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 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 (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 - JOUR A1 - Wittwer, Philipp A1 - Roesch, Philipp A1 - Vogel, Christian A1 - Simon, Fabian A1 - Gehrenkemper, Lennart A1 - Feldmann, Ines A1 - Simon, Franz-Georg T1 - Less Is More: Influence of Cross-Linking Agent Concentration on PFOS Adsorption in Chitosan N2 - As a result of the continuous use of persistent per- and polyfluoroalkyl substances (PFAS), e.g., in aviation firefighting foams, contamination with PFAS has been found in soil, groundwater, and surface water around thousands of industrial and military installations. Due to their harmful (environmental) potential, further dispersion in the environment needs to be stopped, which can be achieved by appropriate absorption materials. In this work, the influence of the cross-linking agent epichlorohydrin (ECH) concentration on the perfluorooctanesulfonic acid (PFOS) adsorption capacity of chitosan gel was investigated. It was found that higher ECH concentration during the cross-linking step decreases the PFOS adsorption capacity of the cross-linked chitosan gel from 0% to 4% ECH solution by about 15%. Using a concentration of 1%, ECH resulted still in an acid-stable material, and a maximum PFOS loading capacity of 4.04 mmol/g was obtained, one of the highest described in the literature. Furthermore, we used a rapid small-scale column test to compare the PFOS adsorption capacity of chitosan and activated carbon, each in both milled and unmilled form. Unmilled chitosan showed the highest PFOS adsorption capacity considering adsorption material dry masses (>0.9 and <0.4 mmol/g for both types of chitosan and activated carbon, respectively). Milled activated carbon proved to be the better adsorption material, considering the fixed volume of the adsorber (>99.9% PFOS adsorbed). Overall, the cross-linking agent concentration in chitosan is a crucial factor influencing its PFOS absorption potential. Our results feature cross-linked chitosan as an effective economic and ecologic alternative for PFOS adsorption in aqueous solutions. KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Remediation PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-618406 DO - https://doi.org/10.3390/app142311145 VL - 14 IS - 23 SP - 1 EP - 13 PB - MDPI AN - OPUS4-61840 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Sekine, R. A1 - Huang, J. A1 - Steckenmesser, D. A1 - Steffens, D. A1 - Huthwelker, T. A1 - Borca, C. A1 - Pradas del Real, A. A1 - Castillo-Michel, H. A1 - Adam, Christian T1 - Effects of a nitrification inhibitor on nitrogen species in the soil and the yield and phosphorus uptake of maize N2 - Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P fertilizers from recycled materials, which often have low plant availability. Specific co-fertilization with ammoniumcan enhance P plant availability in soils amended with these P fertilizers, and thus the yield of plants. To investigate this effect, we performed a pot experiment with maize in slightly acidic soil (pH 6.9) with one water-soluble (triple superphosphate [TSP]) and two water-insoluble (sewage sludge-based and hyperphosphate [Hyp]) P fertilizers and anammoniumsulfate nitrate with or without a nitrification inhibitor (NI). The dry matter yield of maize was significantly increased by the NI with the Hyp (from 14.7 to 21.5 g/pot) and TSP (from 40.0 to 45.4 g/pot) treatments. Furthermore, P uptake was slightly increased in all three P treatments with the NI, but not significantly. Olsen-P extraction and P K-edge micro-X-ray absorption near-edge structure (XANES) spectroscopy showed that apatite-P of the water insoluble P fertilizers mobilized during the plant growth period. In addition, novel nitrogen (N) K-edge micro-XANES spectroscopy and the Mogilevkina method showed that the application of an NI increased the fixation of ammonium in detectable hot spots in the soil. Thus, the delay in the nitrification process by the NI and the possible slow-release of temporarily fixed ammoniumin the soil resulted in a high amount of plant available Ammonium in the soil solution. This development probably decreases the rhizosphere pH due to release of H+ by plants during ammoniumuptake, whichmobilizes phosphorus in the amended soil and increases the dry matter yield of maize. This is especially important for water-insoluble apatite-based P fertilizers (conventional and recycled), which tend to have poor plant availability. KW - Fertilzer KW - Phosphorus recovery KW - Ammonium KW - Nitrification inhibitor KW - XANES spectroscopy KW - Diffusive gradients in thin films (DGT) PY - 2020 DO - https://doi.org/10.1016/j.scitotenv.2020.136895 SN - 1879-1026 VL - 715 SP - 1 EP - 8 PB - Elsevier CY - Amsterdam AN - OPUS4-50477 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steckenmesser, D. A1 - Vogel, Christian A1 - Herzel, Hannes A1 - Félix, R. A1 - Adam, Christian A1 - Steffens, D. T1 - Thermal treatment of sewage sludge for phosphorus fertilizer production: a model experiment N2 - Phosphorus (P) resource availability and quality is declining and recycling P-fertilizers from waste materials are becoming increasingly important. One important secondary P resource is sewage sludge (SSL) where P is often bound as aluminum phosphate (Al-P), iron phosphate (Fe-P) and polyphosphate (poly-P), respectively. Thermal treatment in different ways is a promising way in P recycling to produce highly plant-available P-fertilizers. To investigate mechanisms behind transformation of hardly available P-species toward plant-available P forms we treated a model SSL containing different kinds of defined P sources by low-temperature conversion (LTC) at 500 °C and subsequent thermochemical treatment of the LTC product with Na additives (TCT) at 950 °C, respectively. Pot experiments with ryegrass were carried out to determine the plant availability of P of the different treatments. The poly-P (here pyrophosphates) based fertilizers had a very high plant availability after both thermal treatments. During LTC treatment the plant availability of the Fe-P and Al-P variants increased because of the Formation of Fe(II) phosphates and/or pyro-/polyphosphates. Especially the formation of Al-polyphosphate shows a high plant availability. The subsequent TCT further increased strongly the plant availability of the Fe-P variants because of the formation of highly plant-available CaNaPO4. Thus, a direct TCT without prior LTC probably also produce CaNaPO4 and is recommended for Fe-P based SSL. However, a molar Ca/P ratio of � 1 in the fertilizer is favorable for CaNaPO4 formation. Thus, the knowledge on the source of primary P in SSL is essential for choosing the accurate thermal treatment method to produce highly plant-available P-fertilizers from SSL. KW - Phosphorus KW - Sewage sludge KW - X-ray diffraction KW - X-ray absorption near-edge structure (XANES) spectroscopy KW - Fertilizer PY - 2021 DO - https://doi.org/10.1080/01904167.2021.1994595 SN - 0190-4167 VL - 45 IS - 8 SP - 1123 EP - 1133 PB - Taylor & Francis Online AN - OPUS4-53755 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Hoffmann, Marie A1 - Taube, Mareike A1 - Krüger, O. A1 - Baran, R. A1 - Adam, Christian T1 - Uranium and thorium species in phosphate rock and sewage sludge ash based phosphorus fertilizers N2 - Phosphorus (P) is an essential element for all forms of life and is thus often applied as phosphate rock-based P-fertilizers in agriculture to enable continuous farming. However, these P-fertilizers contain also hazardous uranium (U) and thorium (Th), up to 660 and 220 mg/kg, respectively. On the contrary, novel P-fertilizers made from sewage sludge (ash) contain only low mass fractions of U and Th. In addition to the total amount of U and Th in P-fertilizers, their mobility and bioavailability is important, which depends to a large extent on their chemical state, especially oxidation state and chemical bonding. Thus, we analyzed their chemical state in various P-fertilizers by U and Th L3-edge HERFD-XANES spectroscopy. Phosphate rocks and sewage sludge-based P-fertilizers contain mainly U(IV) compounds which have only a low bioavailability. In contrast, acidic treatment of phosphate rock to produce super phosphates lead to an oxidation to U(VI) compounds (including formation of uranium phosphates) with a strongly increased bioavailability. On the contrary, all analyzed P-fertilizers contain Th in form of strongly insoluble phosphates and oxides with a low bioavailability. Additionally performed water extractions and Diffusive Gradients in Thin-films (DGT) experiments support these findings. KW - Phosphorus fertilizer KW - Sewage sludge KW - X-ray absorption near-edge structure (XANES) spectroscopy KW - Diffusive Gradients in Thin-films (DGT) KW - Extraction PY - 2020 DO - https://doi.org/10.1016/j.jhazmat.2019.121100 SN - 0304-3894 VL - 382 SP - 121100, 1 EP - 6 AN - OPUS4-48872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herzel, Hannes A1 - Dombinov, V. A1 - Vogel, Christian A1 - Willbold, S. A1 - Levandowski, G. V. A1 - Meiller, M. A1 - Müller, F. A1 - Zang, J. W. A1 - da Fonseca-Zang, W. A. A1 - Jablonowski, N. D. A1 - Schrey, S. D. A1 - Adam, Christian T1 - Soybean Fertilized by P-Phases from Bagasse-Based Materials: P-Extraction Procedures, Diffusive Gradients in Thin Films (DGT), and X-ray Diffraction Analysis (XRD) N2 - The Brazilian sugarcane industry produced around 173 million tons (Mt) of bagasse in 2018. Bagasse is a by-product of juice extraction for ethanol and sugar production and is combusted in order to generate power, producing up to 10 Mt of ash per year. This ash contains various concentrations of plant nutrients, which allow the ash to be used as a crop fertilizer. However, the concentration and extractability of phosphorus (P), an essential plant nutrient, are low in bagasse ash. To increase the P content, we co-gasified and co-combusted bagasse with P-rich chicken manure. The resulting ash was thermochemically post-treated with alkali additives (Na2SO4 and K2SO4) to increase the availability of P to plants. We aimed to: (i) investigate the effect of thermochemical post-treatment of co-gasification residue and co-combustion ash on P availability to soybeans, (ii) explore the potential of chemical extraction methods (citric acid, neutral ammonium citrate, formic acid, and Mehlich-I) and diffusive gradients in thin films (DGT) to predict the availability of P to soybeans, and (iii) identify the responsible P-phases using X-ray diffraction . We evaluated P availability to soybeans growing in Brazilian Oxisol soil in two independent greenhouse pot experiments. The positive effect of thermochemical treatment on P availability from gasification residue was confirmed through the observation of increased P uptake and biomass in soybean plants. These findings were confirmed by chemical extraction methods and DGT. The gasification residue contained whitlockite as its main P-bearing phase. Thermochemical post-treatment converted whitlockite into highly soluble CaNaPO4. In contrast, co-combustion ash already contained highly soluble Ca(Na,K)PO4 as its main P-bearing phase, making thermochemical post-treatment unnecessary for increasing P availability. In conclusion, increased extractability and availability of P for soybeans were closely connected to the formation of calcium alkali phosphate. Our findings indicate that this combined methodology allows for the prediction of P-fertilization effects of ash. KW - Sugar cane bagasse KW - Chicken manure ash KW - Thermochemical treatment KW - Nutrient KW - Plant availability PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509735 DO - https://doi.org/10.3390/agronomy10060895 VL - 10 SP - 895 EP - 6 PB - MDPI AN - OPUS4-50973 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gentzmann, Marie A1 - Schraut, Katharina A1 - Vogel, Christian A1 - Gäbler, H.-E. A1 - Huthwelker, T. A1 - Adam, Christian T1 - Investigation of scandium in bauxite residues of different origin N2 - This paper focuses on the scandium speciation in bauxite residues of different origin. Insights into mineralchemical similarities and differences of these materials will be presented and links to their natural geological background discussed. The presented research should provide fundamental knowledge for the future development of efficient and viable technologies for Sc-recovery from bauxite residues derived from different bauxites and accumulating at different localities. In total, five bauxite residues were investigated which originated from Greece, Germany, Hungary and Russia (North Ural & North Timan) using a combination of different analytical tools. Those included: laser ablation inductively coupled plasma mass spectrometry, X-ray absorption near Edge structure (XANES) spectroscopy, μ-Raman spectroscopy as well as scanning electron microscopy and electron microprobe analyses. X-ray fluorescence and inductively coupled plasma mass spectrometry were used to determine the overall chemical composition. The investigated samples were found to exhibit a relatively homogenous distribution of Sc between the larger mineral particles and the fine-grained matrix except for Al-phases like diaspore, boehmite and gibbsite. These phases were found to be particularly low in Sc. The only sample where Sc mass fractions in Al-phases exceeded 50 mg/kg was the Russian sample from North Ural. Fe-phases such as goethite, hematite and chamosite (for Russian samples) were more enriched in Sc than the Al-phases. In fact, in Greek samples goethite showed a higher capacity to incorporate or adsorb Sc than hematite. Accessory minerals like zircon, rutile/anatase and ilmenite were found to incorporate higher mass fractions of Sc (>150 mg/kg), however, those minerals are only present in small amounts and do not represent major host phases for Sc. In Russian samples from North Ural an additional Ca–Mg rich phase was found to contain significant mass fractions of Sc (>500 mg/kg). μ-XANES spectroscopy was able to show that Sc in bauxite residue occurs adsorbed onto mineral surfaces as well as incorporated into the crystal lattice of certain Fe-phases. According to our observations the bauxite type, i.e. karstic or lateritic, the atmospheric conditions during bauxitization, i.e. oxidizing or reducing, and consequently the dominant Sc-bearing species in the primary Bauxite influence the occurrence of Sc in bauxite residues. In karstic bauxites, underlying carbonate rocks can work as a pH-barrier and stabilize Sc. This prevents the Sc from being mobilized and removed during bauxitization. Hence, karstic bauxites are more prone to show a Sc enrichment than lateritic bauxites. Reducing conditions during bauxitization support the incorporation of Sc into clay minerals such as chamosite, which can dissolve and reprecipitate during Bayer processing causing Sc to be redistributed and primarily adsorb onto mineral surfaces in the bauxite residue. Oxidizing conditions support the incorporation of Sc into the crystal lattice of Fe-oxides and hydroxides, which are not affected in the Bayer process. The genetic history of the bauxite is therefore the major influential factor for the Sc occurrence in bauxite residues. KW - Sc recovery KW - Scandium KW - Bauxite Residue KW - Red Mud KW - XANES PY - 2021 DO - https://doi.org/10.1016/j.apgeochem.2021.104898 SN - 0883-2927 VL - 126 SP - 104898 PB - Elsevier Ltd. AN - OPUS4-52123 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meiers, Emelie A1 - Scholl, Juliane A1 - Droas, Morten A1 - Vogel, Christian A1 - Leube, Peter A1 - Sommerfeld, Thomas A1 - Bagheri, A. A1 - Adam, Christian A1 - Seubert, A. A1 - Koch, Matthias T1 - Development and evaluation of analytical strategies for the monitoring of per- and polyfluoroalkyl substances from lithium-ion battery recycling materials N2 - Per- and polyfluoroalkyl substances (PFAS) are well-known as “forever chemicals” and persistent pollutants released by different anthropogenic sources. The potential release of PFAS from accumulating electronic waste and lithium-ion battery (LIB) recycling activities has gained increasing attention in the past years. This creates a need for analytical methods tailored for the determination of PFAS out of environmental matrices related to the named activities or directly out of the concerned materials. In this work, analytical strategies for the monitoring of PFAS in LIB recycling materials were explored for a group of legacy perfluoro sulfonic- and carbonic acids (PFSA and PFCA) and of fluorinated sulfonylimides suspected to be LIB electrolyte ingredients. These analytical strategies comprehend PFAS target approaches with a herein optimized liquid chromatography tandem mass spectrometry (LC–MS/MS) method equipped with a HILIC (hydrophilic interaction liquid chromatography) column in combination with the TOP (total oxidizable precursor) assay and an adapted sample preparation method for high-matrix LIB recycling materials. The validated target method was applied to a set of LIB recycling materials: end-of-life batteries, black masses from hydrometallurgical recycling, and gas absorption solutions from thermal treatment of black masses as part of the recycling procedure. Investigation results show that the LIB industry can be connected to the release of both “LIB”-PFAS, such as the target sulfonylimides, and “already-legacy” PFAS, like the PFSA and PFCA. Especially, the presence of trifluoroacetic acid (TFA) as an emerging pollutant in every investigated LIB material type underlines the threat of PFAS emissions from LIB waste and recycling activities. KW - Per- and polyfluoroalkyl substances (PFAS) KW - Battery PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647015 DO - https://doi.org/10.1007/s00216-025-06165-8 SN - 1618-2642 VL - 417 SP - 6567 EP - 6583 PB - Springer Science and Business Media LLC AN - OPUS4-64701 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -