TY - JOUR A1 - Gehrenkemper, Lennart A1 - Simon, Fabian A1 - Roesch, Philipp A1 - Fischer, E. A1 - von der Au, Marcus A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Wittwer, Philipp A1 - Vogel, Christian A1 - Simon, Franz-Georg A1 - Meermann, Björn T1 - Determination of organically bound fluorine sum parameters in river water samples - Comparison of combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) N2 - In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically Bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples fromriver Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum Parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 μg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14–0.81% of TF (determined using CIC) and EOF 0.04–0.28% of TF (determined using HR-CSGFMAS). The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in Risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct. KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Combustion ion chromatography (CIC) KW - Per- and polyfluorinated alkyl substances (PFASs) KW - Adsorbable organically bound fluorine (AOF) KW - Extractable organically bound fluorine (EOF) KW - Surface waters PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515351 DO - https://doi.org/10.1007/s00216-020-03010-y SN - 1618-2650 VL - 413 IS - 28 SP - 103 EP - 115 PB - Springer CY - Berlin AN - OPUS4-51535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gehrenkemper, Lennart T1 - Organically bound fluorine in river water - A methode comparison of CIC and HR-CS-GFMAS N2 - Abstract: Since it is unknown for many applications, which PFASs are used and how they enter the environment, target analysis-based methods reach their limits. The two most frequently used sum parameters are the adsorbable organically bound fluorine (AOF) and the extractable organically bound fluorine (EOF). Both can be quantified using either combustion ion chromatography (CIC) or high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Here we provide an insight on the advantageous and disadvantageous of both sum parameters and both detection methods. Our study is based on the analysis of surface water samples. Next to total fluorine (TF) analysis, AOF and EOF were determined as well as CIC and HR-CS-GFMAS are compared and results are comparatively discussed. Fluorine mass balancing revealed that, the AOF/TF proportion was higher than the EOF/TF proportion. The AOF made up 0.14–0.81% of TF and the EOF 0.04–0.28% of TF. Although, organically bound fluorine represents only a small portion of TF, PFASs are of worldwide concern, because of their extreme persistence and their bioaccumulation potential. The EOF-HR-CS-GFMAS method turned out to be more precise and sensitive than the AOF-CIC method and is a promising tool for future monitoring studies/routine analysis of PFASs in the environment. T2 - SALSA Make and Measure 2020: Advanced Characterization of Materials CY - Online meeting DA - 15.10.2020 KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Combustion ion chromatography (CIC) KW - Per- and polyfluorinated alkyl substances (PFASs) KW - Adsorbable organically bound fluorine (AOF) KW - Extractable organically bound fluorine (EOF) KW - Surfacewaters PY - 2020 AN - OPUS4-52451 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Simon, Fabian 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 - Dinter, Adelina-Elisa ED - Dinter, Adelina-Elisa T1 - Development of a MIC single archaea-ICP-ToF-MS-method for analysis of various elements in solid steel samples N2 - With the latest ICP-MS technology - ICP-ToF (time of flight)-MS - it is possible to analyze the multi-element fingerprint of individual cells. The interface between material and environmental analysis thus receives special attention, e.g. when considering corrosion processes. Microbiologically influenced corrosion (MIC) is highly unpredictable due to the diversity of microbial communities involved. The development of the MIC-specific ICP-ToF-MS analytical method presented here at the single cell level, in combination with the investigation of steel-MIC interactions, contributes significantly to progress in instrumental MIC analysis and will enable clarification of the processes taking place. The supplied document shows the basis of a four minutes lightning talk. T2 - EuroMIC 2021 CY - Online meeting DA - 22.06.2021 KW - SC-ICP-ToF-MS KW - Single cell analysis KW - Microbiologically influenced corrosion KW - Lightning talk PY - 2021 AN - OPUS4-52905 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - von der Au, Marcus A1 - Wittwer, Phillip A1 - Roesch, Philipp A1 - Pfeifer, Jens A1 - Cossmer, Antje A1 - Meermann, Björn T1 - A fast and simple PFAS extraction method utilizing HR–CS–GFMAS for soil samples N2 - Here, we describe an optimized fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) in soils utilizing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR–CS–GFMAS). To omit the bias of the solid phase extraction (SPE) step commonly used during the analysis of extractable organically bound fluorine (EOF) we optimized a fast and simple SPE-free extraction method. The developed extraction method consists of a liquid-solid extraction using acidified methanol without any additional SPE. Four extraction steps were representative to determine a high proportion of the EOF (>80% of eight extractions). Comparison of the optimized method with and without an additional SPE clean-up step revealed a drastic underestimation of EOF concentrations using SPE. Differences of up to 94% were observed which were not explainable by coextracted inorganic fluoride. Therefore, not only a more accurate but also a more economic as well as ecologic method (bypassing of unnecessary SPE) was developed. The procedural limit of quantification (LOQ) of the developed method was 10.30 μg/kg which was sufficient for quantifying EOF concentrations in all tested samples. For future PFAS monitoring and potential regulative decisions the herein presented optimized extraction method can offer a valuable contribution. KW - Per- and polyfluorinated alkly substances (PFASs) KW - High resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) KW - Soils KW - Solid phase extraction (SPE) KW - Extractable organically bound fluorine (EOF) KW - Solid-liquid extraction PY - 2022 DO - https://doi.org/10.1016/j.chemosphere.2022.133922 VL - 295 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-54359 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zweigle, J. A1 - Capitain, C. A1 - Simon, Fabian Michael A1 - Roesch, Philipp A1 - Bugsel, B. A1 - Zwiener, C. T1 - Non-extractable PFAS in functional textiles − Characterization by complementary methods: oxidation, hydrolysis, and fluorine sum parameters N2 - Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from 150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. KW - Combustion ion chromatography KW - Per- and polyfluoroalkyl substances (PFAS) KW - Sewage sludge KW - Fertilizer PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-583429 DO - https://doi.org/10.1039/d3va00178d SN - 2754-7000 VL - 2 IS - 10 SP - 1436 EP - 1445 PB - Royal Society of Chemistry (RSC) CY - London AN - OPUS4-58342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - Per- and Polyfluoroalkyl Substances (PFAS) in Sewage Sludge and Wastewater-based Fertilizers N2 - Per- and polyfluoroalkyl substances (PFAS) are chemicals which were developed to improve humanity’s quality of life. Due to their high chemical stability and resistance to degradation by heat or acids, PFAS were used in a variety of consumer products. The continuous use of PFAS in household products and the discharge of PFAS from industrial plants into the sewer system resulted in the contamination of effluents and sewage sludge from wastewater treatment plants (WWTPs) (Roesch et al. 2022). Since sewage sludge is often used as fertilizer, its application on agricultural soils has been observed as a significant entry path for PFAS into the environment, specifically in our food chain. In Germany the sewage sludge/biosolid application on agricultural land was banned with the amendment of the German Sewage Sludge Ordinance and by 2029 sewage sludge application will be totally prohibited. However, phosphorus (P) from sewage sludge should still be recycled in WWTPs of cities with a population larger than 50,000 residents. To produce high-quality P-fertilizers for a circular economy, PFAS and other pollutants (e.g. pesticides and pharmaceuticals) must be separated from sewage sludge. Due to the strong diversity of industrial PFAS usage it is not clear if a safe application of novel recycled P-fertilizers from WWTPs can be guaranteed. Therefore, we analyzed various sewage sludges and wastewater-based fertilizers. Sewage sludge (SL) samples from various WWTPs in Germany and Switzerland, six sewage sludge ashes (SSA) from Germany, six thermally treated SL and SSA samples with different additives (temperatures: 700-1050 °C), two pyrolyzed SL samples (temperature: 400 °C) and two struvite samples from Germany and Canada were analyzed. The goal was to quantify PFAS in sewage sludges and wastewater-based P-fertilizers with the sum parameter extractable organic fluorine (EOF) by combustion ion chromatography (CIC). The results were compared with data from classical LC-MS/MS target analysis as well as selected samples by HR-MS suspect screening. The EOF values of the SLs mainly range between 154 and 538 µg/kg except for one SL which showed an elevated EOF value of 7209 µg/kg due to high organofluorine contamination. For the SSA samples the EOF values were lower and values between LOQ (approx. 60 µg/kg) and 121 µg/kg could be detected. For the pyrolyzed SLs no EOF values above the LOQ were detected. Moreover, the two wastewater-based struvite fertilizers contain 96 and 112 µg/kg EOF, respectively. In contrast to the EOF values, the sum of PFAS target values were relatively low for all SLs. Additional applied PFAS HR-MS suspect screening aimed to tentatively identify PFAS that could contribute to the hitherto unknown part of the EOF value. The majority of the detected fluorinated compounds are legacy PFAS such as short- and long-chain perfluorocarboxylic acids (PFCA), perfluorosulfonic acids (PFSA), polyfluoroalkyl phosphate esters (PAPs) and perfluorophosphonic acids (PFPA). Moreover, fluorinated pesticides, pharmaceutical as well as aromatic compounds were also identified, which are all included in the EOF parameter. Our research revealed that the current PFAS limit of 100 µg/kg for the sum of PFOS + PFOA in the German Fertilizer Ordinance is no longer up to date. Since the number of known PFAS already exceeds 10,000, the ordinance limit should be updated accordingly. Recent regulations and restrictions on using long-chain PFAS (≥C8) have resulted in a significant shift in the industry towards (ultra-)short-chain alternatives, and other, partly unknown, emerging PFAS. Ultimately, also fluorinated pesticides and pharmaceuticals, which end up as ultrashort PFAS in the WWTPs, have to be considered as possible pollutants in fertilizers from wastewater, too. T2 - Dioxin Konferenz CY - Maastricht, Netherlands DA - 10.09.2023 KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Sewage sludge KW - Fertilizer PY - 2023 AN - OPUS4-58345 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Vogel, Christian T1 - Combining DGT and combustion ion chromatography (CIC) as screening tool for per- and polyfluoroalkyl substances (PFAS) contamination in wastewater-based fertilizers N2 - Per- and polyfluoroalkyl substances (PFAS) are a large group of organofluorine surfactants used in the formulations of thousands of consumer goods. The continuous use of PFAS in household products and the discharge of PFAS from industrial plants into the sewer system have been resulted in contaminated effluents and sewage sludge from wastewater treatment plants (WWTPs) which became an important pathway for PFAS into the environment. Because sewage sludge is often used as fertilizer its application on agricultural soils has been observed as significant input path for PFAS into our food chain. To produce high-quality phosphorus fertilizers for a circular economy from sewage sludge, PFAS and other pollutants (e.g. pesticides and pharmaceuticals) must be separated from sewage sludge. Normally, PFAS are analyzed using PFAS protocols typically with time-consuming extraction steps and LC-MS/MS target quantification. However, for screening of PFAS contaminations in wastewater-based fertilizers also the DGT technique can be used for the PFAS extraction. Afterwards, combustion ion chromatography (CIC) can be applied to analyze the “total” amount of PFAS on the DGT binding layer. The DGT method was less sensitive and only comparable to the extractable organic fluorine (EOF) method values of the fertilizers in samples with >150 µg/kg, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. However, the DGT approach has the advantage that almost no sample preparation is necessary. Moreover, the PFAS adsorption on the DGT binding layer was investigated via surface sensitive spectroscopical methods, such as Fourier-transform infrared (FT-IR) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy. T2 - DGT Konferenz CY - Paris, France DA - 11.10.2023 KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Sewage sludge PY - 2023 AN - OPUS4-58575 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -