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Paper des Monats
- ja (18)
Thermal Destruction of PFAS
(2023)
Thermal treatment processes are currently the only full-scale option for thedestruction of per- and polyfluoroalkyl substances (PFAS) in large waste streams. While all organic molecules including PFAS are susceptible to thermal destruction, their decomposition rates are controlled by process variables such as temperature, reaction atmosphere, and residence time. Concerns exist about the formation of products of incomplete destruction and their emission from hazardous waste incinerators. This talk will summarize the current stateof-the-art of thermal PFAS destruction, identify research needs, and showcase future research designed to address critical knowledge gaps.
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.
Treatment and reusing of hazardous wastes have become significant issues of modern societies. Blast furnace sludge (BFS) and electric arc furnace dust (EAFD) are such typical wastes, because they usually contain high amounts of undesirable elements such as zinc (Zn) and lead (Pb).
These elements can cause operational problems in reusing of BFS and EAFD. In this study, the Ferro Duo GmbH and the Federal Institute for Materials Research and Testing have investigated a novel approach for eliminating and/or recovering Zn and Pb from both wastes. Applied was a selective chlorination and volatilization of Zn and Pb as chlorides at temperatures between 500 °C and 1100 °C. Both product obtained, Zn and Pb in the form of ZnCl2 and PbCl2 and the purified solid mineral compound are attractive materials for further use. Hydrochloric acid and iron(II) chloride were used as chlorination agents. Exceptionally high Zn and Pb removal efficiencies of >99.5 % could be achieved with both chlorination agents, whereby iron(II) chloride exhibited better performance.
We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1−x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1−x-struvites exhibit high surface areas and pore volumes (240 m2 g−1 and 0.32 cm−3 g−1 for Mg and 90 m2 g−1 and 0.13 cm−3 g−1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis.
Carbonfaser verstärkte Kunststoffe (CFK) sind aus dem Leichtbau nicht mehr wegzudenken. Da die Produktion der Fasern viel Energie benötigt ist deren Recycling anzustreben. Durch Bearbeitung und Handling während des Recyclings verkürzen sich die Carbonfasern (CF) analog zur Papierfaser. Zu kurze Fasern können nicht mehr in eine Flächenstruktur eingebracht werden und müssen daher aus dem Kreislauf ausgeschleust und einer Verwertung zugeführt werden. Untersuchungen des Lehr- und Forschungsgebiets Technologie der Energierohstoffe (TEER) der RWTH Aachen University haben gezeigt, dass die Bedingungen für eine energetische Nutzung von CF-Abfällen in Abfallverbrennungsanlagen nicht geeignet sind. Zudem können CF Betriebsprobleme verursachen. Des Weiteren können bei einer unzureichenden thermischen Behandlung sogenannte WHO-Fasern entstehen, die als gesundheitsschädlich einzustufen sind. Eine Alternative können Hochtemperaturverfahren mit höheren Verweilzeiten sein. Es kommt die Herstellung von Calciumcarbid in Frage, bei der CF als Kohlenstoffträger und der Kunststoff als Energieträger genutzt werden. Eine weitere Verwertungsoption stellt die Stahlproduktionsroute dar. Erste Untersuchungen der Bundesanstalt für Materialforschung und -prüfung (BAM) und TEER am kleintechnischen Lichtbogen der BAM zeigen, dass CF-Abfälle potentiell als Reduktionsmittel und Energieträger eingesetzt werden können.
Thermo-Desorption Gas Chromatography-Mass Spectrometry (TD-GC-MS) was used to investigate the thermal degradation of two different polyurethanes (PU). PU samples were heated at different heating rates and the desorbed products were collected in a cold injection system and thereafter submitted to GC-MS. Prospects and limitations of the detection and quantification of semi-volatile degradation products were investigated. A temperature dependent PU depolymerization was
found at temperatures above 200 °C proved by an increasing release of 1,4-butanediol and methylene diphenyl diisocyanate (MDI) representing the main building blocks of both polymers. Their release was monitored quantitatively based on external calibration with authentic compounds. Size Exclusion Chromatography (SEC) of the residues obtained after thermodesorption confirmed the initial competitive degradation mechanism indicating an equilibrium of crosslinking and depolymerization as previously suggested. Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry of SEC fractions of thermally degraded PUs provided additional hints on degradation mechanism.
Klärschlammaschen können eine hohe Phosphatkonzentration aufweisen und stellen damit einen geeigneten Sekundärrohstoff für die Produktion von Phosphatdüngemitteln dar. Bisher wird dieses Potential der Klärschlammaschen für die Phosphor-Rückgewinnung jedoch kaum genutzt, da die in den Aschen enthaltenen Phosphate für Pflanzen kaum verfügbar und die Aschen teilweise mit toxischen Schwermetallen belastet sind.
Im AshDec®-Verfahren wird die Klärschlammaschen im Drehrohrofen im Temperaturbereich 800-1000°C unter Zugabe von Alkali-Additiven (bsp. Na2CO3) thermochemisch behandelt, um ein wirksames und schadstoffarmes Phosphatdüngemittel herzustellen. Aktuell bereitet die Firma Emter GmbH den Bau der ersten großtechnischen AshDec®-Anlage mit einer Kapazität von 30.000 Jahrestonnen Klärschlammasche am Standort ihrer Klärschlammverbrennungsanlage (Altenstadt / Oberbayern) vor. Die erste Ausbaustufe dieser Anlage wird durch das BMBF-Projekt R-Rhenania im Rahmen der Förderinitiative RePhoR begleitet.
Phosphorus (P) recovery from sewage sludge ash (SSA) is one of the most promising approaches of phosphate rock substitution in mineral fertilizers and might be a sustainable way to secure supply of this raw material in the future. In the current investigation, the process of thermochemical treatment of SSA was applied to SSA coming from selected mono-incineration plants of municipal sewage sludge in Poland (Cracow, Gdansk, Gdynia, Lodz, Kielce and Szczecin).
The Polish SSA was thermochemically converted in the presence of sodium (Na) additives and a reducing agent (dried sewage sludge) to obtain secondary raw materials for the production of marketable P fertilizers. The process had a positive impact on the bioavailability of phosphorus and reduced the content of heavy metals in the obtained products. The P solubility in neutral Ammonium citrate, an indicator of its bioavailability, was significantly raised from 19.7–45.7% in the raw ashes and 76.5–100% in the thermochemically treated SSA. The content of nutrients in the recyclates was in the range of 15.7–19.2% P2O5, 10.8–14.2% CaO, 3.5–5.4% Na2O, 2.6–3.6% MgO and 0.9–1.3% K2O. The produced fertilizer raw materials meet the Polish norms for trace elements covered by the legislation: the content of lead was in the range 10.2–73.1 mg/kg, arsenic 4.8–22.7 mg/kg, Cadmium 0.9–2.8 mg/kg and mercury <0.05 mg/kg. Thus, these products could be potentially directly used for fertilizer production. This work also includes an analysis of the possibilities of using ashes for fertilizer purposes in Poland, based on the assumptions indicated in the adopted strategic and planning documents regarding waste management and fertilizer production.
During iron and steel production, several by-products such as slags, dusts, and sludges are generated in addition to pig iron and steel as primary products. Especially for filter dusts and sludges containing zinc and lead from gas purification, there are still considerable recycling problems. However, the high heavy metal contents make landfilling of these dusts and sludges cost-intensive and ecologically problematic. In addition, the relatively high zinc and iron loads represent a valuable resource, which can make reprocessing of the material with recovery of the zinc and iron loads as secondary raw materials ecologically as well as economically attractive. Nevertheless, established recycling methods like the Waelz process fall short in regaining more than one valuable metal from the dusts and operate only under narrow ranges of material compositions, which makes it problematic to adapt these processes to new dust compositions as are to be formed in future steel work operations.
To tackle these problems, the German Federal Institute for Materials Research and Testing (BAM) and Ferro Duo GmbH investigate innovative recycling methods for steelwork dusts and sludges in a joint project. This mainly focusses on regaining valuable metals such as iron as well as zinc from blast furnace sludge (BFS) and electric arc furnace dust (EAFD) by thermochemical treatment.
Therefore, mixtures of these materials are heated under inert atmosphere employing the carbon present in BFS as internal reducing agent. During the process, metallic iron is formed in the solid reaction product while zinc and other volatile heavy metals are evaporated. This paves the way for the generation of zinc as well as sponge iron as two separate products valuable for metallurgical processes. The process basically consists of heating a mixture of BFS and EAFD to temperatures between 700 and 1100 °C under inert (e.g., nitrogen) or reducing (e.g., CO) gas flow. When a suitable mixing ratio is applied, the carbon present in the BFS can be effectively used as reducing agent for iron and zinc present in both starting materials generating a solid residue with high metallic iron and low carbon content as well as a gas stream laden with zinc and other volatile heavy metals, that can be regained by off-gas treatment.
The project aims at testing this concept as a continuous process in a pilot plant established by Ferro Duo GmbH with BAM supplying comprehensive scientific support by lab- and small scale-experiments.
Additionally, considering the necessity to mitigate CO2 emissions and the resulting shift in compositions of steel work dusts and sludges, our research also investigates replacement of carbon present in the sludges by hydrogen as potentially carbon-neutral reducing agent. Here, the use of non-explosive forming gas as reducing agent for EAFD shows potential to give a product high in metallic iron while zinc and other heavy metals are effectively evaporated from the solid material making it possible to regain them from the exhaust gas stream.
Blast furnace (BF) sludge and electric arc furnace (EAF) dust are typical wastes that incur from iron and steel production. In addition to iron, calcium, carbon, and silicon they usually contain high concentrations of heavy metals such as zinc, lead, and cadmium that are potentially hazardous to the environment, rendering disposal in landfills ecologically problematic and costly. Consequently, pyrometallurgical, hydrometallurgical, and hybrid methods for selective elimination of non-ferrous heavy metals from BF sludge and EAF dust have been conceived, of which only the carbothermic reduction route taken in the so-called Waelz rotary kiln process has been proven to be economically successful. However, this process has several drawbacks regarding efficiency of heavy-metal removal and recovery of iron, and it does not allow processing of BF sludge. In this study, we investigated the efficiency and feasibility of selective chlorination and evaporation of non-ferrous heavy metals, particularly zinc and lead, in both BF sludge and EAF dust as an alternative, thermochemical processing route. To this end, hydrochloric acid and iron(II) chloride solution have been used as chlorinating agents, and the process of heavy-metal chlorination and evaporation has been investigated under inert operating conditions, at variable chlorine concentrations, and at temperatures between 500 and 1200 °C.
High zinc and lead removal efficiencies of > 99.5 % were achieved with both chlorinating agents, but iron(II) chloride turned out to be overall more efficient for removal of zinc and lead from BF sludge and EAF dust. Interestingly, and in contrast to previous studies, the iron was completely retained in the processed solid residue, therefore rendering the processed residues virtually zinc- and lead-free raw materials that may either be used internally (e.g., feeding processed BF sludge and EAF dust back into the respective furnaces) or externally (e.g., for cement production).
Thermochemische Aufarbeitung von Stahlwerksstäuben und -schlämmen zur Zink- und Eisenrückgewinnung
(2024)
Stahlwerksstäube und -schlämme enthalten in der Regel Schwermetalle wie Zink, Blei und Cadmium, die ein direktes Recycling verhindern und diese Stoffe potenziell umweltgefährdend machen. Um diese Schwermetalle aus den Materialien zu entfernen, werden drei thermochemische Verfahren zur Aufarbeitung von Gichtgasschlamm, Elektroofenstaub und ähnlichen Stahlwerksstäuben vorgestellt. Zum einen kann die Mischung von Elektroofenstaub mit chloridhaltigen Lösungen, wie sie z. B. in der Titandioxidproduktion anfallen, gemischt werden, um bei der thermischen Behandlung Schwermetallchloride zu effektiv verdampfen. Weiterhin kann der im Gichtgasschlamm enthaltene Kohlenstoff genutzt werden, um in Mischungen aus Gichtgasschlamm und Elektroofenstaub bei der thermischen Behandlung als Reduktionsmittel zu wirken. Dieses Verfahren führt zur Rückgewinnung von Zink und metallischem Eisen und wird im Technikums- und Pilotmaßstab erprobt. Abschließend wird die Nutzung von Wasserstoff als Reduktionsmittel für Elektroofenstaub vorgestellt. Hierbei lässt sich der Reststoff potenziell klimaneutral in Eisenschwamm umwandeln, wobei die chemischen Grundlagen anhand von DTA-Experimenten und thermodynamischen Simulationen ergründet werden.
Thermochemische Behandlung von Klärschlammaschen - Phosphorrückgewinnung mit dem AshDec Prozess
(2021)
Klärschlammaschen können eine hohe Phosphatkonzentration aufweisen und stellen damit einen geeigneten Sekundärrohstoff für die Produktion von Phosphatdüngemitteln dar. Bisher wird dieses Potential der Klärschlammaschen für die Phosphor-Rückgewinnung jedoch kaum genutzt, da die in den Aschen enthaltenen Phosphate für Pflanzen kaum verfügbar und die Aschen teilweise mit toxischen Schwermetallen belastet sind.
Im AshDec®-Verfahren wird die Klärschlammaschen im Drehrohrofen im Temperaturbereich 800-1000°C unter Zugabe von Alkali-Additiven (bsp. Na2CO3) thermochemisch behandelt, um ein wirksames und schadstoffarmes Phosphatdüngemittel herzustellen. Aktuell bereitet die Firma Emter GmbH den Bau der ersten großtechnischen AshDec®-Anlage mit einer Kapazität von 30.000 Jahrestonnen Klärschlammasche am Standort ihrer Klärschlammverbrennungsanlage (Altenstadt / Oberbayern) vor. Die erste Ausbaustufe dieser Anlage wird durch das BMBF-Projekt R-Rhenania im Rahmen der Förderinitiative RePhoR begleitet.
Im Verbundprojekt R-Rhenania wird eine industrielle Demonstrationsanlage am Standort der Monoverbrennungsanlage Altenstadt der Firma Emter errichtet und im Jahr 2024 den Betrieb aufnehmen. Die vorhandene Rostfeuerung-Monoverbrennung wird so umgebaut, dass ein neues thermochemisches Verfahren integriert werden kann, welches hochwirksame und schadstoffarme Dünger produziert (bis zu 17.000 t/a). Die thermochemischen Produkte werden in Gefäß- und Feldversuchen im ökologischen Landbau auf ihre Düngewirkung getestet. Die Umweltverträglichkeit der Demonstrationsanlage wird untersucht, wie auch die Übertragbarkeit des Verfahrens auf weitere Regionen.
Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from - 2018.3 ± 2.2 kJ mol-1 to - 2030.5 ± 2.1 kJ mol-1 and standard entropy from 137.2 ± 1.0 J mol-1 K-1 to 148.6 ± 1.0 J mol-1 K-1 from sodium endmember b-CaNaPO4 to potassium endmember b0-CaKPO4.
Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase b-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases c-Ca(Na0.4K0.6)PO4 and c-Ca Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.
An understanding of the interactions of 2D nanomaterials with pathogens is of vital importance to developing and controlling their antimicrobial properties. In this work, the interaction of functionalized graphene with tunable hydrophobicity and bacteria is investigated. Poly-(ethylene glycol)-block-(poly-N-isopropylacrylamide) copolymer (PEG-b-PNIPAM) with the triazine joint point was attached to the graphene Surface by a nitrene [2 + 1] cycloaddition reaction. By thermally switching between hydrophobic and hydrophilic states, functionalized graphene sheets were able to bind to bacteria. Bacteria were eventually disrupted when the functionality was switched to the hydrophobic state. On the basis of measuring the different microscopy methods and a live/dead viability assay, it was found that Escherichia coli (E. coli) bacteria are more susceptible to hydrophobic interactions than B. cereus bacteria, under the same conditions. Our investigations confirm that hydrophobic interaction is one of the main driving forces at the presented graphene/bacteria interfaces and promotes the antibacterial activity of graphene derivatives significantly.
ABSTRACT: A collection of thioimidazolium salts were synthesized and used as a new class of nonvolatile alkylating agents. Their nonvolatility prevents exposure during use or handling and are thus drastically safer than conventional alkylating agents. We discovered that thioimidazolium Iodide salts cannot release volatile compounds in the solid state, but instead only decompose when molten. Since decomposition proceeds via alkyl iodide elimination, SN2 of iodide on the thioimidazolium cation is constrained in the solid state, and instead can occur only upon melting when ions are mobile. By smart design of these alkylators, the melting point and thus the decomposition temperature of these salts can be increased from 106 to 169 °C and release negligible volatile organic compounds prior to melting. Thioimidazolium-bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids act as a completely nonvolatile and air-stable TFSI-based alkylating agent and can be used for high-throughput Synthesis of TFSI ionic liquids without solvent. Alkyl groups from methyl to dodecyl can be transferred to a nucleophile and the product purified by sublimation of the thione byproduct, which can then be recycled. We also found that thioimidazolium salts with a dodecyl chain are bactericidal, yet can hydrolyze in water to form benign neutral products, and thus wont accumulate in the environment. These results demonstrate that thioimidazolium salts are a designable platform for the pursuit of safer and more environmentally friendly alkylating and antiseptic agents.
Background. Disinfection is an important mitigation strategy to control and prevent the spread of infections. Incomplete or incorrect usage of disinfection may promote evolution of resistance against disinfectants and antibiotics. Ideally, disinfection reduces the number of surviving bacteria and the chance for resistance evolution. Resistance describes the ability to grow in previously inhibitory concentrations of an antimicrobial, whereas tolerance is associated with enhanced survival of lethal doses. Individual bacteria from the same population can display considerable heterogeneity in their ability to survive treatment (i.e. tolerance) with antimicrobials, which can result in unexpected treatment failure.
Objective. In this study, we investigated six active substances of disinfectants, preservatives, and antiseptics against a population of E. coli to identify the presence of a tolerant subpopulation.
Methods. We performed time-kill experiments and analyzed the data with a mathematical model to statistically infer whether the data is best explained by the presence of a tolerant subpopulation.
Results. The analysis identified bimodal kill kinetics for benzalkonium chloride, didecyldimethylammonium chloride, and isopropanol. In contrast, kill kinetics by chlorhexidine, glutaraldehyde, and hydrogen peroxide were best explained by unimodal kill kinetics. These findings have implications for the risk of disinfection failure. In addition, we are currently performing adaptive laboratory evolution (ALE) experiments with the different disinfectants to investigate the potential consequences of tolerant sub-populations for the evolution of antimicrobial resistance and tolerance.
Background. Disinfection is an important mitigation strategy to control and prevent the spread of infections. Incomplete or incorrect usage of disinfection may promote evolution of resistance against disinfectants and antibiotics. Ideally, disinfection reduces the number of surviving bacteria and the chance for resistance evolution. Resistance describes the ability to grow in previously inhibitory concentrations of an antimicrobial, whereas tolerance is associated with enhanced survival of lethal doses. Individual bacteria from the same population can display considerable heterogeneity in their ability to survive treatment (i.e. tolerance) with antimicrobials, which can result in unexpected treatment failure.
Objective. In this study, we investigated six active substances of disinfectants, preservatives, and antiseptics against a population of E. coli to identify the presence of a tolerant subpopulation.
Methods. We performed time-kill experiments and analyzed the data with a mathematical model to statistically infer whether the data is best explained by the presence of a tolerant subpopulation.
Results. The analysis identified bimodal kill kinetics for benzalkonium chloride, didecyldimethylammonium chloride, and isopropanol. In contrast, kill kinetics by chlorhexidine, glutaraldehyde, and hydrogen peroxide were best explained by unimodal kill kinetics. These findings have implications for the risk of disinfection failure. In addition, we are currently performing adaptive laboratory evolution (ALE) experiments with the different disinfectants to investigate the potential consequences of tolerant sub-populations for the evolution of antimicrobial resistance and tolerance.
In recent years, the fabrication of laser-generated surface structures on metals such as titanium surfaces have gained remarkable interests, being technologically relevant for applications in optics, medicine, fluid transport, tribology, and wetting of surfaces.
The morphology of these structures, and so their chemistry, is influenced by the different laser processing parameters such as the laser fluence, wavelength, pulse repetition rate, laser light polarization type and direction, angle of incidence, and the effective number of laser pulses per beam spot area.
However, the characterization of the different surface structures can be difficult because of constraints regarding the analytical information from both depth and the topographic artifacts which may limit the lateral and depth resolution of elemental distributions as well as their proper quantification. A promising technique to investigate these structures even at the nano-scale is Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), a very surface sensitive technique that at the same time allows to perform depth-profiling, imaging and 3D-reconstruction of selected ion-sputter fragment distributions on the surface.
In this study we combine chemical analyses such as Energy Dispersive X-ray spectroscopy (EDX) and high-resolution scanning electron microscopy (SEM) analyses with ToF-SIMS to fully characterize the evolution of various types of laser-generated micro- and nanostructures formed on Ti and Ti alloys at different laser fluence levels, effective number of pulses and at different pulse repetition rates (1 – 400 kHz), following irradiation by near-infrared ultrashort laser pulses (925 fs, 1030 nm) in air environment or under argon gas flow.
We show how this combined surface analytical approach allows to evaluate alteration in the surface chemistry of the laser-generated surface structures depending on the laser processing parameters and the ambient environment.
Black microcolonial fungi represent a group of ascomycetes with similar adaptations for existing in natural and anthropogenically created extreme habitats. They exhibit slow yeast-like or meristematic growth, do not form specialized reproduction structures and accumulate the black pigment 1,8-dihydroxynaphthalene (DHN) in the multilayered cell walls. We chose the rock inhabitant Knufia petricola of the Chaetothyriales as a representative for developing methods for genetic manipulation, simulation of mineral weathering and study of symbiotic interactions. Here, we report on the expansion of the genetic toolkit by more efficient multiplex CRISPR/Cas9 using a plasmid-based system for expression of Cas9 and multiple sgRNAs and three additional resistance selection markers. The targeted integration of expression constructs by replacement of essential genes for pigment synthesis allows for an additional color screening of the transformants. The black-pink screening due to the elimination of pks1 (melanin) was applied for promoter studies using GFP fluorescence as reporter, while the black-white screening due to the concurrent elimination of pks1 (melanin) and phs1 (carotenoids) was used to identify transformants that contain the two expression constructs for co-localization or bimolecular fluorescence complementation (BiFC) studies. In addition, two intergenic regions (igr1, igr2) were identified in which expression constructs can be inserted without causing obvious phenotypes. Plasmids of the pNXR-XXX series (Schumacher, 2012) and new compatible entry plasmids were used for fast and easy generation of expression constructs and are suitable for use in other fungal systems as well.
Microcolonial black fungi are inhabitants of exposed natural and man-made surfaces in all climate zones. Genetic studies are hampered by slow growth, lacking sexual cycles and difficulties to transform these fungi. Recently, we implemented CRISPR/Cas9-based genetic tools enabling efficient targeted mutations of the rock inhabitant Knufia petricola (Eurotiomycetes/Chaetothyriales) for studying stress responses, the unusual types of cell division, mineral weathering and symbiotic interactions with phototrophic microbes (Voigt, Knabe et al. 2020, Sci Rep; Erdmann et al. 2022, Front Fungal Biol). To further explore the genome of this fungus as representative of the polyphyletic group of black fungi and to assign functions to yet unknown genes, a forward genetics approach is aimed. We chose the two-component Activator/ Dissociation (Ac/Ds) transposon system from maize for generating a collection of insertional mutants by in-vivo mutagenesis. For the optimal use of this genetic tool, an inducible promoter for the expression of the Ac transposase and by this the regulatable transposition of the resistance cassette-containing Ds transposon is requested. However, endogenous promoters for nitrate assimilation and galactose catabolism that are often used in fungi for regulatable gene expression are not inducible by their substrates in K. petricola suggesting that the regulatory networks for nutrient acquisition differ significantly in the oligotrophic black fungi. Therefore, the metabolism-independent Tet-on system was adopted and validated using a Ptet::gfp construct. No GFP fluorescence was detected in absence of the inducer doxycycline (DOX) while fluorescence intensities increased with increasing inducer concentrations. Consequently, the Tet-on system is suitable for regulatable expression of endogenous and foreign genes in K. petricola.
Tools for the characterization of secondary raw materials - status of leaching test application
(2018)
Leaching tests are used as tools for the assessment of environmental compatibility of granular waste materials with potential for reuse. The presentation gives an overview on available leaching tests, their field of application and relation to legislation. Furthermore robustness testing to elaborate optimized test conditions as well as performance characteristics from validation studies by BAM are addressed.
Tools for the characterization of secondary raw materials - status of leaching test application
(2018)
Leaching tests are used as tools for the assessment of environmental compatibility of granular waste materials with potential for reuse. The presentation gives an overview on available leaching tests, their field of application and relation to legislation. Furthermore robustness testing to elaborate optimized test conditions as well as performance characteristics from validation studies by BAM are addressed.
Tools for the characterization of secondary raw materials - status of leaching test application
(2018)
Leaching tests are used as tools for the assessment of environmental compatibility of granular waste materials with potential for reuse. The presentation gives an overview on available leaching tests, their field of application and relation to legislation. Furthermore robustness testing to elaborate optimized test conditions as well as performance characteristics from validation studies by BAM are addressed.
Tour de table - BAM
(2021)
This poster summarizes the points that need to be addressed towards the standardization of an efficient procedure for the analysis of VVOC emissions: Standard mixture generation and investigations on mutual reactivity, selection of an appropriate sorbent combination, water management and choice of a suited GC column.
In the transition to the Circular Economy (CE) model, where the added value of products is kept as long as possible and waste is eliminated, the sustainable management of raw materials plays a key role. In above CE model, especial attention is paid to CRMs which are economically and strategically important for the European economy, but have a high-risk associated with their supply.
One of the most important element which can not be replaced and is an essential element for human nutrition, yet limited resource is phosphorus (P). An importance of issues related to sustainable P management results from EU legislation, which indicated P as a Critical Raw Material (CRM).
The sustainable management of P-resources is especially important for the Baltic region. A consequence of waterborne loads passing into the sea, mainly as wastewater with a high P content is the eutrophication of the Baltic Sea environment. Due to the largest inputs of P (37%) into the Baltic Sea originate from Poland, the development of sustainable solutions aimed at more rational P management for this country is externally important.
While studying the socio-geographic history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis.
It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques. The XRF elemental analysis aims primarily at identifying and characterizing metallic components of inks. Besides the instrumental methods, the paper presents an overview of historic inks in the period of transition from carbon inks of the Antiquity to iron-gall inks commonly used in the Middle Ages.
Transformation of carbendazim, diuron, octylisothiazolinone and terbutryn was investigated in two paints containing either white titanium dioxide or a red iron oxide pigment.
Test specimens of these coatings on glass were exposed to water contact and UVA-radiation under laboratory conditions. Panels of birch plywood were coated and exposed to natural weather conditions in a field experiment. Concentrations of biocides and transformation products were analysed in leachates from laboratory tests, runoff samples and remaining coatings. Water contact, UVA radiation as well as pigments in the paints affected the pattern and amount of transformation products.
Wie Länder mit ihren Abfällen umgehen, hängt nicht nur von der Wirtschaftskraft eines Landes ab. Selbst in einem reichen Land wie Australien werden unbehandelte Abfälle einfach deponiert. Im Rahmen der Travelling Conference, einer vom Bundesministerium für Bildung und Forschung (BMBF) geförderten Vortragsreihe, besuchten Fachleute die Länder Südkorea, Vietnam und Australien, um mit Experten vor Ort Fragestellungen aus der Abfallwirtschaft zu diskutieren. Zu den Schwerpunktthemen zählte die Steigerung der Ressourceneffizienz im Spannungsfeld von ökonomischen und umweltpolitischen Interessen. Eine Frage war beispielsweise die Bewertung der Umweltverträglichkeit von mineralischen Abfällen, wenn diese als Ersatzbaustoffe eingesetzt werden. In diesem Beitrag werden Ähnlichkeiten und Unterschiede bei der Entsorgung von Siedlungsabfällen, beim Recycling und bei der Bewertung der Umweltverträglichkeit der Wiederverwertung von Abfällen in den drei besuchten Ländern im Vergleich zu Deutschland aufgezeigt. Dabei ist man sich in Deutschland und den drei besuchten Ländern einig, dass die Abfallbeseitigung auf Deponien ohne Rückgewinnung von Ressourcen oder Energie die schlechteste Abfallentsorgungsoption ist. Einigkeit besteht auch darin, dass die Ziele einer nachhaltigen Abfallwirtschaft der Schutz der menschlichen Gesundheit und der Umwelt sowie die Schonung von Ressourcen sind. In allen drei Ländern werden große Mengen an mineralischen Abfällen erzeugt, die bei Nachweis der Umweltverträglichkeit einen Teil von natürlichem Sand und Kies für die Bauindustrie ersetzen könnten. Ähnlich wie in Deutschland werden recycelte Abfälle im Tiefbau jedoch nur in geringem Maße eingesetzt. Gründe dafür sind fehlende Behandlungsanlagen für mineralische Abfälle und Bedenken im Hinblick auf die Umweltverträglichkeit.
For more than 110 years, BAM has been producing reference materials for a wide range of application fields. With the development of new analytical methods and new applications as well as continuously emerging more stringent requirements of laboratory accreditation with regard to quality control and metrological traceability, the demand and requirements for reference materials are increasing. This trend article gives an overview of general developments in the field of reference materials as well as developments in selected fields of application in which BAM is active. This includes inorganic and metal analysis, gas analysis, food and consumer products, and geological samples. In addition to these more traditional fields of application, developments in the areas of optical spectroscopy, particulary fluorescence methods, and nanomaterials are considered.
The bipartite interactions between insect hosts and their bacterial gut microbiota, or their bacterial pathogens, are empirically and theoretically well-explored. However, direct, and indirect tripartite interactions will also likely occur inside a host. These interactions will almost certainly affect the trajectory of pathogen virulence evolution, an area that is currently under researched. The interactions within tripartite associations can be competitive, that is, exploitative-competition, interference-competition or apparent-competition. Competitive interactions will be significantly influenced by non-competitive effects, for example, immunopathology, immunosuppression, and microbiota-mediated tolerance. Considering a combination of these interactions and effects, will enable an increased understanding of the evolution of pathogen virulence. This new perspective allows us to identify several novel research questions, which we hope will be a useful framework for future research.
Tuschenanalyse im P 11702
(2021)
Near-inframed reflectography and imaging X-Ray flourescence analysis reveal that carbon inks of two different compositions were used in the papyrus manuscript Berlin P 11702. in contrast with the writing ink, one of the carbon drawing inks contained a significant addition of iron. This result emphasises the need for routine instrumental ink analysis.
Two new approaches towards an emission reference material for use in quality assurance measures for materials emissions testing were developed and intensively tested. The overall goal was to obtain solid materials with homogenous and reproducible (S)VOC release. Since the application in inter-laboratory comparisons is aimed at, it should furthermore be long-term stable to ensure safe shipment to the customer without sustaining compound losses. In the first approach, thermoplastic polyurethane (TPU) was impregnated with the VOC texanol under high-pressure with liquid CO2 as solvent. In the second, styrene (VOC) and the SVOC 2,6-diisopropylnaphthalene (DIPN) were spiked into vacuum grease (VG) and a mixture of paraf-fin/squalane (P/S). For the prediction of the emission rates a finite element model (FEM) was developed for the VG and P/S type materials. All requirements for reference materials were fulfilled, whereas the TPU samples need to be aged for about 10 days until repeatable and reproducible emission rates were obtained.
Two new approaches towards an emission reference material for use in quality assurance measures for materials emissions testing were developed and intensively tested. The overall goal was to obtain solid materials with homogenous and reproducible (S)VOC release. Since the application in inter-laboratory comparisons is aimed at, it should furthermore be long-term stable to ensure safe shipment to the customer without sustaining compound losses. In the first approach, thermoplastic polyurethane (TPU) was impregnated with the VOC texanol under high-pressure with liquid CO2 as solvent. In the second, styrene (VOC) and the SVOC 2,6-diisopropylnaphthalene (DIPN) were spiked into vacuum grease (VG) and a mixture of paraf-fin/squalane (P/S). For the prediction of the emission rates a finite element model (FEM) was developed for the VG and P/S type materials. All requirements for reference materials were fulfilled, whereas the TPU samples need to be aged for about 10 days until repeatable and re-producible emission rates were obtained.
Drei grundlegend verschiedene Ansätze für Umweltsimulation werden an Beispielen illustriert:
(i) Ganzheitlicher Ansatz - Nachstellen von Umweltmilieus im Labor
Ziel ist hier das Nachstellen von (kombinierten) Umweltbedingungen im Labor; die Umweltparameter werden mit all ihren Wechselwirkungen aufgebracht.
Hauptnutzen ist eine gegenüber der natürlichen Beanspruchung erhöhte Reproduzierbarkeit der Umweltbedingungen. Hat man sein Laborsetup entwickelt, ist es auf verschiedene Materialien anwendbar.
Unter solchen Laborbedingungen ermittelte Lebensdauern sind dabei nicht auf die typischerweise sehr variablen Real-Umweltbedingungen übertragbar.
(ii) Parametrisierter Ansatz - Ermittlung einzelner Materialempfindlichkeiten
Hierbei werden im Labor die Wirkungen separater Umweltparameter auf Materialien nachgestellt. Für eine solche Separation der Einflussfaktoren ist insbesondere die Aufschlüsselung möglicher Wechselwirkungen der Umwelt-parameter (z.B. Mikroklima an bestrahlten Oberflächen) erforderlich. Einzelne (meist Alterungs-) Empfindlichkeiten können qualitativ nachgewiesen werden oder sogar – als Beanspruchungs-Wirkungs-Funktionen – quantifiziert werden, was einen wesentlichen Schritt in Richtung der Digitalisierung der Material¬prüfung darstellt. Insbesondere ist dann auch eine Lebensdauer-vorhersage für vorgegebene Zeitreihen der Beanspruchungs¬parameter umsetzbar.
(iii) Rückwirkungen auf die Umwelt
Umweltbeanspruchungen können zur Freisetzung von Schadstoffen in die Umwelt führen. Durch die Nachstellung kritischer, aber realitätsnaher Einsatzszenarien kann die Menge an freigesetzten Substanzen abgeschätzt werden.
Egal, welcher Ansatz verfolgt wird – ein Vergleich mit der oder einer Real-beanspruchung ist unerlässlich, ebenso wie die Messdatenaufzeichnung (data logging) aller potenziell relevanten Beanspruchungsparameter während dieser Realbeanspruchung.
Obwohl die naturnahe Umwelt – sowohl in der BAM als auch bei der GUS – gegenüber der technischen Umwelt eher untergeordnet auftritt, werden zur Illustration Beispiele aus der naturnahen Umwelt verwendet.
The leaching behavior of scandium (Sc) from bauxite residues can differ significantly when residues of different geological backgrounds are compared. The mineralogy of the source rock and the physicochemical environment during bauxitization affect the association of Sc in the bauxite i.e., how Sc is distributed amongst different mineral phases and whether it is incorporated in and/or adsorbed onto those phases. The Sc association in the bauxite is in turn crucial for the resulting Sc association in the bauxite residue. In this study systematic leaching experiments were performed on three different bauxite residues using a statistical design of experiments approach. The three bauxite residues compared originated from processing of lateritic and karstic bauxites from
Germany, Hungary, and Russia. The recovery of Sc and Fe was determined by ICP-OES measurements. Mineralogical changes were analyzed by X-ray-diffraction and subsequent Rietveld refinement. The effects of various parameters including temperature, acid type, acid concentration, liquid-to-solid ratio and residence time were studied. A response surface model was calculated for the selected case of citric acid leaching of Hungarian bauxite residue. The investigations showed that the type of bauxite residue has a strong influence. The easily leachable fraction of Sc can vary considerably between the types, reaching ~20–25% in German Bauxite residue and ~50% in Russian bauxite residue. Mineralogical investigations revealed that a major part of this fraction was released from secondary phases such as cancrinite and katoite formed during Bayer processing of the bauxite.
The effect of temperature on Sc and Fe recovery is strong especially when citric acid is used. Based on the exponential relationship between temperature and Fe-recovery it was found to be particularly important for the selectivity of Sc over Fe. Optimization of the model for a maximum Sc recovery combined with a minimum Fe
recovery yielded results of ~28% Sc recovery at <2% Fe recovery at a temperature of 60 ◦C, a citric acid normality of 1.8, and a liquid-to-solid ratio of 16 ml/g. Our study has shown that detailed knowledge about the Sc association and distribution in bauxite and bauxite residue is key to an efficient and selective leaching of Sc
from bauxite residues.
Understanding Stimulation of Conjugal Gene Transfer by Nonantibiotic Compounds: How Far Are We?
(2024)
A myriad of nonantibiotic compounds is released into the environment, some of which may contribute to the dissemination of antimicrobial resistance by stimulating conjugation. Here, we analyzed a collection of studies to (i) identify patterns of transfer stimulation across groups and concentrations of chemicals, (ii) evaluate the strength of evidence for the proposed mechanisms behind conjugal stimulation, and (iii) examine the plausibility of alternative mechanisms. We show that stimulatory nonantibiotic compounds act at concentrations from 1/1000 to 1/10 of the minimal inhibitory concentration for the donor strain but that stimulation is always modest (less than 8-fold). The main proposed mechanisms for stimulation via the reactive oxygen species/SOS cascade and/or an increase in cell membrane permeability are not unequivocally supported by the literature. However, we identify the reactive oxygen species/SOS cascade as the most likely mechanism. This remains to be confirmed by firm molecular evidence. Such evidence and more standardized and high-throughput conjugation assays are needed to create technologies and solutions to limit the stimulation of conjugal gene transfer and contribute to mitigating global antibiotic resistance.
Cryomyces antarcticus – a cryptoendolithic black fungus endemic to Antarctica – is taxonomically classified in phylum Ascomycota, class Dothideomycetes incertae sedis. C. antarcticus has shown high capability to survive extreme environmental conditions like those found in space (ionizing radiation, vacuum, microgravity), thus fueling fundamental astrobiological questions like “searching for life beyond Earth” (Onofri et al. 2020, Extremophiles Astrobiol Model). Its extraordinary resilience has been attributed to the presence of thick, highly melanized cell walls, which may contain both DHN and DOPA melanins (Pacelli et al. 2020, Appl Microbiol Biotechnol). To better understand the contribution of DHN melanin to the overall resilience of C. antarcticus, we initially adopted chemicals e.g., tricyclazole to inhibit the DHN melanin synthetic pathway; however, these studies gave inconclusive results. Eventually, we decided to generate melanin-deficient mutants by genetic engineering. Using the genetic toolkit developed for the black fungus Knufia petricola (Voigt et al. 2020, Sci Rep; Erdmann et al. 2022, Front Fungal Biol), we designed a strategy for mutating the key enzyme (polyketide synthase)-encoding gene capks1 by transient delivery of Cas9 and capks1-specific sgRNA from AMA-containing plasmids and PCR-generated donor DNA i.e., resistance cassettes flanked by ~75-bp-long sequences homologous to capks1. For this, the melanin-PKS encoding ortholog was identified in the C. antarcticus CBS 116301 genome (mycocosm.jgi.doe.gov) and used to design primers for re-sequencing of the capks1 locus in the strain CCFEE 515. Transformation of C. antarcticus is challenging because of its very slow growth; we expect that 4-6 months are needed from obtaining enough biomass for cell wall lysis until transferring putatively resistant transformants for genotyping. Important parameters were evaluated: protoplasts can be generated, and they survive the transformation procedure, and suitable concentrations of selective agents have been identified. Nowadays, we are waiting for the first C. antarcticus mutants considered to be deficient in DHN melanogenesis.
While studying the socio-geographic history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink and a subsequent in-depth analysis using several spectroscopic techniques: XRF, FTIR, and Raman. In most cases, we can obtain satisfactory results using a non-invasive protocol. However, mixed inks that contain no metals evade such a protocol. These inks constitute a heterogeneous group of media used especially in the Middle East and the Islamicate world since at least the 10th century; they are characterized by blending carbon ink and tannins, with or without the addition of vitriol.
Our own research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo). During many years of study, we concluded that the continuous production of Coptic manuscripts from late Antiquity to the Middle Ages offers a unique opportunity for historical study of the ink in a large geographic area. Thanks to the collaboration with the ERC project “PAThs” (www.paths.uniroma1.it), based at the University of Rome La Sapienza, and within the activities of a PhD research dedicated to this topic, we therefore created a new branch of our project focused entirely on the analysis of Coptic inks, pigments, and dyes. This pioneering systematic study of writing materials coming from a specific area and time frame (5th-10th century) aims not only at a better understanding of the complex Coptic multicultural and plurilingual society, but also and mainly at clarifying the links among the Coptic and other societies between the ancient and medieval eras. Finally, it will cast light on the history of the technological development of inks in the eastern world, from Antiquity to the middle ages.
Gemeiner Nagekäfer und Kleidermotte sind unerwünscht im Museum. Kulturgüter mit Anteilen von Holz, Federn, Wolle, Haare, etc. wie ethnologische oder naturkundliche Sammlungsstücke, aber auch Bilderahmen oder Freilichtmuseen werden von ihnen gerne besucht. Dabei sind es die Jugendstadien (Larven) dieser Insekten, die sich von ungeschützten Exponaten oder Depotstücken, die diese natürlichen Materialien enthalten, ernähren. Die Entwicklung der Larven findet verborgen im Inneren der Materialien statt. Die geflügelten erwachsenen Formen, die sich im freien Raum bewegen, sich fortpflanzen und den Neubefall herbeiführen, treten saisonal sehr begrenzt auf. Eine frühzeitige Detektion der Schädlinge, als erwachsenes Insekt oder als Larve, ist dadurch erschwert. Es gilt folglich deren Präsenz und erste Anzeichen eines Befalls zuverlässig und vor allem frühzeitig feststellen zu können, um geeignete Maßnahmen zum Schutz des Kulturgutes einzuleiten.
Neben dem Wissen um die Materialeigenschaften des Kulturgutes sind umfängliche Kenntnis über die Biologie der Schädlinge, zu ihren grundsätzlichen Lebensansprüchen und insbesondere zum Verhalten, das zum Neubefall führt, wichtig. Die Larvenstadien von Holz- und Textilschädlingen zeichnen sich durch hohe Toleranzen gegenüber extremen Temperaturen und Luftfeuchten aus. Für sie ungünstige Bedingungen können sie sehr lange in Ruhephasen überdauern. Nicht erkannter, versteckter Befall von Materialien sind häufige Infektionsquellen für Neubefall von Sammlungen. Verborgene natürliche Befallsquellen im eigenen Museumssystem spielen bei Neubefall von Exponaten eine größere Rolle als der Zuflug von Schadinsekten aus Reservoiren von außen.
Der Vortrag stellt beispielhaft Lebenszyklen relevanter Schädlingsarten vor und zeigt Möglichkeiten gezielter Interventionen auf, die in ein IPM Konzept einfließen können. Dies umfasst vorbeugende Maßnahmen wie geeignetes Klima in Ausstellungs- und Lagerräumen, das sogenannte Monitorring sowie eine konsequente Quarantäne bis hin zu physikalischen, biologischen oder chemischen Bekämpfungsmaßnahmen.
Uninvited and Welcomed Guests in Museums – Biological management of
clothes moths and woodworms
(2019)
In museums and historic houses clothes, moths (Tineola bisselliella, Tinea pellionella) and the furniture beetle (Anobium punctatum) are the most economically important pests on textiles or wooden artifacts, respectively. Their management is essential to protect cultural ethnological heritage and natural history collections for future generations.
Pest management strategies have changed over time. Today, intensive knowledge on pest biology and overall material science are key cornerstones in IPM concepts - also for the museum environment. The important first steps for sustainable pest management are risk assessment, early pest detection and identification of pathways of infestation. These steps are followed by physical and biological means of control, which have lately gained more importance than applying biocides.
Several potentially effective biological enemies of clothes moths and woodworm have been known for a long time, but their promotion for pest control in museums and historic houses is just beginning.
This short review summarizes current concepts of pest life cycle interruption by applying good quarantine and very specific biological measures. The lessons learned from recent faunistic surveys, life-history studies as well as behavioral observations of parasitoids and predators of clothes moths and woodworm may supplement the pest management tool box. The need for further research in this field is addressed.
Uninvited and welcomed guests in museums – biological management of clothes moths and woodworms
(2020)
In museums and historic houses clothes, moths (Tineola bisselliella, Tinea pellionella) and the furniture beetle (Anobium punctatum) are the most economically important pests on textiles or wooden artifacts, respectively. Their management is essential to protect cultural ethnological heritage and natural history collections for future generations.
Pest management strategies have changed over time. Today, intensive knowledge on pest biology and overall material science are key cornerstones in IPM concepts - also for the Museum environment. The important first steps for sustainable pest management are risk assessment, early pest detection and identification of pathways of infestation. These steps are followed by physical and biological means of control, which have lately gained more importance than applying biocides. Several potentially effective biological enemies of clothes moths and woodworm have been known for a long time, but their promotion for pest control in Museums and historic houses is just beginning.
This short review summarizes current concepts of pest life cycle interruption by applying good quarantine and very specific biological measures. The lessons learned from recent faunistic surveys, life-history studies as well as behavioral observations of parasitoids and predators of clothes moths and woodworm may supplement the pest management tool box. The need for further research in this field is addressed.
In der Berliner Sammlung "Manuscripta Americana" befinden sich Fragmente von Bilderhandschriften, die Alexander von Humboldt 1804 in Mexiko erwarb und der Königlichen Bibliothek schenkte. Die in der frühen Kolonialzeit hergestellten verschiedenartigen Codices waren damals schon nicht mehr an den Orten ihrer ursprünglichen Verwendung. Entsprechend ihres Seltenheitswertes gelangten einzelne Schriftstücke seit der Conquista in die Bestände bedeutender Persönlichkeiten. Hierzu fertigte man auch Abschriften oder Kopien an, oder zerstückelte sogar einzelne Blätter, so dass die Darstellungen auf den abgetrennten Fragmenten oft nur zum Teil abgebildet vorliegen.
Um herauszufinden, ob einige Schriftstücke der "Humboldt Codices" in Bezug zu einander stehen, werden die Dokumente, ihre Symbole und Schriftzeichen und das zur Herstellung verwendete Material miteinander verglichen.
Mit den für die Analyse von Manuskripten bewährten Untersuchungsmethoden werden Papier und Farbmittel identifiziert. Hierzu zählen Raman-, FTIR-, Röntgenfluoreszenz- und VIS- Spektroskopie. Charakteristisch für die Herstellung von schriftlichen Dokumenten in der Kolonialzeit von Amerika ist die Verwendung von indigenem Material wie Papier aus Baumrinde und Pflanzenfarben zusammen mit den aus Europa bekannten Materialien. Geklärt wird, inwieweit neben den bekanntesten Farbstoffen wie Cochenille, Mayablau oder Mischungen mit Tonmineralen auch mineralische Pigmente zum Einsatz kamen.
Vorgestellt werden die auf Tafel 36 in den "Vues des Cordillères et Monuments des Peuples Indigènes de l`Amerique, Voyage de Humboldt et Bonpland" abgebildeten Fragmente. Die hier von Humboldt vorgenommene Zusammenstellung wird mit der Farbpalette der in Berlin archivierten originalen Schriftstücke verglichen. Die Interpretation der Ergebnisse gibt einen Hinweis auf die Zuordnung oder auch Zusammengehörigkeit dieser einzigartigen Dokumente amerikanischer Geschichte. Hierbei wird die Frage aufgeworfen, inwiefern davon auszugehen ist, dass diese mit weiteren Fragmenten in Verbindung gebracht werden können, was für die Beleuchtung der kulturhistorischen Zusammenhänge von großer Bedeutung ist.
Im Beitrag wurden erste Ergebnisse eines laufenden UFOPLAN-Vorhabens zu den neuen Kriterien der Verwertungsmöglichkeiten von Bodenmaterialien außerhalb der durchwurzelbaren Bodenschicht nach den §§ 6 bis 8 der Novelle der BBodSchV vorgestellt. Der Schwerpunkt lag auf Untersuchungen der Schadstoffgruppe der PAK. Dabei wurden Probleme der Vergleichbarkeit und Leistungsfähigkeit verschiedener Elutions- und Analyseverfahren der PAK-Analytik diskutiert.
Im Januar 2018 wurde die DIN EN 16516 „Bauprodukte: Bewertung der Freisetzung gefährlicher Stoffe – Bestimmung von Emissionen in die Innenraumluft“ als harmonisierte europäische Prüfnorm veröffentlicht. Für die Etablierung der DIN EN 16516 als neue Referenznorm wurden verschiedene Emissionsprüfungen mit dem Ziel durchgeführt, ein neues Prüfverfahren für Formaldehydemissionen aus Holzwerkstoffen zu erarbeiten. Das übergeordnete Ziel ist die Minimierung des Risikos von Überschreitungen des Innenraumrichtwertes für Formaldehyd. Die Untersuchungen ergaben teilweise hohe Formaldehydemissionen, insbesondere bei höheren Beladungsfaktoren und Temperaturen, sowie bei niedrigen Luftwechselraten. Eine getestete Spanplatte hätte aufgrund ihrer hohen Formaldehydemission nicht auf den deutschen Markt gebracht werden dürfen. Durch vergleichende Untersuchungen konnte ein Umrechnungsfaktor in Höhe von 2,0 für die Umrechnung von Prüfwerten nach DIN EN 717-1 zu DIN EN 16516 abgeleitet werden.
Uranium and thorium species in phosphate rock and sewage sludge ash based phosphorus fertilizers
(2020)
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.
More sustainable waste management practices are an important element in the Transformation towards a circular economy (CE). Activities in this area should be dedicated to all groups of waste, including those generated in the water and sewage sector. This paper presents the characteristics of sewage sludge ash (SSA) coming from Polish municipal waste incineration plants. Due to the high content of nutrients such as phosphorus (8.01% P2O5), calcium (5.11% CaO) and magnesium (2.75% MgO), the analyzed SSA may constitute a valuable source of raw materials for the fertilizer industry.
Despite the good fertilizing properties of the SSA, in some cases the presence of heavy metals such as cadmium (0.74–1.4 mg/kg dry matter), lead (49.8–99 mg/kg dry matter), mercury (3.93 mg/kg dry matter) and arsenic (4.23–4.43 mg/kg dry matter) and poor bioavailability of P from SSA disqualifies this waste from direct use as a fertilizer. Therefore, it is necessary to look for methods that will allow the municipal SSA to be processed, for example, technologies for the extraction of phosphorus and the production of phosphate fertilizer. This way of SSA management is in the line with the CE assumptions, in which waste becomes a valuable source of secondary raw materials. Fertilizer produced from waste meeting quality, safety and labelling requirements and limits of organic, microbiological and physical contaminants will be able to be traded freely within the European Union (EU) and receive the CE marking. The idea of use of SSA for fertilizer purposes is consistent not only with the objectives of the CE but also with the Polish National Waste Management Plan 2022 and the Municipal Sewage Sludge Strategy 2019–2022, which emphasizes the necessity to maximize the use of biogenic substances contained in wastewater. Therefore, sustainable management of SSA, in particular its storage in a way enabling the recovery of phosphorus, should be promoted.