TY - JOUR A1 - Roesch, Philipp A1 - Vogel, Christian A1 - Wittwer, Philipp A1 - Huthwelker, T. A1 - Borca, C. A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Piechotta, Christian A1 - Kalbe, Ute A1 - Simon, Franz-Georg T1 - Taking a Look at the Surface: µ-XRF Mapping and Fluorine K-edge µ-XANES Spectroscopy of Organofluorinated Compounds in Environmental Samples and Consumer Products N2 - For the first time, µ-X-ray fluorescence (µ-XRF) mapping combined with fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substances (PFAS) contamination and inorganic fluoride in samples concentrations down to 100 µg/kg fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheet) were investigated. µ-XRF mapping allows for a unique element-specific visualisation at the sample surface and enables localisation of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analysed via fluorine K-edge µ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded µ-XANES spectra. Complementarily, solvent extracts of all samples were target-analysed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg/kg dry weight (dw). All environmentally exposed samples revealed higher concentration of PFAS with a chain length >C8 (e.g. 580 µg/kg dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent from quantified PFAS amounts via target analysis, µ-XRF mapping combined with µ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples. KW - PFAS KW - XRF KW - LC-MS/MS KW - XANES KW - Fluoride KW - Soil PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576109 DO - https://doi.org/10.1039/D3EM00107E SN - 2050-7887 SP - 1 EP - 12 PB - Royal Society of Chemistry AN - OPUS4-57610 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Sommerfeld, Thomas A1 - Riedel, Maren A1 - Leube, Peter A1 - Kalbe, Ute A1 - Schoknecht, Ute A1 - Simon, Franz-Georg T1 - Per- and Polyfluoroalkyl Substances (PFAS) in Ski Waxes and Snow from Cross-Country Skiing in Germany - Comparative study of Sum Parameter and Target Analysis N2 - Per- and polyfluoroalkyl substances (PFAS) are often environmentally exposed via discharge through human consumer products, such as ski waxes. In our study we analyzed various ski waxes from the 1980s and 2020s, to determine both the sum parameter values total fluorine (TF), extractable organically bound fluorine (EOF), hydrolysable organically bound fluorine (HOF) as well as targeted PFAS analysis. This showed that modern high-performance waxes contain up to 6 % TF, but also PFAS-free labelled ski waxes contain traces of PFAS with EOF/HOF values in the low mg kg-1 range. With the ban of all fluorine-based waxes with the start of the 2023/2024 winter season this will probably change soon. Moreover, we applied our analysis methods to snow samples from a frequently used cross country ski trail (Kammloipe) in the Ore Mountain region in Germany, assessing the potential PFAS entry/discharge through ski waxes. Melted snow samples from different spots were analyzed by the adsorbable organically bound fluorine (AOF) sum parameter and PFAS target analysis and confirmed the abrasion of the ski waxes into the snow. Moreover, on a PFAS hotspot also soil samples were analyzed, which indicate that PFAS from the ski waxes adsorb after snow melting into the soil. KW - Combustion Ion Chromatography KW - Per- and Polyfluoroalkyl substances (PFAS) KW - Consumer Products PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612760 DO - https://doi.org/10.1016/j.hazadv.2024.100484 VL - 16 SP - 1 EP - 5 PB - Elsevier B.V. AN - OPUS4-61276 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 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 - Urban, Klaus A1 - Ackerhans, C. A1 - Gorbushina, Anna T1 - Analysis of Carbon and Nitrogen from Atmospheric Sources by Bulk Deposition Sampling at various locations in Germany N2 - Atmospheric deposition of particulate matter is an important indicator of air pollution and a significant factor in material surface fouling. The elemental composition of this nutrient-containing dust depends largely on the exposure region and time as well as on climate. Therefore, in this paper we report an analysis of atmospheric pollutions with a self-made low-cost bulk deposition sampler directed at sampling deposition via air transport and rainfall. We used the device in diverse environments - thus comparing an urban region, an area surrounded by forest and an area mainly dominated by agriculture. The total organic carbon (TOC) and total nitrogen (TN) amounts were selected as indicator parameters and analyzed in a biweekly rhythm for three and a half and two years, respectively. The TOC value responded to particulate matter in the urban area, especially significant were the influences of the New Year's firework in urban and pollen in the rural forest area. In contrast, the TN value was more under the influence of the nitrogen emissions in the agriculture-dominated area. However, the TN value did not correlate with the NOx values in the urban area because the atmospheric nitrogen emissions in the city might originate from various emission sources. Summarizing, the TOC and TN values of the self-made low-cost bulk deposition sampler were in good agreement with environmental events of their immediate surrounding. Moreover, the selected containers and sampling procedures are universally applicable to monitor and analyze organic as well as inorganic parameters (e.g. metal ions) of atmospheric deposition. KW - Passive sampling KW - Biomonitoring KW - Air Analysis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-609373 DO - https://doi.org/10.1016/j.envadv.2024.100583 SN - 2666-7657 VL - 17 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-60937 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 -