TY - JOUR A1 - Vogel, Christian A1 - Roesch, Philipp A1 - Wittwer, Philipp A1 - Piechotta, Christian A1 - Lisec, Jan A1 - Sommerfeld, Thomas A1 - Kluge, Stephanie A1 - Herzel, Hannes A1 - Huthwelker, T. A1 - Borca, C. A1 - Simon, Franz-Georg T1 - Levels of per- and polyfluoroalkyl substances (PFAS) in various wastewater-derived fertilizers - Analytical investigations from different perspectives N2 - Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values of the fertilizers in samples with >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 A1 - Herzel, Hannes A1 - Wittwer, Philipp A1 - Leube, Peter A1 - Adam, Christian T1 - Per- und polyfluorierte Alkylsubstanzen (PFAS) während der Klärschlammverbrennung – Analytische Methoden zur Überwachung N2 - Per- and polyfluoroalkyl substances (PFAS) are a group of more than 12,000 anionic cationic, zwitterionic and neutral anthropologic substances which have been used extensively in a variety of products and industries due to their lipo- and hydrophobic properties, and inert physical and chemical stability. As a result of continuous use of fluorinated consumer products, effluents and sewage sludge from wastewater treatment plants (WWTPs) have been shown to be an important source of PFAS contamination into the environment. While environmental exposure of organic pollutants like PFAS, pesticides and pharmaceuticals have to be avoided, phosphorus from sewage sludge must be used in Germany among other things to produce high-quality P-fertilizers for a circular economy. However, the fate of legacy and emerging PFAS compounds during sewage sludge incineration or pyrolysis is for the most parts still unknown. In particular, PFAS analysis in exhaust air from industrial facilities has not yet been standardized in Germany, which means that no comparable results are available for possible regulation. T2 - Berliner Klärschlamm Konferenz CY - Berlin, Germany DA - 11.11.2024 KW - Klärschlamm KW - Per- and Polyfluoroalkyl substances (PFAS) PY - 2024 SN - 978-3-911006-83-5 SP - 230 EP - 241 PB - Thomé-Kozmiensky Verlag GmbH CY - Neuruppin AN - OPUS4-61627 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Helfenstein, J. A1 - Massey, M. A1 - Sekine, R. A1 - Kretzschmar, R. A1 - Beiping, L. A1 - Peter, T. A1 - Chadwick, O. A1 - Tamburini, F. A1 - Rivard, C. A1 - Herzel, Hannes A1 - Adam, Christian A1 - Pradas del Real, A. A1 - Castillo-Michel, H. A1 - Zuin, L. A1 - Wang, D. A1 - Félix, R. A1 - Lassalle-Kaiser, B. A1 - Frossard, E. T1 - Microspectroscopy reveals dust-derived apatite grains in acidic, highly-weathered Hawaiian soils N2 - Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic Gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure) and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to co-location with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils through atmospheric deposition. KW - Phosphorus KW - soil KW - microspectroscopy KW - Raman spectroscopy KW - XANES spectroscopy KW - x-ray diffraction PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-511522 DO - https://doi.org/10.1016/j.geoderma.2020.114681 SN - 0166-0918 SN - 1872-6259 VL - 381 SP - 114681-1 EP - 114681-11 PB - Elsevier CY - Amsterdam AN - OPUS4-51152 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 - CONF A1 - Müller, S. A1 - Herzel, Hannes A1 - Adam, Christian A1 - Montag, D. ED - Holm, O. ED - Thomé-Kozmiensky, E. ED - Quicker, P. ED - Kopp-Assenmacher, S. T1 - Langzeitlagerung von Klärschlammaschen ab 2029? Erste Erfahrungen zur Phosphorrückgewinnung aus deponierten Klärschlammverbrennungsaschen N2 - Das Institut für Siedlungswasserwirtschaft (ISA) der RWTH Aachen University sowie die Bundesanstalt für Materialforschung und -prüfung (BAM) untersuchen gemeinsam fünf deponierte KSA, die von drei Deponiebetreibern ausgebaut und zur Verfügung gestellt wurden sind. Im Fokus der Untersuchungen stehen die physikalische und chemische Charakterisierung der deponierten KSA sowie deren P-Rückgewinnungspotenzial bei der Behandlung in thermochemischen sowie nasschemischen Verfahren. Diese Ergebnisse werden im Vergleich mit „frischen“, also nicht deponierten KSA-Proben vergleichbarer Herkunft bewertet, um so den Einfluss der Lagerung auf die KSA zu erfassen. T2 - Berliner Klärschlamm Konferenz CY - Berlin, Germany DA - 11.11.2025 KW - Klärschlammasche KW - Recycling KW - Deponie KW - Monoverbrennung PY - 2025 SN - 978-3-911006-63-7 VL - 8 SP - 192 EP - 202 PB - Thomé-Kozmiensky Verlag GmbH CY - Neuruppin AN - OPUS4-65017 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Leers, K. A1 - Herzel, Hannes A1 - Emter, J. A1 - Brey, C. A1 - Leimkötter, D. A1 - Künstler, J. A1 - Arnold, U. A1 - Burkhardt, J. A1 - Adam, Christian T1 - Untersuchungen zur agronomischen Wirksamkeit des R-Rhenania Phosphats aus der ersten großtechnischen Anlage N2 - Aufgrund ihrer Phosphorgehalte bieten Klärschlammaschen (KSA) Potentiale für die Herstellung von Phosphatdüngern. Da die agronomische Wirksamkeit von KSA häufig gering ist, bedarf es einer Aufbereitung. Diese kann sowohl vor oder während der Verbrennung des Klärschlamms als auch nachgeschaltet durch eine Aufbereitung der KSA erfolgen. Mit dem nachgeschalteten, thermochemischen AshDec® Verfahren können unter Hinzugabe eines Natrium-Additivs bereits wirksame aschebasierte Düngerprodukte aus KSA hergestellt werden. Im Rahmen des BMBF-Projekts „R-Rhenania“ wurde auf dieser Basis ein thermochemisches Verfahren für eine Rostfeuerung entwickelt, bei dem die Zugabe des Natrium-Additivs direkt bei der Klärschlammverbrennung erfolgt. So sollen die hochwirksamen aschebasierten Dünger direkt bei der Klärschlammverbrennung entstehen (R-Rhenania-Prozess). Der Vergleich von Produkten aus beiden Prozessen (R-Rhenania und nachgeschaltetes AshDec Verfahren) zeigt, dass die chemische Zusammensetzung vergleichbar ist. In Versuchskampagnen in der Monoverbrennungsanlage der Firma Emter GmbH in Altenstadt (Oberbayern) konnte gezeigt werden, dass die Phosphatlöslichkeit in neutraler Ammoniumcitratlösung (PNAC-Löslichkeit) der R-Rhenania Produkte von der Dosierung des Natrium-Additivs abhängt. Am Standort Altenstadt korreliert eine Konzentration von über 8 Gew.-% Na im Produkt mit einer relativen PNAC-Löslichkeit von mindestens 80 % und eine vollständige Löslichkeit mit einem Na-Gehalt von 10,5 Gew.-% Na. Beim Einsatz von R-Rhenania Produkten als P-Dünger für Sommerweizen konnte eine hohe agronomische Wirksamkeit nachgewiesen werden. In den Gefäßversuchen zeigte sich zudem ein Zusammenhang zwischen der PNAC-Löslichkeit und der Düngerwirksamkeit, wobei diese Wirksamkeit der Produkte mit zunehmender Löslichkeit anstieg. Während die Wirksamkeit unbehandelter KSA vergleichbar war zu einer ungedüngten Kontrollvariante, erwiesen sich R-Rhenania Produkte mit einer PNAC-Löslichkeit von mehr als 80 % als besonders effektiv. Die Düngewirkung bei diesen Produkten war sowohl vergleichbar zu einem AshDec-Produkt als auch zu einem konventionellen, wasserlöslichen P-Düngemittel. Auf Grund der erfolgreichen Prozessentwicklung und der nachgewiesenen agronomischen Wirksamkeit der Produkte, wurde am Standort Altenstadt das thermochemische R-Rhenania-Verfahren in die vorhandene Klärschlammmonoverbrennungsanlage integriert. Ab dem Sommer 2024 können dort 15.000 t/a R-Rhenania Dünger hergestellt werden. T2 - Berliner Klärschlamm Konferenz CY - Berlin, Germany DA - 11.11.2024 KW - Phosphor KW - Recycling KW - Dünger KW - Monoverbrennung KW - Klärschlamm PY - 2024 SN - 978-3-911006-83-5 SP - 316 EP - 328 PB - Thomé-Kozmiensky Verlag GmbH CY - Neuruppin AN - OPUS4-61907 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Leers, K. A1 - Herzel, Hannes T1 - Untersuchungen zur agronomischen Wirksamkeit des R-Rhenania Phosphats aus der ersten großtechnischen Anlage N2 - Aufgrund ihrer Phosphorgehalte bieten Klärschlammaschen (KSA) Potentiale für die Herstellung von Phosphatdüngern. Da die agronomische Wirksamkeit von KSA häufig gering ist, bedarf es einer Aufbereitung. Diese kann sowohl vor oder während der Verbrennung des Klärschlamms als auch nachgeschaltet durch eine Aufbereitung der KSA erfolgen. Mit dem nachgeschalteten, thermochemischen AshDec® Verfahren können unter Hinzugabe eines Natrium-Additivs bereits wirksame aschebasierte Düngerprodukte aus KSA hergestellt werden. Im Rahmen des BMBF-Projekts „R-Rhenania“ wurde auf dieser Basis ein thermochemisches Verfahren für eine Rostfeuerung entwickelt, bei dem die Zugabe des Natrium-Additivs direkt bei der Klärschlammverbrennung erfolgt. So sollen die hochwirksamen aschebasierten Dünger direkt bei der Klärschlammverbrennung entstehen (R-Rhenania-Prozess). Der Vergleich von Produkten aus beiden Prozessen (R-Rhenania und nachgeschaltetes AshDec Verfahren) zeigt, dass die chemische Zusammensetzung vergleichbar ist. In Versuc T2 - Berliner Klärschlamm Konferenz CY - Berlin, Germany DA - 11.11.2024 KW - Phosphor KW - Recycling KW - Dünger KW - Monoverbrennung KW - Klärschlamm PY - 2024 AN - OPUS4-61908 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Leers, K. A1 - Arnold, U. A1 - Herzel, Hannes A1 - Adam, Christian A1 - Burkhardt, J. T1 - Thermochemically Treated Sewage Sludge Ash From Pilot-Scale Production as P-Fertilizer for Spring Wheat and Maize in Different Soil Conditions N2 - Background P-fertilizers made from sewage sludge ash (SSA) may be suitable substitutes for rock phosphate (RP)-based fertilizers and contribute to sustainable use of waste. In this context, the thermochemical AshDec treatment of SSA (TC-SSA) has been continuously improved and has emerged as a possible method to produce plant-available and low-pollutant P-fertilizers. Aim Evaluation of the P-fertilizer efficacy of TC-SSA produced in pilot trials in vegetation experiments with different plants, soils, and fertilizer doses. Methods TC-SSA was tested in pot experiments for spring wheat and maize on different soils and at two doses (0.2 and 0.4 g fertilizer P pot−1) and is compared to untreated SSA (USSA), RP, Struvite, triple superphosphate (TSP), and a control without P-fertilization (Zero P). Pot experiments are complemented by an analysis of fertilizer P-solubility. Results P-solubility of SSA with different extraction methods increased due to the thermochemical treatment, whereas the water-insoluble property remained. In contrast to RP or USSA, TC-SSA enriched calcium–acetate–lactate extractable soil P to the same extent as TSP. Plant biomass and P-uptake increased with TC-SSA compared to Zero P, RP, and USSA and were in most cases equal to TSP fertilization under different soil conditions. In contrast, the effects of RP and USSA varied among soils but, mostly, did not exceed plant biomass and P-uptake of the unfertilized control. Conclusion TC-SSA has an increased fertilizer efficacy compared to USSA and is an effective P-fertilizer for spring wheat and maize in different soil conditions. KW - Phosphorus KW - Fertilizer KW - Thermochemical KW - Maize PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-648251 DO - https://doi.org/10.1002/jpln.70035 SN - 1522-2624 VL - 189 IS - 1 SP - 81 EP - 93 PB - Wiley-VCH AN - OPUS4-64825 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herzel, Hannes A1 - Stemann, J. A1 - Simon, Sebastian A1 - Adam, Christian T1 - Comparison of thermochemical treatment of sewage sludge ash with sodium sulphate in laboratory-scale and pilot-scale experiments N2 - There is an ongoing debate on European scale concerning the criticality of phosphorus. In Switzerland and Germany, phosphorus recovery from phosphorus-rich waste streams will become obligatory. Sewage sludge ash is rich in phosphorus and may become an important secondary feedstock. Thermochemical treatment of sewage sludge ash with sodium sulphate under reducing conditions was shown to remove heavy metals from the solid product and produce the fully plant available crystalline phase CaNaPO4. Pilot-scale experiments in a rotary kiln were carried out at temperatures between 750 and 1000 °C and were compared to laboratory-scale experiments with crucibles. Process upscaling was successfully demonstrated but a series of differences were noticed: In comparison to laboratory-scale, solubility of phosphorus in samples from pilot-scale experiments was lower at all chosen treatment temperatures because of shorter retention time and incomplete decomposition of sodium sulphate. X-ray diffraction analysis revealed remaining phase fractions of whitlockite (Ca3-x(Mg,Fe)x(PO4)2) and sodium sulphate from the starting materials in products and thus indicated incomplete reaction. In contrast to the results of laboratory-scale experiments, the crystalline phase CaNaPO4 was clearly absent in the products from the rotary kiln but instead a Mg-bearing phase (Ca,Mg)NaPO4 was formed. Laboratory-scale experiments confirmed (Ca,Mg)NaPO4 is an intermediate phase between whitlockite and CaNaPO4. However, both crystalline phases are characterized by high plant availability. It was shown that heavy metal removal increased at higher temperatures whereas solubility and thus plant availability of phosphorus already reached its maxima at temperatures of 950 °C in pilot-scale and 875 °C in laboratory-scale experiments. KW - Crystalline phase identification KW - Heavy metal removal KW - Phosphorus availability KW - Process upscaling KW - Recovery KW - Rhenanite PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524084 DO - https://doi.org/10.1007/s13762-021-03252-y VL - 19 IS - 3 SP - 1997 EP - 2006 PB - Springer AN - OPUS4-52408 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Herzel, Hannes A1 - Leimkötter, D. A1 - Hermann, L. A1 - Emter, J. A1 - Brey, C. A1 - Künstler, J. A1 - Hartmann, S. A1 - Krannich, G. A1 - Moggert, N. A1 - Kurz, P. A1 - Eder, C. A1 - Grimm, B. A1 - Adam, Christian ED - Holm, O. ED - Thomé-Kozmiensky, E. ED - Quicker, P. ED - Kopp-Assenmacher, S. T1 - Success-Story CaNaPO4: Erfolgreiche REACH Registrierung und Inbetriebnahme großtechnischer Anlagen N2 - The Sewage Sludge Ordinance (AbfKlärV), which was amended in 2017, obligate the recovery of phosphorus from sewage sludge and sewage sludge ash from 2029 and 2032, respectively. Thermal disposal of sewage sludge has established itself as the preferred method of disposal, and the capacities of mono-incineration plants are being continuously expanded. Plants for phosphorus recovery, on the other hand, are currently still mainly in the construction, piloting, or commissioning phase. It is estimated that the plant capacities for P recovery planned today will not even be able to cover a quarter of the volume of these ashes in 2029. Therefore, temporary storage of the remaining ashes is currently being discussed to retrieve it later and process it in the P recovery plants, which will then be sufficiently available. It is currently unclear how such interim or long-term storage (> 1 year) should be organized. In addition to legal (fee) issues, the assessment of the technical feasibility of retrievability and the phosphorus recovery potential of landfilled ash remains open. The Institute of Environmental Engineering (ISA) at RWTH Aachen University and the Federal Institute for Materials Research and Testing (BAM) are jointly investigating five deposited ashes that have been dug out and were provided by three landfill operators. The investigations focus on the physical and chemical characterization of these landfilled ashes and its P recovery potential during treatment in thermochemical and wet chemical processes. These results are evaluated in comparison with “fresh,” i.e., non-landfilled sewage sludge ash samples of comparable origin in order to determine the influence of storage. T2 - Berliner Klärschlamm Konferenz CY - Berlin, Germany DA - 11.11.2025 KW - Phosphor KW - Recycling KW - Thermochemisch KW - Dünger KW - Großtechnik PY - 2025 SN - 978-3-911006-63-7 VL - 8 SP - 236 EP - 256 PB - Thomé-Kozmiensky Verlag GmbH CY - Neuruppin AN - OPUS4-64833 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -