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 JF - Environmental Science and Pollution Research 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 - Thiele, Isabel A1 - Santolin, Lara A1 - Meyer, Klas A1 - Machatschek, Rainhard A1 - Bölz, Uwe A1 - Tarazona, Natalia A. A1 - Riedel, Sebastian L. T1 - Microbially synthesized poly(hydroxybutyrate-co-hydroxyhexanoate) with low to moderate hydroxyhexanoate content: Properties and applications JF - International Journal of Biological Macromolecules N2 - Plastic pollution is the biggest environmental concern of our time. Breakdown products like micro- and nanoplastics inevitably enter the food chain and pose unprecedented health risks. In this scenario, bio-based and biodegradable plastic alternatives have been given a momentum aiming to bridge a transition towards a more sustainable future. Polyhydroxyalkanoates (PHAs) are one of the few thermoplastic polymers synthesized 100 % via biotechnological routes which fully biodegrade in common natural environments. Poly(hydroxybutyrate-cohydroxyhexanoate) [P(HB-co-HHx)] is a PHA copolymer with great potential for the commodity polymers industry, as its mechanical properties can be tailored through fine-tuning of its molar HHx content. We have recently developed a strategy that enables for reliable tailoring of the monomer content of P(HB-co-HHx). Nevertheless, there is often a lack of comprehensive investigation of the material properties of PHAs to evaluate whether they actually mimic the functionalities of conventional plastics. We present a detailed study of P(HB-co-HHx) copolymers with low to moderate hydroxyhexanoate content to understand how the HHx monomer content influences the thermal and mechanical properties and to link those to their abiotic degradation. By increasing the HHx fractions in the range of 2 – 14 mol%, we impart an extension of the processing window and application range as the melting temperature (Tm) and glass temperature (Tg) of the copolymers decrease from Tm 165 ◦C to 126 ◦C, Tg 4 ◦C to − 5.9 ◦C, accompanied by reduced crystallinity from 54 % to 20 %. Elongation at break was increased from 5.7 % up to 703 % at 14 mol% HHx content, confirming that the range examined was sufficiently large to obtain ductile and brittle copolymers, while tensile strength was maintained throughout the studied range. Finally, accelerated abiotic degradation was shown to be slowed down with an increasing HHx fraction decreasing from 70 % to 55 % in 12 h. KW - Molecular Biology KW - General Medicine KW - Biochemistry KW - Structural Biology PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595636 DO - https://doi.org/10.1016/j.ijbiomac.2024.130188 VL - 263 SP - 1 EP - 9 PB - Elsevier B.V. AN - OPUS4-59563 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Roesch, Philipp A1 - Schinnen, Andrea A1 - Riedel, Maren A1 - Sommerfeld, Thomas A1 - Sawal, G. A1 - Bandow, N. A1 - Vogel, Christian A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Investigation of pH-dependent extraction methods for PFAS in (fluoropolymer-based) consumer products: A comparative study between targeted and sum parameter analysis JF - Chemosphere N2 - Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (