS, LC-MSn, aber auch GC-MS und die 1H- bzw. 13C-NMR zum Einsatz. In einem zweiten Ansatz werden erste Phase-I-Metaboliten dieser Verbindungen gezeigt, die beim Umsatz in Modellsystemen mit Human- und Rattenleber-mikrosomen entstanden sind. T2 - LC-MS in der Umweltanalytik 2016 CY - Leipzig, Germany DA - 06.06.2016 KW - AHTN PY - 2016 AN - OPUS4-38521 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Characterization of new disinfection by-products of polycyclic musks (AHTN and HHCB) and their metabolites N2 - The polycyclic musks 6-Acetyl-1,1,2,4,4,7-hexamethyltetraline (AHTN) and 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-ɣ-2-benzopyran (HHCB) are widely used fragrances in cosmetics, products of daily care and cleaning products for households and industry. They are in the focus of interest due to their estrogenic potential. Both compounds can be found at low μg/L concentrations in surface water where they are introduced mainly by sewage treatment plants supplied by municipal wastewater. In order to disinfect wastewater in sewage treatment plants or water in swimming pools, chlorine can be added to water as gas or hypochlorite solution. This disinfectant has a high oxidation potential resulting in the formation of disinfection by-products, the estrogenicity and toxicity of which might differ from their precursor. In this work the behaviour of AHTN and HHCB upon treatment with sodium hypochlorite solution was investigated and chlorinated possible disinfection by-products could be identified as well as a carboxylic acids and lactones derived from AHTN and HHCB. The identified species were characterized by GC-MS, LC-MSn and 1H-NMR. The elucidated structures of potential disinfection by-products are verified by X-ray crystallography. Finally the estrogenicity between the parent analytes and generated transformation products were compared. For that task, MCF-7 assay has been chosen for being most relevant to humans. Moreover metabolism studies were carried out using AHTN, HHCB and their disinfection by-products. T2 - ISEB 2016 CY - Barcelona, Spain DA - 30.05.2016 KW - AHTN PY - 2016 AN - OPUS4-38523 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Traceability for mercury measurements - MeTra N2 - The aim of this work is to develop measurement procedures to provide full traceability and robust uncertainty statements for dissolved elemental mercury (Hg(0)), inorganic mercury (Hg(II)) and methyl-mercury (MeHg) in freshwater and sea water, and inorganic mercury (Hg(II)) and methyl-mercury (MeHg) in biota. Accurate measurements with low uncertainties e.g. <50 % at the EQS level are required to assess concentration levels and trends in these important environmental reservoirs for mercury. In particular this work aims to: Develop and validate primary measurement procedures for Hg speciation (Hg(II), MeHg and Hg(0)) in fresh and sea waters at sub-ng levels in the presence of suspended particular matter and/or colloidal fractions, Apply the developed IDMS procedures in water in order to evaluate possible artefacts associated with sample collection and preparation, preserving speciation and/or correcting for possible post-sampling interconversions, Develop and validate primary measurement procedures for the accurate quantification of Hg(II) and MeHg in biota, using samples from the Federal Environmental Specimen Bank, Apply the developed IDMS procedures in biota in order to evaluate the effect of different treatments for fish sample preparation. T2 - EMRP MeTra Meeting CY - Geel, Belgium DA - 01.02.2016 KW - Methyl mercury PY - 2016 AN - OPUS4-38519 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Analytik arsenorganischer Verbindungen In Umweltproben N2 - Seit 1968 wird durch Lunde vermutet, dass sich lipidlösliche Arsenverbindungen im Muskelgewebe fettreicher Fische, wie dem Hering (clupea harengus) anreichern. Obwohl marine Organismen ausgiebig untersucht worden sind, gibt es bisher wenige Arbeiten zur analytischen Charakterisierung dieser Spezies. In den 60iger Jahren konnte Gulbrand Lunde erstmalig den Arsengehalt in Fischölen von bis zu 20 mg/kg bestimmen. Seitdem wurden drei Klassen an Arsenolipiden identifiziert und in Ansätzen charakterisiert: Arsenokohlenwasserstoffe (As-HC), Arsenofettsäuren (As-FA) und die Arsenozuckerphospholipide (As-SugPL). In der vorzustellenden Arbeit konnten erstmalig mehr als 20 fettlösliche Arsenolipide in Heringsfilet mittels der Kopplungen HPLC-ICP-MS und ESI-Q-TOF-MS identifiziert und semiquantifiziert werden. Dabei erfolgte die strukturelle Zuordnung über die exakten Massen und durch gezielte MS-MS-Experimente, deren Fragmente eine eindeutige Charakterisierung ermöglichten. Es konnten bisher unbekannte Arsenolipide im Hering nachgewiesen werden. Eine Untersuchung weiterer Fischarten ergab, dass diese Arsenverbindungen in unterschiedlichen marinen Speisefischen weiter verbreitet sind, als bisher angenommen. In Stoffwechselstudien konnte gezeigt werden, dass es zu einer erhöhten Konzentration des kanzerogenen Dimethylarsinats (DMA) in menschlichem Urin nach dem Verzehr von Hering kommt. Weiterhin konnte aufgrund der Ergebnisse eventuell im Hering enthaltenes anorganisches Arsen, Monomethylarsonat und DMA als Ursache ausgeschlossen werden. Da Arsenobetain nachweislich nicht im menschlichen Körper metabolisiert wird, sind die in den durchgeführten Arbeiten erzielte Ergebnisse zweckdienlich, die These zu bestärken, dass die identifizierten Arsenolipide zu DMA abgebaut werden können. T2 - GDCh AK Umweltmonitoring CY - Berlin, Germany DA - 05.07.2016 KW - Arsenolipide PY - 2016 AN - OPUS4-38520 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Muelow-Stollin, Ulrike A1 - Lehnik-Habrink, Petra A1 - Kluge, Stephanie A1 - Bremser, Wolfram A1 - Piechotta, Christian T1 - Efficiency Evaluation of Extraction Methods for Analysis of OCPs and PCBs in Soils of Varying TOC N2 - Organochlorine pesticides and polychlorinated biphenyls are toxic, carcinogenic, and have a high potential for bioaccumulation. Due to their stability, they are still considered an environmental problem even though the use of most of them has been phased out several decades ago. Soil is a matrix which can retain these contaminants to a great extent. This ability is often associated with the total organic carbon content (TOC). In order to judge the pollution status of soil and to make monitoring data more easily comparable a simple, yet robust extraction method is needed. Agitation solid-liquid-extraction is well suited for this purpose. However, the influence of TOC on the analyte recovery has to be known. For the presented study, 12 organochlorine pesticides and 7 polychlorinated biphenyls were spiked into four model soils with organic carbon contents between 1.6% - 13.3%. The matrices were extracted using solid-liquid extraction between 45 minutes and 16 hours. For comparison, all soils were also extracted using pressurised liquid extraction and Soxhlet extraction. After clean-up the extracts were measured using a gas chromatography-mass spectrometry (GC-MS) system. Statistical analysis of the results implied that the TOC content of the soils did not have significant influence on the extraction efficiency. A longer solid-liquid extraction time did not necessarily increase analyte recovery: Extraction for one hour resulted in 88% recovery while 16 hour extraction led to 89%. Thus, the efficiency of all the methods was comparable for all model soils. Additional investigations regarding GC liner performance highlighted the need for isotopically labelled standards during the analysis of thermolabile pesticides. KW - POP KW - Soil organic matter KW - Solid-liquid-extraction KW - Pressurised liquid extraction PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-430238 DO - https://doi.org/10.4236/jep.2017.86045 SN - 2152-2219 VL - 08 IS - 06 SP - Article ID:77202, 693 EP - 713 PB - Scientific Research Publishing AN - OPUS4-43023 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Transformation of the antidiabetic drug metformin N2 - For years there have been more and more reports on the presence of drugs in the aquatic environment. Due to the demographic change, the consumption of pharmaceuticals has risen sharply. After taking the drugs, they are partly metabolized in the human body. However, the metabolism is not complete so that both the metabolites and non-metabolized amounts of the parent compounds are excreted. These compounds reach the waste water and afterwards the sewage treatment plants. In sewage treatment plants transformation products can be formed by the oxidative conditions during wastewater treatment processes. The transformation products may have a higher toxicity than the actual environmental pollutants and are often only partly removed during the waste water treatment. Since a lot of these compounds are still unknown, the transformation products are not detected by target analysis used in sewage treatment plants and are often released undetected in the aquatic ecosystems. The released substances may be subject to additional transformation processes in the environment. Pharmaceuticals produced in high amounts can be already detected in the μg/L range in water bodies worldwide. Metformin and its major transformation product guanylurea are one of the main representatives. Metformin is the drug of choice for treating type 2 diabetes. The drug therapy for diabetes mellitus has increased significantly in recent years. In the year 2015 1500 tons of metformin were prescribed in Germany (for statutory insured persons). Metformin is not metabolized in the human body and is excreted unchanged therefore concentrations between 57 μg/L and 129 μg/L are found in German waste water treatment plants influents. In this work the transformation of the antidiabetic drug metformin is investigated. The degradation of metformin is initialize by commercial water treatment techniques like UV-radiation or noncommercial techniques like heterogenous photocatalysis based on titanium dioxide. The degradation of metformin and resulting transformation products are analyzed by LC-MS/MS and LC-HRMS. T2 - SPEA 10 CY - Almeria, Spain DA - 04.06.2018 KW - Metformin KW - Photocatalysis PY - 2018 AN - OPUS4-47030 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Structural Investigations of Transformation Products of the Anticoagulant Drug and Rodenticide Warfarin N2 - Warfarin (Coumadin) is one of the most popular anticoagulant drugs used as a therapeutic in humans to prevent thrombosis, atrial fibrosis, and fibrillation since the 1950s. Because of its ability to hinder blood coagulation by blocking vitamin K-depending carboxylation of blood clotting precursors, it is also used as a rodenticide worldwide. Until today it has been partially substituted by far more potent anticoagulant rodenticides (ARs), so-called superwarfarins. Numerous studies are confirming secondary and tertiary poisoning with ARs in non-target-animals and wildlife. Up to now, relatively little is known about persistence and toxicity of ARs and naturally, nor technically formed transformation products (TPs) in the environment, food chain, and transformations occurring during wastewater treatment. Herein, we present liquid and gas chromatographic methods coupled to (high-resolution) mass spectrometry for the analysis of warfarin’s transformation products. Methodologies such as UV-irradiation, ozonation, and chlorination were utilised to simulate technical water treatment. Resulting compounds were elucidated and examined by numerous analytical methods. Moreover, the oxidative phase I metabolism was mimicked by an electrochemical flow cell to synthesise and confirm major metabolites. The further aim is the toxicological assessment of all substances formed, as well as, the quantification of warfarin and its TPs under environmentally relevant conditions employing the introduced methods. T2 - SETAC 2024 CY - Sevilla, Spain DA - 05.06.2024 KW - Warfarin PY - 2024 AN - OPUS4-61898 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species N2 - Warfarin (Coumadin) is one of the most popular anticoagulant drugs used as a therapeutic in humans to prevent thrombosis, atrial fibrosis, and fibrillation since the 1950s. Because of its ability to hinder blood coagulation by blocking vitamin K-depending carboxylation of blood clotting precursors, it is also used as a rodenticide worldwide. Until today it has been partially substituted by far more potent anticoagulant rodenticides (ARs), so-called superwarfarins. Numerous studies are confirming secondary and tertiary poisoning with ARs in non-target-animals and wildlife. Up to now, relatively little is known about persistence and toxicity of ARs and naturally, nor technically formed transformation products (TPs) in the environment, food chain, and transformations occurring during wastewater treatment. Herein, we present liquid and gas chromatographic methods coupled to (high-resolution) mass spectrometry for the analysis of warfarin’s transformation products. Methodologies such as UV-irradiation, ozonation, and chlorination were utilised to simulate technical water treatment. Resulting compounds were elucidated and examined by numerous analytical methods. Moreover, the oxidative phase I metabolism was mimicked by an electrochemical flow cell to synthesise and confirm major metabolites. The further aim is the toxicological assessment of all substances formed, as well as, the quantification of warfarin and its TPs under environmentally relevant conditions employing the introduced methods. T2 - SETAC 2024 CY - Sevilla, Spain DA - 05.06.2024 KW - Mass spectrometry KW - Warfarin PY - 2024 AN - OPUS4-61902 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Analytische Betrachtung von neu identifizierten Arsenolipiden in Hering T2 - LC-MS in der Umweltanalytik 2014 CY - Leipzig DA - 2014-06-16 PY - 2014 AN - OPUS4-31855 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Synthesis of arsenolipids and their characterization by LC-MS and NMR techniques T2 - LC-MS in der Umweltanalytik 2014 CY - Leipzig DA - 2014-06-16 PY - 2014 AN - OPUS4-31856 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Identifizierung und analytische Betrachtung von Arsenolipiden in Hering T2 - Fachtagung 2013 des NRL für Schwermetalle in Futter- und Lebensmitteln CY - Berlin, Germany DA - 2013-12-03 PY - 2013 AN - OPUS4-29807 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fettig, Ina A1 - Krüger, Simone A1 - Deubel, Jan A1 - Werrel, Martin A1 - Raspe, Tina A1 - Piechotta, Christian T1 - Evaluation of a headspace solid-phase microextraction method for the analysis of ignitable liquids in fire debris N2 - The chemical analysis of fire debris represents a crucial part in fire investigations to determine the cause of a fire. A headspace solid-phase microextraction (HS-SPME) procedure for the detection of ignitable liquids in fire debris using a fiber coated with a mixture of three different sorbent materials (Divinylbenzene/Carboxen/Polydimethylsiloxane, DVB/CAR/PDMS) is described. Gasoline and diesel fuel were spiked upon a preburnt matrix (wood charcoal), extracted and concentrated with HS-SPME and then analyzed with gas chromatography/mass spectrometry (GC/MS). The experimental conditions—extraction temperature, incubation and exposure time—were optimized. To assess the applicability of the method, fire debris samples were prepared in the smoke density chamber (SDC) and a controlled-atmosphere cone calorimeter. The developed methods were successfully applied to burnt particleboard and carpet samples. The results demonstrate that the procedure that has been developed here is suitable for detecting these ignitable liquids in highly burnt debris. KW - Forensic science KW - Arson analysis KW - Fire debris KW - Ignitable liquids KW - Solid-phase microextraction KW - Smoke density chamber KW - Cone calorimeter PY - 2013 DO - https://doi.org/10.1111/1556-4029.12342 SN - 0022-1198 SN - 1556-4029 VL - 59 IS - 3 SP - 743 EP - 749 PB - Wiley CY - Hoboken, NJ, USA AN - OPUS4-30038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Piechotta, Christian T1 - Umweltverträglichkeit und -beständigkeit von Materialien und Produkten hinsichtlich der Migration von Schadstoffen N2 - Gegenstand des Projekts ist die Prüfung der Umweltbeständigkeit und -verträglichkeit von Materialien und Produkten hinsichtlich der Emission von potenziellen Schadstoffen in die Umwelt. Hierzu werden chemisch-physikalische Einflüsse (Bewitterung) und mikrobielle Beanspruchungen an Modellmaterialien evaluiert. So werden die Freisetzungsraten von Schadstoffen in Abhängigkeit der Beanspruchung beschrieben. Als Modellmaterialien kommen die Polymere Polycarbonat, Polytetrafluorethylen, Polystyrol und Polypropylen zum Einsatz. Synergistische Effekte der Bewitterungsparameter und der mikrobiologischen Beanspruchung sollen dabei ebenso betrachtet werden, wie die gezielte Alterung. Auch findet eine Beschreibung des Verhaltens der ausgetragenen Schadstoffe in den Umweltkompartimenten Boden oder Wasser statt. Hier sind mit Hilfe der zu entwickelnden Screening- und non-Target-Analyseverfahren die Transformation und der Metabolismus durch Mikroorganismen zu beschreiben. Aus den Ergebnissen sollen Korrelationen zwischen den künstlichen Alterungsverfahren und realen Szenarien abgeleitet werden, die es gestatten, Schnellprüfverfahren zu etablieren, die die Simulation der realen Beanspruchungen im Zeitraffermodell anwendbar machen. Somit sollen standardisierbare Schnellbeanspruchungs-verfahren erarbeitet werden, die als Prüfeinrichtungen etabliert werden und von externen Auftraggebern zur Prüfung der Umweltbeständigkeit und -verträglichkeit von neuen Materialien genutzt werden können. Die Umweltwirkungen (chemisch-physikalisch und mikrobiologisch) sollen so definiert eingesetzt werden, dass eine reproduzierbare Prüfung möglich wird. Aus diesen Verfahren und Methoden sollen Normen abgeleitet werden, die eine standardisierte Materialprüfung ermöglichen. T2 - 46. Jahrestagung der GUS CY - Stutensee-Blankenloch, Germany DA - 22.03.2017 KW - Umweltsimulation KW - Schadstoffe KW - Materialien PY - 2017 AN - OPUS4-40259 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -