4 Material und Umwelt
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- 4 Material und Umwelt (136)
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8. Netzwerktreffen PerFluSan
(2020)
Terrestrial mud volcanoes are unique structures driven by tectonic pressure and fluids from the deep subsurface. These structures are mainly found in active tectonic zones, such as the area near the Los Bajos Fault in Trinidad. Here we report a chemical and microbiological characterization of three mud volcanoes, which included analyses of multiple liquid and solid samples from the mud volcanoes. Our study confirms previous suggestions that at least some of the mud volcano fluids are a mixture of deeper salt-rich water and surficial/precipitation water. No apparent water quality differences were found between sampling sites north and south of a major geological fault line. Microbiological analyses revealed diverse communities, both aerobic and anaerobic, including sulfate reducers, methanogens, carbon dioxide fixing and denitrifying bacteria. Several identified species were halophilic and likely derived from the deeper salt-rich subsurface water, while we also cultivated pathogenic species from the Vibrionaceae, Enterobacteriaceae, Shewanellaceae, and Clostridiaceae. These microorganisms were likely introduced into the mud volcano fluids both from surface water or shallow ground-water, and perhaps to a more minor degree by rain water. The identified pathogens are a major health concern that needs to be addressed.
A genetic toolbox for exploring the life style of the rock-inhabiting black fungus Knufia petricola
(2020)
After their discovery on rock surfaces in cold and hot deserts, a polyphyletic group of ascomycetous black fungi was found to dominate a range of hostile environments – natural and man-made, from salterns to dishwashers, roofs and solar panels. Together with bacteria and algae they may establish subaerial biofilms and cause weathering of the surfaces they grow on. Their impressive survival abilities as well as their constitutive protective pigmentation and cluster-like microcolony organisation are similar in environmental isolates as well as in heat-tolerant opportunistic pathogens of animals and humans. The exact genetic properties that ensure their survival in extreme environments can be studied if some black fungi were amenable to genetic manipulations. We selected the rock-inhabiting fungus Knufia petricola (class Eurotiomycetes, order Chaetothyriales) that grows moderately in axenic culture and exhibits all the characteristics of microcolonial black fungi such as yeast-like cell growth, absence of reproductive structures and constitutive dihydroxynaphthalene (DHN) melanogenesis (Nai et al. 2013, Fungal Genet Biol). We developed protocols to efficiently generate and transform protoplasts resulting in stable homokaryotic transformants by targeting genes involved in pigment synthesis and expressing fluorescent reporter genes. Hence, endogenous and foreign genes can be expressed from episomal AMA1-containing plasmids and genome-integrated DNA constructs. Moderate rates of homologous recombination allow for both ectopic and targeted integrations. CRISPR-Cas9 was further validated as a strategy for obtaining selection marker-free mutants and silencing via RNA interference as an approach to study essential genes. Availability of this genetic toolbox and an annotated genome sequence of the strain A95 is paving the way for studying interactions of K. petricola with environmental stressors, material surfaces, soil matrices and phototrophic symbionts.
Es wird über aktuelle Arbeitsthemen und Entwicklungen im Fachbeirat berichtet. So wurde in einer Sondersitzung des Fachbeirats über die Entlassung aus der Nachsorgephase beim Einsatz von Geokunststoffprodukten in Böschungen diskutiert. Die Unterarbeitsgruppe Fremdüberwachung in der Produktion hat getagt. Darüber hinaus werden Änderungen in den Zulassungsrichtlinien für Kunststoffdichtungsbahnen, Kunststoff-Dränelemente und für die Fremdüberwachung kurz vorgestellt.
Es wird über aktuelle Arbeitsthemen und Entwicklungen im Fachbeirat berichtet. So wurde in einer Sondersitzung des Fachbeirats über die Entlassung aus der Nachsorgephase beim Einsatz von Geokunststoffprodukten in Böschungen diskutiert. Die Unterarbeitsgruppe Fremdüberwachung in der Produktion hat getagt. Darüber hinaus werden Änderungen in den Zulassungsrichtlinien für Kunststoffdichtungsbahnen, Kunststoff-Dränelemente und für die Fremdüberwachung kurz vorgestellt.
Microcolonial black fungi are a group of ascomycetes that exhibit high stress tolerance, yeast-like growth and constitutive melanin formation. They dominate a range of hostile natural and man-made environments, from desert rocks and salterns to dishwashers, roofs and solar panels. Due to their slow growth and a lack of genetic tools, the underlying mechanisms of black fungi’s phenotypic traits have remained largely unexplored. We chose to address this gap by genetically engineering the rock-inhabiting fungus Knufia petricola (Eurotiomycetes, Chaetothyriales), a species that exhibits all characteristics of black fungi. A cell biological approach was taken by generating K. petricola strains expressing green or red fluorescent protein variants. By applying: (1) traditional gene replacement; (2) gene editing and replacement via plasmid-based or ribonucleoprotein (RNP)-based CRISPR/Cas9, and (3) silencing by RNA interference (RNAi), we constructed mutants in the pathways leading to melanin, carotenoids, uracil and adenine. Stable single and double mutants were generated with homologous recombination (HR) rates up to 100%. Efficient, partially cloning-free strategies to mutate multiple
genes with or without resistance cassettes were developed. This state-of-the-art genetic toolkit, together with the annotated genome sequence of strain A95, firmly established K. petricola as a model for exploring microcolonial black fungi.
Pseudomonas aeruginosa MPAO1 is the parental strain of the widely utilized transposon mutant collection for this important clinical pathogen. Here, we validate a model system to identify genes involved in biofilm growth and biofilm-associated antibiotic resistance. Our model employs a genomics-driven workflow to assemble the complete MPAO1 genome, identify unique and conserved genes by comparative genomics with the PAO1 reference strain and genes missed within existing assemblies by proteogenomics. Among over 200 unique MPAO1 genes, we identified six general essential genes that were overlooked when mapping public Tn-seq data sets against PAO1, including an antitoxin. Genomic data were integrated with phenotypic data from an experimental workflow using a user-friendly, soft lithography-based microfluidic flow chamber for biofilm growth and a screen with the Tn-mutant library in microtiter plates. The screen identified hitherto unknown genes involved in biofilm growth and antibiotic resistance. Experiments conducted with the flow chamber across three laboratories delivered reproducible data on P. aeruginosa biofilms and validated the function of both known genes and genes identified in the Tn-mutant screens. Differential Protein abundance data from planktonic cells versus biofilm confirmed the upregulation of candidates known to affect biofilm formation, of structural and secreted proteins of type VI secretion systems, and provided proteogenomic evidence for some missed MPAO1 genes. This integrated, broadly applicable model promises to improve the mechanistic understanding of biofilm formation, antimicrobial tolerance, and resistance evolution in biofilms.
Popioły pochodzące z instalacji do spalania komunalnych osadów ściekowych, znajdującej się na terytorium Polski, poddano procesom termochemicznego przekształcania, dzięki czemu otrzymano produkty nawozowe spełniające kryteria dopuszczające je do obrotu jako nawozy mineralne. Ponadto dokonano analizy możliwości wykorzystania popiołów na cele nawozowe zgodnie z obecnie przyjętymi dokumentami strategicznymi i planistycznymi dotyczącymi gospodarki odpadami na poziomie krajowym i europejskim.
Biofilms cause complications and high costs in both industry and medicine. Of particular interest are bacterial infections of prosthetic materials, which usually cannot be eliminated due to the high antibiotic resistance known for bacteria forming biofilms. The search for new materials and coatings with lower colonization potential and antibacterial activity is of great importance to reduce biofilm formation. However, there is no standardized procedure to examine the colonization characteristics of bacteria in the Biofilm state in situ. Here, we describe an automated epifluorescence microscopy system for the semi-quantitative analysis of three-dimensional (3D) biofilms on various surfaces. To analyze adherent bacteria, three materials (glass, steel and titanium) were incubated with bacteria in a flow chamber system. After fluorescence staining of the bacteria, automated image capturing, quantification of the bacteria, measurement of the colonized area and determination of the 3D biofilm height were carried out by using novel software.
Furthermore, the materials were examined for their surface topography using white light scanning interferometry. Titanium compared to glass showed a significantly higher number of adherent bacteria.
We argue that this was due to the higher microroughness of titanium. The colonized area was in accordance with the number of adherent bacteria and was also significantly larger on titanium coupons compared to glass. Maximum 3D biofilm height on glass coupons was significantly lower compared to the ones on steel and titanium. This novel method enables the standardized, automated investigation of the colonization with bacteria on different materials. This approach can considerably support the characterization of new material surfaces and their innovative coatings by analyzing the amount of attached Bacteria and thickness of biofilms in situ and eliminates the need of conventional cultivation.
With the advent of widely accessible and cost-effective next-generation sequencing technologies, it has become increasingly feasible to study insect immunity on a deep genomic or transcriptomic level. Here we introduce a protocol that is aimed at exploiting transcriptomic data to study immunity in non-model insect organisms. We provide instructions for an entire workflow, starting with successfiil extraction of insect RNA through to bioinformatic guidelines for the effective analysis of mRNA sequencing data. The RNA extraction procedure is based on TRIzol Reagent and a spin-column clean-up Step. The bioinformatic pipeline is intended to help users identify immune genes from de novo transcriptome data and includes guidelines for conducting differential gene expression analyses on transcriptomic data. The immune gene prediction method is based on inferring protein homologs with HMMERand Blastp and talces Advantage ofthe ImmunoDB database, which is a valuable resource for research on insect immune-related genes and gene families. The differential gene expression analysis procedure utilizes the DESeq2 package as implemented in R. We hope this protocol will serve as a usefi.il resource for researchers aiming to study immunity in non-model insect species.
Salt tolerance in the γ-proteobacterium Halomonas elongata is linked to its ability to produce the compatible solute ectoine. The metabolism of ectoine production is of great interest since it can shed light on the biochemical basis of halotolerance as well as pave the way for the improvement of the biotechnological production of such compatible solute. Ectoine belongs to the biosynthetic family of aspartate-derived amino-acids. Aspartate is formed from oxaloacetate, thereby connecting ectoine production to the anaplerotic reactions that refill carbon into the tricarboxylic acid cycle (TCA cycle). This places a high demand on these reactions and creates the need to regulate them not only in response to growth but also in response to extracellular salt concentration. In this work, we combine modeling and experiments to analyze how these different needs shape the anaplerotic reactions in H. elongata. First, the stoichiometric and thermodynamic factors that condition the flux distributions are analyzed, then the optimal patterns of operation for oxaloacetate production are calculated. Finally, the phenotype of two deletion mutants lacking potentially relevant anaplerotic enzymes: phosphoenolpyruvate carboxylase (Ppc) and oxaloacetate decarboxylase (Oad) are experimentally characterized. The results show that the anaplerotic reactions in H. elongata are indeed subject to evolutionary pressures that differ from those faced by other gram-negative bacteria. Ectoine producing halophiles must meet a higher metabolic demand for oxaloacetate and the reliance of many marine bacteria on the Entner-Doudoroff pathway compromises the anaplerotic efficiency of Ppc, which is usually one of the main enzymes fulfilling this role. The anaplerotic flux in H. elongata is contributed not only by Ppc but also by Oad, an enzyme that has not yet been shown to play this role in vivo. Ppc is necessary for H. elongata to grow normally at low salt concentrations but it is not required to achieve near maximal growth rates as long as there is a steep sodium gradient. On the other hand, the lack of Oad presents serious difficulties to grow at high salt concentrations. This points to a shared role of these two enzymes in guaranteeing the supply of oxaloacetate for biosynthetic reactions.
New antibacterial agents are urgently required to fight the emergence of antibiotic-resistant bacteria. We recently synthesized the first thioimidazolium ionene, which has antibacterial properties and can degrade in various media. This dual functionality is crucial in order to limit the environmental impact of these biocides. We have found that our polymer is stronger than benzalkonium chloride (BAC) against Pseudomonas aeruginosa and also readily degrades in the presence of base, while remaining stable in acidic environments. These results highlight a new emerging class of antibacterial degradable polymers.
Biocides are in contact with soils through direct application and passive leaching from protected materials. Consequently, soil microorganisms are exposed to biocides even though they are not their primary targets. Soil is a large reservoir of microbial diversity and has been hypothesized to be a crucial factor for the evolution and spread of antimicrobial resistance.
Currently, there is little knowledge on how biocides used to protect materials affect the evolution and spread of resistance. Thus, our aim is to investigate the risk for the evolution of biocide resistance and cross-resistance to antibiotics. In addition, we aim to elucidate the affect of biocides on the spread of resistance via horizontal gene transfer (HGT).
In adaptive laboratory evolution experiments we cultured selected model soil microorganism with representative biocides under selection regimes with increasing and stable biocide concentrations followed by antibiotic and biocide cross-resistance determination. Moreover, we investigate if the selected biocides affect the rates of de novo mutations and HGT of plasmids that carry resistance genes among soil microorganism.
Our results show only small increases of biocide resistance during serial transfers under increasing biocide concentrations. One reason for this might be the narrow selective window for biocide resistance due to steep dose-response relationships. Furthermore, our results indicate that a stable low-level biocide regime did not select for high level cross-resistance to antibiotics and other biocides.
Moreover, material preservatives affected the rates of HGT via conjugation and the mutation rates at sub-inhibitory concentrations. The results will enable future risk assessment regarding resistance evolution for biocides used as material preservatives.
Antimony in incineration bottom ash – Leaching behavior and conclusions for treatment processes
(2020)
Antimony (Sb) is used in industrial products mainly as flame retardant in plastic material. Due to such additives in plastics, about a half of Sb ends up in municipal solid waste incineration at the end-of-life and consequently in relevant amounts in the generated bottom ash. In contact with water, the initial leachability is low, as antimonates form sparingly soluble compounds with Ca2+. Following the carbonation of the incineration bottom ash (IBA) during the proceeding ageing the pH in the leachates decreases. With decreasing concentration of Ca in the eluate the solution equilibrium changes and antimonates dissolve. In Germany it is intended to regulate Sb in IBA with the planned implementation of the so called Mantelverordnung (MantelVO, containing provisions on the utilisation of mineral waste) in the near future. The limit values set in the draft might be critical for IBA and therefore pose a risk for the utilisation of the mineral fraction of IBA in the well-established recycling routes.
The application of fracture mechanics to the determination of the fatigue behavior of weldments is discussed with the focus on classic fatigue, i.e., the overall fatigue life and the fatigue strength in terms of an S-N curve and the endurance limit. The following issues are addressed: specific features of short fatigue crack propagation, an adequate initial crack size, multiple crack propagation and its statistical treatment as well as welding residual stresses. As an example, an approach of the authors is applied to the determination of FAT classes for a butt weld with varying weld toe geometry.
In the last decade, applications of X-rays to the study of manuscripts significantly spread in both diversity and extent. They range from writing material analysis, mostly with X-ray fluorescence (XRF), permitting non-invasive characterization of inks and pigments used, to the investigation of the origin of writing supports. In addition, XRF mapping has proved to be an invaluable tool for recovering erased text. Finally, computed-tomography (CT) has shown potential in virtually unrolling rolls, making text readable without using-damaging mechanical methods. Despite their growing use, little attention has been paid to the side effects of such analytical tools. We observed irreversible parchment colour changes during some experiments on dead-sea scrolls with synchrotron radiation sources. Furthermore, partial photo-reduction of iron under high intensity beam during X-ray absorption near edge structure spectroscopy (XANES) measurements of iron-gall ink on paper has been reported several times [5,6]. Such phenomena have mostly been overlooked so far, although there is an increasing awareness of the necessity to study them. We conducted experiments at the Deutsches Elektronen-Synchrotron (DESY) facilities to investigate X-ray induced structural alteration of paper and parchment to see whether the presence of absorption centres (ink and pigments) has an impact. In addition to better understanding degradation processes, we are aiming to define an appropriate methodology of analysis of manuscripts with a tolerable risk of damage. The first results concerning X-ray induced damage of cellulose materials have already been presented at the Synchrotron Radiation and Neutrons in Art and Archaeology (SR2A). We are focusing here on the results on parchment materials.
In 2018, the production of Municipal SolidWaste (MSW) in EU-28 reached 250.6 Mt, with the adoption of different management strategies, involving recycling (48 wt %), incineration and thermal valorization (29 wt %) and landfilling (23 wt %). This work was based on the analysis of the baseline situation of MSW management in EU-28 in 2018, considering its progress in 2008–2018, and discussed the possible improvement perspectives based on a framework involving incineration and recycling as the only possible alternatives, specifically evaluating the capability of already-existing incineration plants to fulfill the EU needs in the proposed framework. The results of the assessment showed two main crucial issues that could play a pivotal role in the achievement of Circular Economy action plan targets: the need to increase the recycling quotas for specific MSW fractions through the separate collection, and therefore the improvement of definite treatment process chains; the optimization of the recovery of secondary raw materials from incineration bottom ash, involving the Recycling of ferrous and nonferrous metals and the mineral fraction. Both issues need to find an extensive application across all member states to decrease the actual differences in the adoption of sustainable MSW management options.
Biofilm formation in industrial or medical settings is usually unwanted and leads to serious health problems and high costs. Inhibition of initial bacterial adhesion prevents biofilm formation and is, therefore, a major mechanism of antimicrobial action of surfaces. Surface topography largely influences the interaction between bacteria and surfaces which makes topography an ideal base for antifouling strategies and eco-friendly alternatives to chemical surface modifications. Femtosecond laser-processing was used to fabricate sub-micrometric surface structures on silicon and stainless steel for the development of antifouling topographies on technical materials.
The Montserrat Codex Miscellaneus (TM 59453/LDAB 552) has been the subject of numerous studies since the publication of ist first text by its owner, father Ramon Roca-Puig. Scholars have dealt with the content of its texts, as well as interrogated its origin and materiality. It is a fourth-century papyrus single quire codex, which contains texts in both Latin and Greek. It has been argued that it belonged to the Bodmer library, connected to a Pachomian library in the Thebaid. In this paper we want to contribute to the material study of the codex by presenting the first results of an archaeometric analysis performed upon the inks. The Analysis was carried out within the framework of the ‘PAThs’ project based at Sapienza University of Rome, and executed with the close cooperation of DVCTVS, a team of scholars who curate the Roca-Puig collection. The results obtained have not only cast light on the history of production of the codex, but also, and perhaps most importantly, point out that a meaningful interpretation of the analytical data is only possible through an interdisciplinary collaboration between the humanities and the natural sciences.
The growth rate of single bacterial cells is continuously disturbed by random fluctuations in biosynthesis rates and by deterministic cell-cycle events, such as division, genome duplication, and septum formation.
It is not understood whether, and how, bacteria reject these growth-rate disturbances. Here, we quantified growth and constitutive protein expression dynamics of single Bacillus subtilis cells as a function of cell-cycle progression. We found that, even though growth at the population level is exponential, close inspection of the cell cycle of thousands of single Bacillus subtilis cells reveals systematic deviations from exponential growth.
Newborn cells display varying growth rates that depend on their size. When they divide, growth-rate Variation has decreased, and growth rates have become birth size independent. Thus, cells indeed compensate for growth-rate disturbances and achieve growth-rate homeostasis. Protein synthesis and growth of single cells displayed correlated, biphasic dynamics from cell birth to division. During a first phase of variable duration, the absolute rates were approximately constant and cells behaved as sizers. In the second phase, rates increased, and growth behavior exhibited characteristics of a timer strategy. These findings demonstrate that, just like size homeostasis, growth-rate homeostasis is an inherent property of single cells that is achieved by cell-cycle-dependent rate adjustments of biosynthesis and growth.
We present here our methodological approach applied to the study of Egyptian inks in Late Antiquity. It is based on an interdisciplinary strategy, bringing together a variety of disciplines from humanities and natural sciences, and it aims at systematically collecting a statistically relevant amount of data regarding the composition of the inks. The application of a wellestablished, non-invasive protocol that includes near-infrared imaging and X-ray fluorescence spectroscopy for in situ measurements enables the identification and characterisation of inks dating from the end of Late Antiquity onwards. However, sometimes this method limits our understanding when characterising more ancient inks. Trying to overcome these limitations, the potential of a new device for the characterisation of organic compounds is here explored by conducting preliminary tests on mock samples.
In this work, we present the results from 77 codicological units that include some of the earliest manuscripts of our corpus that presently lists 159 units.
The aim of the lecture is to present the productive interplay of connoisseurs and material analysis using the example of selected drawings from the Rembrandt collection of the Klassik Stiftung Weimar. We try to determine the point at which the question of the materiality of the drawings makes sense in the traditional discourse of connoisseurship. On the one hand, this involves the question of authorship – Rembrandt – or not? – and the locating of attributed drawings in the context of the work. On the other hand, it is about making drawing processes visible, characterizing ways of drawing and workshop practices as well as distinguishing different forms of reworking and copying within the Rembrandt workshop. The material analyses culminate in the question of whether Rembrandt’s inks can be distinguished at all.
It becomes apparent that the newly gained knowledge about the materiality of the drawing no longer reveals itself to the “mere” view of the connoisseur. Rather, it is only generated by the digital image. The rhetoric of connoisseurs must therefore be contrasted with the necessity of a hermeneutics of the digital image. The envisaged “material turn” of drawing science is thus simultaneously able to take up the critique of the question of authorship, which has been growing ever more recently, and to transfer it to a more comprehensive perspective of aesthetics of production.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray Absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr).
One of the key elements in the transformation towards a circular economy (CE) is providing more sustainable practices for resources and waste management. Improvement actions focused on transformation towards a CE should be targeted at all groups of materials and waste. As water is essential for human survival and well-being and plays a significant role in sustainable development (SD), the actions related to the reuse of water and the recovery of raw materials from wastewater and other water-based waste should be taken. The paper presents a proposition for a new CE model framework in the water and wastewater sector, which includes the six following actions: reduction—prevent wastewater generation in the first place by the reduction of water usage and pollution reduction at source; reclamation (removal)—an application of effective Technologies for the removal of pollutants from water and wastewater; reuse—reuse of wastewater as an alternative source of water supply (non-potable usage), recycling—recovery of water from wastewater for potable usage; recovery—recovery of resources such as nutrients and energy from water-based waste, and rethink—rethinking how to use resources to create a sustainable economy, which is `free` of waste and emissions. The novelty of the proposed CE model framework is that it presents possible ways of implementing CE principles in the water and wastewater sector, with a strong emphasis not only technological but also organisational and societal changes. Application of the proposed model may help to further transform the European economy to the CE model. Moreover, the indicated model can be significant tool supporting an assessment of local or regional progress towards CE in the water and wastewater sector and further environmental management and planning.
There are viral, fungal, bacterial and trypanosomal pathogens that negatively impact the individual and superorganismal health of the western honey bee. One fungal pathogen, Ascosphaera apis , affects larvae and causes the disease chalkbrood. A previous genome analysis of As. apis revealed that its genome encodes for RNA interference genes, similar to other fungi and eukaryotes. Here, we examined whether As. apis -targeting double-stranded RNA species could disrupt the germination of As. apis.
We observed that when spores were co-incubated with As. apis -targeting dsRNA, fewer spores were activated for germination, suggesting an uptake of exogenous genetic material at the very onset of germination and consequent damage to essential transcripts needed for germination. Overall, these results indicate that the causative agent of chalkbrood disease, As. apis , can be successfully targeted using an RNAi-based strategy.
Aluminum is an often-used building material in modern architecture. In recent years buildings from the 1950th and 1960th are increasingly subject of conservation works including the aluminum parts. Typical surface damages are signs of corrosion caused by weathering processes or scratches in the anodized layer due to extensive wear. To repair damaged aluminum surfaces, there are usually two options: smaller areas are repaired by using a touch-up pen, for larger damages it is necessary to remove the anodized layer completely. Both possibilities are disadvantageous for the objects; the touch-up pen often does not match the color together with an insufficient corrosion protection, while newly anodized layers often differ in color and gloss from the original surface.
For this reason, a research project was initiated to develop a mobile method to repair anodized aluminum parts. The first step focusses on the mobile anodization process by using the electrolyte with a gel substrate. Different cathodic materials are to be tested together with appropriate cooling material. The anodized area should be isolated to protect undamaged areas. Examinations of the produced layers are conducted by using Keyence microscope, eddy current testing and ESEM analysis. Further steps are to transform the coloring and sealing process for mobile application. Color could be applied by using a brush or by spray while the sealing process could be performed with water vapor. An heatable putty knife could be used, if heating up the area will be necessary. Once the application process is developed, the anodization will be tested on samples with artificial damages, fixed in horizontal and vertical positions. The stability of the anodized surface will be examined by accelerated ageing in a climate chamber and outdoor weathering.
The electrolyte (diluted sulfuric acid) was combined with a gel binder to enable a mobile application. Several thickening agents were tested concerning their conductivity and stability in acid systems. Anodization tests with different cathodic material and shapes were conducted. The temperature during anodization was controlled and adjusted if necessary. The anodized area was restricted by using either a lacquer, an adhesive or a removable silicon barrier. The fist results show the feasibility of the method on enclosed areas. The achieved thickness was measured by eddy current testing and the structure was controlled by ESEM analysis. The examinations show a connection between thickness and porosity of the anodized layers and the temperature during the application process.
Next steps are testing mobile coloring and sealing methods followed by mobile anodization on artificial damaged areas.
For osmoadaptation the halophilic bacterium Halomonas elongata synthesizes as its main compatible solute the aspartate derivative ectoine. H. elongata does not rely entirely on synthesis but can accumulate ectoine by uptake from the surrounding environment with the help of the osmoregulated transporter TeaABC. Disruption of the TeaABC-mediated ectoine uptake creates a strain that is constantly losing ectoine to the medium. However, the efflux mechanism of ectoine in H. elongata is not yet understood. H. elongata possesses four genes encoding mechanosensitive channels all of which belong to the small conductance type (MscS). Analysis by qRT-PCR revealed a reduction in transcription of the mscS genes with increasing salinity. The response of H. elongata to hypo- and hyperosmotic shock never resulted in up-regulation but rather in downregulation of mscS transcription. Deletion of all four mscS genes created a mutant that was unable to cope with hypoosmotic shock. However, the knockout mutant grew significantly faster than the wildtype at high salinity of 2 M NaCl, and most importantly, still exported 80% of the ectoine compared to the wildtype. We thus conclude that a yet unknown system, which is independent of mechanosensitive channels, is the major export route for ectoine in H. elongata.
The paper presents the results of the radiocarbon dating and ink analysis of a leather fragment bearing an important liturgical text in Hebrew from the early centuries of the common era. The work initiated by the scholarly interest in the text stresses the importance of the date and materiality of the manuscripts and closes with an appeal to the curators of manuscript collections.
Per- and polyfluoralkyl surfactants (PFASs) are industrially produced surface chemicals used in daily applications that have gained public and political attention due their unnaturally high appearance in drinking water, nourishments and soils. Their chemical structures exhibit both lipophilic and hydrophilic properties, leading to a highly inert and persistent character. Various PFASs have shown to be bioaccumulative in plants and animals, and some have been characterized as highly toxic when ingested. When exposed to the environment, PFASs slowly get mobilized by natural water resources, leading to contamination of large areas of soil and natural water sources. While PFASs contamination of drinking water has been investigated intensively, perfluoralkyl contamination of soils has been rarely examined as of yet. At the same time, an increasing amount of PFASs contamination sites are being discovered worldwide, calling for a sophisticated strategy towards analytical characterization. Since the number of known PFASs already exceeds 4700, the established sum parameters like extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF) are key elements to fully survey the impact of exposure. Simultaneously, innovative soil remediation strategies are required to contain environmental destruction and to minimize further
spreading of contaminants. Addressing these challenges requires suitable analytical devices that are capable of mobilizing PFASs in the solid as well as in the liquid phase. The use of combustion ion
chromatography (CIC) enables analysis of both immobile and volatile PFASs and allows the detection of both total fluorine (TF) and EOF or AOF of a given soil or aqueous sample. Based on preliminary results, the clean-up of a PFAS contaminated solid matrix is monitored via EOF detection over time.
Additionally, we demonstrate the pH dependency of hydrogen fluoride absorption on active carbon (AC) and found a simple organic additive to be an effective fluoride scavenger. The presented findings can be contributive with regard to future AOF/EOF sum parameter development and application.
This paper addresses the sensitive issue of authenticating unprovenanced manuscripts of high monetary value to certify they are genuine. Over the last decade, the popularity of material studies of manuscripts using non-destructive testing (NDT) has increased enormously. These studies are held in especially high esteem in the case of suspicious writings due to the methodological rigour they are reputed to contribute to debate. We would like to stress that materials analysis alone cannot prove that an object is genuine. Unfortunately, audiences with a humanities background often tend to disregard the technical details and treat any published interpretation of instrumental analysis as an objective finding. Four examples are outlined here to illustrate what questionable contributions the natural sciences can make in describing manuscripts that have actually been forged.
In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically Bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples fromriver Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum Parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 μg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14–0.81% of TF (determined using CIC) and EOF 0.04–0.28% of TF (determined using HR-CSGFMAS).
The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in Risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct.
The reliable measurement of very volatile organic compounds (VVOC) in indoor air by use of thermal desorption gas chromatography (TD-GC) in order to include them into evaluation schemes for building products even nowadays is a great challenge. For capturing these small molecules with carbon numbers ranging from C 1 –C 6 , strong adsorbents are needed. In the present study, recovery rates of nine suitable adsorbents of the groups of porous polymers, graphitised carbon blacks (GCB) and carbon molecular sieves (CMS) are tested against a complex test gas standard containing 29 VVOC. By consideration of the recovery and the relative humidity (50% RH), combinations of the GCB Carbograph 5TD, the two CMS Carboxen 1003 and Carbosieve SII as well as the porous polymer Tenax® GR were identified to be potentially suitable for sampling the majority of the VVOC out of the gas mix. The results reveal a better performance of the adsorbents in combination than being used alone, particularly under humid sampling conditions. The recovery rates of the chosen compounds on each adsorbent should be in the range of 80–120%.
This work presents a spectroscopic study of metallic pigments and metal foils used in reverse glass paintings that were created between 1912 and 1954. Metallic pigments induce a notable sparkling effect by means of the lateral incidence of light, whereas metal foils enhance the gloss and create a glittering effect when the painting is viewed in reflected light. Both effects were desired features especially in modern reverse paintings on glass and applied by artists in manifold creative manner. The paper gives an overview on the composition of the metalfoils and metal pigments in 14 works as determined in situ by X-ray spectrometry. Metal foils made of tin, brass, aluminium and silver were found in nine paintings. Gold imitating Cu-Zn pigments in different hues and with various Cu/Zn net intensity ratios were recorded for six paintings. Silvery pigments were identified mainly as Al pigments, but also as Cu-Zn-Ni alloy in one case. Other uncommon metallic pigments were detected in Arlequin vindicatif (c. 1925) by Floris Jespers, who used not only Cu-Zn and Al pigments, but also brownish Cu and Cu-Zn-Sn pigments. Non-invasive diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) was used to classify the binding media of the metallic pigments. Drying oil and natural resin probably mixed with oil were the most common binding media. A polysaccharide-based binder was found in the silvery Cu-Zn-Ni pigment of Ohne Titel (1954) by Marianne Uhlenhuth.
The feasibility of microbial hydrogen consumption to mitigate the hydrogen embrittlement (HE) under different cathodic potentials was evaluated using the Devanathan-Stachurski electrochemical test and the hydrogen permeation efficiency h. The hydrogen permeation efficiency h in the presence of strain GA-1 was lower than that in sterile medium. The cathodic potential inhibited the adherence of strain GA-1 to AISI 4135 steel surface, thereby reducing the hydrogen consumption of strain GA-1. The adherent GA-1 cells were capable of consuming ‘cathodic hydrogen’ and reducing the proportions of absorbed hydrogen, indicating that it is theoretically possible to control HE by hydrogen-consuming microbes.
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.
EI‐GEO is a multinational research project (Germany, Latvia, Russia) funded under the ERA.Net RUS Plus Call 2017. Aim of the project is the investigation whether geosynthetics in hydraulic engineering applications could be a source of microplastics (MPs) and other contaminants to the aquatic environment causing negative effects to aquatic organisms.
Whereas the behavior of geosynthetics in landfill engineering is well studied and documented since decades, little is known on application in applications such as coastal protection or ballast layers for wind energy plants. However, due to the rapid expansion of offshore wind energy, rising water levels and more extreme weather conditions as a result of climate change more and more hydraulic engineering projects will be realized in the future.
Applied methods are artificial ageing of geosynthetics in environmental simulation chambers, storage of samples under environmental condition for comparison with laboratory simulation, sample characterization by microscopic methods and ecotoxicological testing of water in contact with geosynthetics.
In parallel a case study at the Baltic Sea shore at Kaliningrad Oblast (Russia) will be performed. The aim of study is to estimate the level of pollution of the beaches by geosynthetic debris and identify the possible sources.
The ISO 16000 standard series provide guidelines for emission measurements of volatile organic compounds (VOCs) from building materials. However, polymer-based consumer products such as toys may also release harmful substances into indoor air. In such cases, the existing standard procedures are unsuitable for official control laboratories due to high costs for large emission testing chambers. This paper aims at developing and comparing alternative and more competitive methods for the emission testing of consumer products. The influence of the emission chamber size was investigated as smaller chambers are more suited to the common size of consumer products and may help to reduce the costs of testing. Comparison of the performance of a 203 l emission test chamber with two smaller chambers with the capacity of 24 l and 44 ml, respectively, was carried out by using a polyurethane reference material spiked with 14 VOCs during the course of 28 days. The area-specific emission rates obtained in the small chambers were always similar to those of the 203 l reference chamber after a few hours. This implies that smaller chambers can provide at least useful numbers on the extent of polymer-based consumer product emissions into indoor air, thereby supporting meaningful exposure assessments.
As one of the most energy and carbon consuming industries, steelmakers have an intrinsic interest in the development of technologies, reducing their carbon footprint as well as their carbon input. Besides generating new feedstocks from biomass or waste polymers, the valorization of carbon fiber reinforced polymer (CFRP) waste streams seems to be extremely promising based on the high carbon content of carbon fibers (CF), chars from CFRP and even unprocessed CFRP waste of >92%, 98% and 79%, respectively. Although, reduction of environmental impact from those high-performance materials was achieved by the development of smart recycling solutions, the continuous truncation by mechanical treatment of CF over multiple cycles, analogous to paper fibers, and the large global CFRP waste stream of 62 kt/a demand for a sustainable management of end-of-life (EOL) CFRP. Recently it was demonstrated that CF can be used safely as reductant in pyrometallurgical processes in a downhole electric furnace without significant WHO fiber emission. Therefore we anticipate a huge potential of CF based materials as sustainable reductant for steelmaking in an electric arc furnace (EAF). To facilitate the applicability of EOL CFRP in steelmaking, we investigated the interaction between CF based materials and liquid metal phases, appearing during the process, on different scales. Particularly, we examined the reactivity, wettability and dissolution behavior of CF and CFRP concerning liquid slag and steel. The presented results indicate that understanding the impact of the microstructure of CF on their behavior is crucial for their application in EAF steelmaking without risking potential hazards by WHO fiber emission. Besides the detailed elucidation of structure reactivity relationships of CF, the broader impact on circular economy will be presented.
Up to now, different analytical methods for single cell analysis exist focusing on key features such as size, shape, morphology and elemental composition. The combination of the latest ICP-MS techniques - ICP-ToF-MS - together with the latest developments in the field of sample delivery - micro droplet generator (MDG) – will allow a Deep insight into the composition and size of cells.
Microbiologically influenced corrosion (MIC) is an oxidation of metals affected by the presence or activity (or both) of microorganisms e.g. Shewanella Putrefaciens in biofilms on the surface of the corroding material. As this can happen for example in the soil on iron pipes of water pipes, in oil tanks or on steel sheet piling, there is great interest in MIC research, not only from various industrial sectors, but also from the environmental aspect.
This study shows that formaldehyde Emission results in micro-scale emission chambers are comparable with results in bigger chambers both for particle boards and wooden toys. On the contrary, the WKI flask method was leading to more variable results depending on sample geometry. Thus, microchambers could be used for reliable routine market surveillance. An exposure assessment led to noticeable formaldehyde indoor air concentration values, pointing out the need for an effective Surveillance of such samples.
Low-molecular-weight organic acids (LMWOAs) are crucial for the mobilization and acquisition of mineral phosphorus by plants. However, the role of LMWOAs in mobilizing organic phosphorus, which is the predominant phosphorus form in at least half of the world’s ecosystems, especially in humid climates, is unclear. The mechanisms of phosphorus mobilization by LMWOAs depend on climate, mainly precipitation, and shape the phosphorus nutrition strategies of plants. We disentangled the impact of roots and associated microorganisms on mechanisms of phosphorus cycling mediated by LMWOAs by studying soils along an ecosystem-sequence (ecosequence) from arid shrubland (~70 mm yr-1), and Mediterranean woodland (~370 mm yr-1) to humid-temperate forest (~1470 mm yr-1). Phosphorus speciation in soil was examined by X-ray absorption near edge structure analysis (XANES). LMWOAs were quantified as biological rock-weathering and organic phosphorus mobilization agents and compared to kinetics of acid phosphatase as a proxy for organic phosphorus mineralization. Calcium-bound phosphorus in topsoils decreased from 126 mg kg-1 in the arid shrubland, to 19 mg kg-1 in the Mediterranean woodland and was undetectable in the humid-temperate forest. In contrast, organic phosphorus in topsoils in close root proximity (0–2 mm distance to roots) was absent in the arid shrubland but raised to 220 mg kg-1 in the Mediterranean woodland and to 291 mg kg-1 in the humid-temperate forest. The organic phosphorus content in topsoils was 1.6 to 2.4 times higher in close root proximity (0–2 mm distance to roots) compared to bulk soil (4–6 mm distance to roots) in the Mediterranean woodland and humid-temperate forest, showing intensive phosphorus bioaccumulation in the rhizosphere. Redundancy analysis (RDA) revealed that LMWOAs were explained by the content of hydroxyapatite and variscite phosphorus-species in the arid shrubland, indicating that LMWOAs contribute to mineral weathering in this soil. LMWOA contents, phosphatase activity, and microbial biomass carbon correlated strongly with organic phosphorus in the humid-temperate forest soil, which implies a high relevance of LMWOAs for organic phosphorus recycling. In the Mediterranean woodland soil, however, oxalic acid correlated with organic phosphorus in the topsoil (suggesting phosphorus recycling), whereas in the subsoil malic and citric acid were correlated with primary and secondary phosphorus minerals (implying mineral weathering). We conclude that phosphorus acquisition and cycling depend strongly on climate and that the functions of LMWOAs in the rhizosphere change fundamentally along the precipitation gradient. In the arid shrubland LMWOAs facilitate biochemical weathering (rock eating), while in the humid-temperate forest their functions change towards supporting organic phosphorus recycling (vegetarian).
An interdisciplinary approach to the study of manuscript traditions is here applied to the analysis of the leaves from the White Monastery, one of the greatest centres of literary production in Late Antique Egypt. In the framework of the ‘PAThs’ project, archaeometric analyses complement the information pieced together by a range of disciplines in the field of humanities. The use of different complementary analytical techniques provides information on the type of ink used and its elemental composition, unveiling interesting details regarding the materials and methodology of manufacturing of writing media. Moreover, this contribution takes a step forward and discusses the possible existence of a regional arrangement in the elemental composition revealed in the inks studied.
Microcolonial black fungi, a polyphyletic group of ascomycetes, exhibit constitutive melanin formation, yeast-like growth and high stress tolerances. They dominate – often together with bacteria and algae in sub-aerial biofilms – a range of hostile environments including natural and man-made ones, from salterns to dishwashers, roofs and solar panels. Because of lacking genetic tools and the slow growth of most isolates, the genetic bases for these specific properties are largely unknown. The rock-inhabiting fungus Knufia petricola (Eurotiomycetes, Chaetothyriales) exhibits all characteristics of microcolonial black fungi and was selected as recipient for genetic engineering to study gene functions and genetic interactions. Different variants of green and red fluorescent proteins were successfully expressed indicating that fluorescence microscopy using genetically encoded fluorescent proteins and fluorescent dyes enables various cell biology approaches. Furthermore, genes of biosynthetic pathways (DHN melanin, carotenoids, uracil, adenine) were successfully mutated by applying traditional gene replacement and plasmid-based or ribonucleoprotein (RNP)-based CRISPR/Cas9 or silenced by RNA interference (RNAi). The availability of this advanced and efficient genetic toolbox and the annotated genome sequence of strain A95 makes K. petricola an excellent model for exploring the secrets of microcolonial black fungi.
Gypsum (calcium sulfate dihydrate) has excellent building material properties and has been widely used in constructions in the last decades in many countries. Accordingly, an increase of waste gypsum in C&D waste is expected in the upcoming years. On one hand, sulfates are unwanted in other secondary building materials (particularly in recycled concrete aggregates) and should be minimized for quality reasons. On the other hand, used gypsum from CDW can also be used in gypsum production if the high quality requirements for the recycled gypsum – especially regarding the sorting accuracy - are met.
A large percentage of the gypsum from buildings was installed as gypsum plasterboards in interior fittings so far. Gypsum plasterboards are comparatively simple to remove and to separate during selective dismantling. Therefore, a high sorting purity can be achieved. In addition, techniques for the recycling of gypsum plasterboards already exist and high quality standards can be achieved. Also, the reuse in gypsum production has been improved in the last decade. Furthermore, an environmental evaluation of the whole process of gypsum plasterboard recycling and reuse showed that this approach can be environmentally advantageous. Therefore, a closed-loop recycling of gypsum plasterboards is feasible.
This poster will show the development of gypsum consumption in different countries as well as a prognosis for the upcoming of gypsum in CDW in the future decades in Germany. Furthermore, a simplified scheme of the recycling process and selected results from an environmental evaluation will be presented.
Microbial communities in the immediate environment of socialized invertebrates can help to suppress pathogens, in part by synthesizing bioactive natural products. Here we characterized the core microbiomes of three termite species (genus Coptotermes) and their nest material to gain more insight into the diversity of termite-associated bacteria.
Sampling a healthy termite colony over time implicated a consolidated and highly stable microbiome, pointing toward the fact that beneficial bacterial phyla play a major role in termite fitness. In contrast, there was a significant shift in the composition of the core microbiome in one nest during a fungal infection, affecting the abundance of wellcharacterized Streptomyces species (phylum Actinobacteria) as well as less-studied bacterial phyla such as Acidobacteria. High-throughput cultivation in microplates was implemented to isolate and identify these less-studied bacterial phylogenetic group.
Amplicon sequencing confirmed that our method maintained the bacterial diversity of the environmental samples, enabling the isolation of novel Acidobacteriaceae and expanding the list of cultivated species to include two strains that may define new species within the genera Terracidiphilus and Acidobacterium.
How the rock-inhabiting fungus K. petricola A95 enhances olivine dissolution through attachment
(2020)
Free-living and mycorrhizal fungi are able to enhance the weathering of rock and other solid substrates. Deciphering the exact mechanisms of these natural processes requires their experimental simulation. Moreover, by performing these simulations with genetically amenable rock-weathering fungi, one can knock-out certain fungal traits and consequently identify their weathering-relevant function. Here, the effect of the rock-inhabiting fungus, Knufia petricola A95, on the dissolution kinetics of an Fe-bearing olivine (Mg1.86Fe0.19SiO4) is investigated at 25 °C and pH 6 using reproducible batch and mixed flow experiments. The availability of a melanin-deficient mutant (ΔKppks) of K. petricola A95, which produces more extracellular polymeric substances (EPS) than the wild type (WT), enables the comparative study of the role of melanin and EPS in olivine dissolution. In abiotic dissolution experiments, the olivine dissolution rate decreased considerably over time at pH 6 but not at pH 3.5. This inhibition of abiotic olivine dissolution at pH 6 was most likely caused by the in-situ oxidation of ferrous Fe and/or the precipitation of ferric hydroxides at the olivine surface. In corresponding biotic experiments at pH 6, both the wild type K. petricola and its melanin-deficient mutant ΔKppks solubilised and bound significant amounts of Fe released by olivine dissolution. Fe oxidation and precipitation were thus prevented and olivine dissolution proceeded faster than in the abiotic experiments. By sequestering Fe directly at the olivine surface, the attached wild type K. petricola cells were particularly efficient at preventing the oxidation of Fe at the mineral surface: the slowdown of olivine dissolution almost completely disappeared. The attachment capacity of these wild type cells is most likely mediated by wild type-specific EPS. Our presented experimental systems allow the oxidation of mineral-released Fe and include a rock-inhabiting fungus, thus simulating chemical, physical and biological conditions that set dissolution rates in a way that is relevant to natural ecosystems.
The hydrogen permeation current increase was noticed for carbon steel in 0.5 mol/L NaCl solution under strong anodic potentials, which is contrary to the common understanding. Hydrogen permeation under cathodic potentials has been widely studied because of possible hydrogen embrittlement failures of high strength steels in seawater, but investigations of anodic polarization on hydrogen permeation are fairly rare, as the hydrogen evolution reaction shall be retarded. To corroborate the observed phenomenon, experiments were conducted using both as-received and vacuum-annealed sheet specimens. It was verified that the observed phenomena originated from the released hydrogen in traps by metal dissolution under anodic polarization.
Due to their ability to penetrate, deteriorate and discolour stone surfaces, rock-inhabiting black fungi represent a remarkable issue for cultural heritage conservation. Black microcolonial fungi (MCF) can also adapt to different environmental conditions, by converting from yeast-like morphology to a peculiar meristematic development with swollen cells (torulose hyphae, TH), to extremely thin structures (filamentous hyphae, FH). Furthermore, black MCF produce protective pigments: melanin, dark pigment particularly evident on light stone surfaces, and carotenoids. Black fungi produce melanin in critical, oligotrophic conditions as well as constitutively. Melanin function is mostly related to stress resistance and the ability of fungi to generate appressorial turgor to actively penetrate plant cells in pathogenic species. An involvement of melanins in stone surface penetration has been suggested, but not experimentally proved. In this work, we tested the role of hyphal melanisation in penetration mechanisms on the model black fungus Knufia petricola A95 in lab conditions. The wild-type and three mutants with introduced targeted mutations of polyketide-synthases (melanin production) and/or phytoene dehydrogenase (carotenoid synthesis) were inoculated on artificial carbonate pellets (pressed Carrara marble powder) of different porosity. After 5, 10, 17 and 27 weeks, hyphal penetration depth and spread were quantified on periodic acid Schiff-stained cross-sections of the pellets, collecting measurements separately for TH and FH. Droplet assay of the mutants on different media were conducted to determine the role of nutrients in the development of different fungal morphologies. In our in vitro study, the hyphal penetration depth, never exceeding 200 μm, was proven to be consistent with observed penetration patterns on stone heritage carbonate substrates. Pellet porosity affected penetration patterns of TH, which developed in voids of the more porous pellets, instead than actively opening new passageways. Oppositely, the thin diameter of FH allowed their penetration independently of substrate porosity. Instead, the long-hypothesized crucial role of melanin in black MCF hyphal penetration should be rejected. TH were developed within the pellets also by melanin deficient strains, and melanized strains showed an endolithic component of non-melanized TH. FH were non-melanized for all the strains, but deeply penetrated all pellet types, with higher penetration depth probably related to their potential exploratory (nutrient-seeking) role, while TH may be more related to a resistance to surface stress factors. In the melanin deficient strains, the absence of melanin caused an increased penetration rate of FH, hypothetically related to an earlier necessity to search for organic nutrients.
In the recent years multispectral imaging and X-ray Fluorescence element mapping have established themselves as a well working two step approach, when dealing with faded, erased or overwritten text in iron gall ink. During the last years a lot was done to improve the mere technical side of the techniques. Especially in the case of XRF mapping experiments the acquisition speed needed to be increased to allow mapping in the high resolution demanded by the challenges at hand. High resolution in moderate times can now be achieved, but with the price of proportionally increased amount of data that needs to be processed ideally in parallel to the measurement. The classical approach in XRF spectroscopy of elemental fitting of the spectral data does not even come close to fulfill any on the fly processing time constraints and will consume too much processing time in the foreseeable future. In this paper we will discuss the applicability of modern statistical data processing methods to XRF mapping of iron gall ink palimpsests. We will present a comparison of a new approach based on principle and independent component analysis (PCA and ICA) and the standard element mapping method. We will show that a reduction in processing time of almost two orders of magnitude can easily be achieved.
Social immune behaviors are described in a great variety of insect societies and their role in preventing emerging infectious diseases has become a major topic in insect research. The social immune system consists of multiple layers, ranging from the synthesis of external immune molecules to the coordination of individual behaviors into sophisticated collective defensive tasks. But our understanding of how complex group-level behavioral defenses are orchestrated has remained limited. We sought to address this gap in knowledge by investigating the relationship between the external activity of an important immune effector molecule in termites, Gram negative binding protein 2 (GNBP-2) and collective grooming and cannibalism. We reasoned that as an external enzyme capable of degrading entomopathogenic fungi, GNBP-2 can facilitate the spread of pathogenic molecules in the colony, and thus serve to trigger collective defenses in a manner analogous to pathogen-associated molecular signatures (PAMPs) of the individual immune system. To test whether GNBP-2 could play a role in regulating social immune behavior, we experimentally inhibited its fungicidal activity using the glycomimetic molecule, D-d-gluconolactone (GDL) and recorded collective behavioral responses to an infected nestmate. Contrary to expectations, GNBP-2 inhibition did not influence the rate or intensity of grooming of either control or fungus-infected
nestmates. By contrast, we found that the probability of being harmed through defensive cannibalistic behaviors was significantly reduced by the inhibition of GNBP-2. Our findings indicate that the regulation of collective immune behaviors may depend in part on the external secretion of an enzyme originating from the individual immune system, but that other cues are also necessary.
The scribe of ‘Erfurt 7’, a thirteenth-century Torah scroll now kept in Berlin, initially left blank spaces for the divine appellations Elohim ( אלהים ) and YHWH Elohim ( ,(יהוה אלהים which were filled in during a second stage of writing. The appearance of the ink employed to write the appellations was significantly darker than that of the surrounding ink.
X-ray fluorescence analysis (XRF) has shown that the light and dark brown inks had similar elemental compositions, but contained different ratios of iron to potassium, which could be explained by the use of different batches of ink.
According to some medieval sources, the divine appellations were sometimes filled in during a second stage of writing in the presence of ten men from the Jewish community. In Erfurt 7, the two-stage procedure was only performed in the first 1.5 columns of the original sheets, suggesting it may have been part of a public ceremony inaugurating the writing of the divine names in the scroll. Erfurt 7 emerges from this study not only as a ritual object used for liturgy, but as a rallying point for the Jews of Erfurt to come together as a community to express their reverence for the written form of God’s name. The divine name YHWH ( יהוה ) was written in a smaller script than the surrounding text on three replacement sheets using the same two-stage procedure. The ink used on the replacement sheets contained zinc, which is characteristic of other Erfurt manuscripts as well. This suggests that Erfurt was the place where the scroll was used, cherished and eventually repaired.
Innovation Network PerFluSan
(2020)
Per- and polyfluorinated alkyl substances (PFAS) are transferred into the environment as part of their broad industrial use, where they pose a problem due to their critical properties. The sustainable protection of people and the environment from this group of substances is an important task for the future. However, available PFAS removal and remediation processes are expensive and often inadequate. PerFluSan would like to make a relevant contribution to solve this problem by developing new PFAS remediation methods for soils and water, as well as innovative analytical methods for PFAS detection.
The long-term vision is to develop PerFluSan into a national contact point for the PFAS topic, which uses synergies between the PerFluSan actors to address all aspects of the problem holistically, sustainably and effectively.
The Scythica Vindobonensia, the new fragments on Gothic incursions into Roman provinces in the Balkans in the middle of the third century AD that were revealed some years ago in a Greek palimpsest at the Austrian National Library in Vienna (ÖNB), are commonly considered as one of the most important additions of the last decades to the corpus of texts from classical Antiquity. Tere is a high degree of confdence among scholars in supposing that the fragments come from the lost work Scythica written in Greek by the third-century historian P. Herennius Dexippus (Δέξιππος) of Athens. The new fragments have hence also been called Dexippus Vindobonensis. In his Scythica, Dexippus recorded wars of the Romans with the Goths (and other tribes) whom he called Scythians.
The work had been hitherto known only from excerpts and quotes by later authors. Eight pages of a Byzantine manuscript copy of the ancient text have survived hidden underneath the visible surface of the last four parchment folios of the Vienna manuscript Historicus graecus 73, f. 192r -195v4. The copy is written in a Greek calligraphic minuscule which has been estimated by palaeographers to be of the middle or the second half of the eleventh century. In the thirteenth century, the text (on each of the eight pages arranged in one column, with 30 lines per page) was washed of the parchment and the valuable material made from animal skin was re-used for Christian texts. The new writing largely covered the faded remnants of the original text. It thus became hidden from the human eye for more than seven hundred years. Its discovery by Jana Grusková, a classical philologist specialized in the transmission of Greek texts, resulted from a systematic review of all Greek palimpsests kept at the Austrian National Library in Vienna at the beginning of the twenty-first century and a detailed examination of the four folios in 2007-20097.
This paper presents an inventory of sewage sludge ashes (SSA) generated in the mono-incineration plants for municipal sewage sludge in Poland. This research focused on the detailed study of mass flows, chemical composition, and phosphorus recovery potential. There are currently 11 sludge mono-incineration plants operated with a total capacity of 160,300 Mg dry weight (d.w.) of sludge annually. Recently, a significant increase in the amount of SSA generated in these plants has been observed, reaching 26,756 Mg in 2018. Chemical composition of SSA showed significant amounts of the main nutrients: calcium (~14%), phosphorus (~13%), magnesium (~3%), and potassium (~1%). Additional main elements were iron (~14.5%), silicon (~13%), and aluminium (~6%). The main trace elements in the SSA were zinc (~3750 mg/kg) and copper (~899 mg/kg). Pollutants, according to fertilizer regulations of different countries, present in Polish SSA were chromium(~703 mg/kg), nickel (~260 mg/kg), lead (~94 mg/kg), and Cadmium (~9 mg/kg). The radionuclides, uranium, and thorium often present in higher amounts in commercial phosphate rock-based fertilizers, were only detected in SSA t low levels of 4–9 mg/kg and 2–3 mg/kg, respectively. Theoretical phosphorus recovery potential from the SSA (from plants in Cracow, Lodz, Gdansk, Gdynia, Szczecin, and Kielce) was estimated at 1613.8 Mg, of which 33.9% is bioavailable. Currently, in Poland, the recommended approach is the production of fertilizers as a result of the extraction of phosphorus from the SSA with its use in the production of secondary mineral fertilizers.
Further research in this area is required considering Polish conditions and legislation.
In recent times, as the need for new high-tech materials is growing steadily to fulfil future sustainability goals, more and more looks turn towards industrial waste streams as potential sources of valuable metals. Bauxite residue (BR), accumulating during alumina production, is one of the major waste streams in the metal industry. Suitable re-use possibilities for BR are intensively investigated including approaches for the recovery of scandium (Sc). This transition metal, even though rarely recognized by the broader audience yet, has recently gained the interest of e.g. aerospace industries and SOFC-producers since its use is strongly improving the performance and durability of the respective materials.
Even though many sources classify Sc as one of the REE, there are many aspects, such as its ionic radius, which significantly differentiate Sc from the REE and cause its behaviour to be distinct as well. The large ionic potential (radius/charge) causes Sc to be incompatible in most rock forming minerals, which results in generally low concentrations in the earth’s crust and rare occurrences of natural Sc-deposits.
The general occurrence of enriched concentrations of Sc in some BRs compared to the earth’s crust is known for some time now and has especially been investigated for Greek materials. However, the (geo)chemical and mineralogical behaviour, the Sc speciation, the association and the variation of Sc occurrences in BRs of different origin is still not fully understood. This study aims to gain better knowledge on the different kinds of Sc-occurrences and their possible impact on future recovery schemes. We therefore apply a diverse set of analytical methods including novel measurement techniques such as X-ray absorption near edge structure (XANES) spectroscopy as well as standard techniques such as electron microprobe analyses, and Raman spectroscopy on BRs from Germany, Hungary and Greece. Information on the local distribution of Sc is determined by high-resolution laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) mappings.
Sc in Greek BR seems to have an affinity towards Fe-Phases such as Goethite and Hematite. However, whereas some of these phases show distinct enrichment of Sc, others are particularly barren, which might be a result of the different input materials. By means of XANES measurements it was possible to show that Sc in the Greek samples occurs adsorbed on the surface of those Fe-Phases, likely in the form of amorphous Sc-hydroxide or -oxyhydroxide or can be incorporated into the crystal lattice as well. The general affinity of Sc to those kinds of phases has been reported for natural rocks such as laterites before, where similar investigations were made using the XANES method [8]. Likewise, the Fe-association has been observed for Greek BR by Vind et al. [7]. Hungarian BRs show similar results as the Greek samples and LA-ICP-MS mappings show distinct Sc enrichment rims surrounding mineral particles. In German BR, Fe as well as Ti-phases occur to be partially enriched in Sc. Depending on the original primary bauxite, the source rock of the bauxite and the bauxite processing route, it is likely that many different parameters influence the occurrence and species of Sc in the BR. Theoretically, it either can therefore remain within its original carrier or can be partially or fully redistributed within the BR. Since the processing of the bauxite involves elevated temperatures, pressure and dissolving reagents, it is however very likely that some of the Sc will be redistributed and adsorb on mineral surfaces of smaller and larger particles, making beneficiation steps rather ineffective.
The study shows that there is no general rule defining how Sc is associated mineralogically or chemically within BRs. Therefore, the effective development of a recovery method needs a case specific background knowledge on the Sc-species present in the BR of interest. This research has received funding from the European Community’s Horizon 2020 Programme SCALE (H2020/2014-2020) under grant agreement n° 730105.
The influence of interfacial pH between AISI 4135 steel and seawater under different polarization potentials on the formation of calcareous deposits has been studied. An interfacial pH of 9.61 at −0.9 V vs. SCE using state of the art iridium oxide microelectrode was found to be the critical pH for the precipitation of magnesium hydroxide. Calcareous deposits with a double-layer structure comprising an inner-brucite layer and an outer-aragonite layer were found to form at potentials between −1.0 V and −1.2 V vs. SCE. Furthermore, the facilitation of hydrogen permeation into steel induced by the formation of calcareous deposits was verified using the Devanathan-Stachurski electrochemical test. The mechanism of calcareous deposits facilitates hydrogen permeation into steel is related to its inhibition on hydrogen recombination and escape processes.
Currently, sulfate-reducing bacteria (SRB) is regarded as the main culprit of microbiologically influenced corrosion (MIC), mainly due to the low reported corrosion rates of other microorganisms. For example, the highest reported corrosion rate for methanogens is 0.065 mm/yr. However, by investigating methanogen-induced microbiologically influenced corrosion (Mi-MIC) using an in-house developed versatile multiport flow test column, extremely high corrosion rates were observed. We analyzed a large set of carbon steel beads, which were sectionally embedded into the test columns as substrates for iron-utilizing methanogen Methanobacterium IM1. After 14 days of operation using glass beads as fillers for section separation, the highest average corrosion rate of Methanobacterium IM1 was 0.2 mm/yr, which doubled that of Desulfovibrio ferrophilus IS5 and Desulfovibrio alaskensis 16109 investigated at the same conditions. At the most corroded region, nearly 80% of the beads lost 1% of their initial weight (fast-corrosion), resulting in an average corrosion rate of 0.2 mm/yr for Methanobacterium IM1-treated columns. When sand was used as filler material to mimic sediment conditions, average corrosion rates for Methanobacterium IM1 increased to 0.3 mm/yr (maximum 0.52 mm/yr) with over 83% of the beads having corrosion rates above 0.3 mm/yr. Scanning electron images of metal coupons extracted from the column showed methanogenic cells were clustered close to the metal surface. Methanobacterium IM1 is a hydrogenotrophic methanogen with higher affinity to metal than H2. Unlike SRB, Methanobacterium IM1 is not restricted to the availability of sulfate concentration in the environment. Thus, the use of the multiport flow column provided a new insight on the corrosion potential of methanogens, particularly in dynamic conditions, that offers new opportunities for monitoring and development of mitigation strategies. Overall, this study shows under certain conditions methanogenic archaea can cause higher corrosion than SRB, specific quantifications, i.e., maximum, average, and minimum corrosion rates can be determined, and that spatial statistical evaluations of MIC can be carried out.
At the end of the sixteenth century, a number of relics and artefacts were discovered in Granada, Spain. They included what became known as the Lead Books of the Sacromonte, twenty-one written artefacts made of circular lead leaves engraved in archaic Arabic characters. The authorship was attributed to some Arab disciples of St James the Greater considered to be the first evangelisers of the Iberian Peninsula. The texts, the materiality and the circumstances of the discoveries fuelled a debate surrounding their authenticity that lasted more than two centuries, a debate so fierce and controversial that not even papal condemnation in 1682 was able to stop it. Soon after the discoveries were made public, scholars highlighted the many contradictions and errors of a historical, linguistic and theological nature present in the texts, identifying members of the local Morisco community as possible forgers. This article focuses on how the scholarly community of the sixteenth and seventeenth centuries handled these findings and looks at the methods employed by the scholars to evaluate the authenticity of the artefacts. It will also look at how the particular interests of the various authorities involved influenced the acceptance or dismissal of relevant academic results.
The evolutionary success of insects is promoted by their association with beneficial microbes that enable the utilization of unusual diets. The synanthropic clothing moth Tineola bisselliella provides an intriguing example of this phenomenon. The caterpillars of this species have adapted to feed on keratin-rich diets such as feathers and wool, which cannot be digested by most other animals and are resistant to common digestive enzymes. Inspired by the hypothesis that this ability may be conferred by symbiotic microbes, we utilized a simple assay to detect keratinase activity and a method to screen gut bacteria for candidate enzymes, which were isolated from feather-fed larvae. The isolation of DNA from keratin-degrading bacterial strains followed by de novo genome sequencing resulted in the identification of a novel bacterial strain related to Bacillus sp. FDAARGOS_235. Genome Annotation identified 20 genes with keratinase domains. Proteomic analysis of the culture supernatant from this gut bacterium grown in non-nutrient buffer supplemented with feathers revealed several candidate enzymes potentially responsible for keratin degradation, including a thiol-disulfide oxidoreductase and multiple proteases. Our results suggest that the unusual diet of T. bisselliella larvae promotes their association with keratinolytic microorganisms and that the ability of larvae to feed on keratin can at least partially be attributed to bacteria that produce a cocktail of keratin-degrading enzymes.
Bottom ash (BA) from municipal solid waste incineration (MSWI) contains harmful substances such as heavy metals, chloride and sulfate which are mobilized in contact with water. Standardized leaching tests are used to measure the extent of mobilization. It is known that fresh bottom ash displays elevated concentrations of various heavy metals such as lead or zinc due to the formation of hydroxo complexes as a result of high pH values of 12 and above. Storage of BA is accompanied by ageing processes, mainly the reaction of CaO and Ca(OH)2 with CO2 leading to lower pH values in contact with water around 11. Usually heavy metals concentrations are minimum at these conditions. Knowledge of the long-term leaching behavior of potentially harmful substances is crucial for the assessment of the environmental compatibility of reusing municipal solid-waste incineration bottom ash (MSWI BA) in construction, i.e., as a road base layer. BA fractions obtained from wet-processing aiming at the improvement of environmental quality were used to investigate the mobility of relevant substances. Eluates from laboratory-scaled leaching procedures (column percolation and lysimeters) were analyzed to learn about the long-term release of substances. Unsaturated conditions and artificial rainwater were used in the lysimeter tests to simulate field conditions. In addition, batch test eluates were generated at usual liquid-to-solid ratios (L/S) for compliance testing purposes. A variety of cations and anions was measured in the eluates. The wet treatment reduces the leaching of chloride and particularly sulfate by more than 60%. The release of typical contaminants for the treated MSWI BA such as the heavy metals Cu and Cr was well below 1% in the conducted leaching tests. An increase in the Sb concentration was observed in the lysimeter experiments starting at L/S 0.75 L/kg and in the column experiment at L/S 4 L/kg is assumed to be related to decreasing concentrations of Ca and thus to the dissolution of sparingly soluble calcium antimonate. The same leaching mechanism applies with V, but the concentration levels observed are less critical regarding relevant limit values. However, on the long term the behavior of Sb could be problematic for the application of MSWI BA as secondary building material.
Almost 500 municipal solid waste incineration plants in the EU, Norway and Switzerland generate about 17.6 Mt/a of incinerator bottom ash (IBA). IBA contains minerals and metals. Metals are mostly separated and sold to the scrap market and minerals are either disposed of in landfills or utilised in the construction sector. Since there is no uniform regulation for IBA utilisation at EU level, countries developed own rules with varying requirements for utilisation. As a result from a cooperation network between European experts an up-to-date overview of documents regulating IBA utilisation is presented. Furthermore, this work highlights the different requirements that have to be considered. Overall, 51 different parameters for the total content and 36 different parameters for the emission by leaching are defined. An analysis of the defined parameter reveals that leaching parameters are significantly more to be considered compared to total content parameters. In order to assess the leaching behaviour nine different leaching tests, including batch tests, up-flow percolation tests and one diffusion test (monolithic materials) are in place.
A further discussion of leaching parameters showed that certain countries took over limit values initially defined for landfills for inert waste and adopted them for IBA utilisation. The overall utilisation rate of IBA in construction works is approximately 54 wt%. It is revealed that the rate of utilisation does not necessarily depend on how well regulated IBA utilisation is, but rather seems to be a result of political commitment for IBA recycling and economically interesting circumstances.
New developments in legislation and technology development for P-recovery were presented with focus on the situation in Germany.
After their discovery on rock surfaces in cold and hot deserts, a polyphyletic group of ascomycetous black fungi was found to dominate a range of hostile environments – natural and man-made, from salterns to dishwashers, roofs and solar panels. Together with bacteria and algae they may establish subaerial biofilms and cause weathering of the surfaces they grow on. Their impressive survival abilities as well as their constitutive protective pigmentation and cluster-like microcolony organisation are similar in environmental isolates as well as in heat-tolerant opportunistic pathogens of animals and humans. We selected the rock-inhabiting fungus Knufia petricola (class Eurotiomycetes, order Chaetothyriales) that exhibits all the characteristics of microcolonial black fungi such as yeast-like cell growth, absence of reproductive structures and constitutive dihydroxynaphthalene (DHN) melanogenesis (Nai et al. 2013, Fungal Genet Biol). We developed protocols to efficiently generate and transform protoplasts resulting in stable homokaryotic transformants by targeting genes involved in pigment synthesis. The differences between the wild-type fungus and its melanin-deficient mutants were tested in geomicrobiological experiments and measured are now discussed in detail, with special accent on the possible effects of the mutation on EPS and other exuded substances.
Fungi that share light-flooded habitats with phototrophs may profit from their excess photosynthetic products. But to cope with sunlight-associated stresses [e.g. high temperatures, UV radiation with associated DNA damage, accumulation of reactive oxygen species (ROS), desiccation and osmotic stresses] it is important for fungi to accurately sense and respond to changes in light. To test the hypothesis that light is an environmental cue that Ascomycota use to coordinate growth, stress responses as well as to establish pathogenic or symbiotic relationships, the photoreceptor (PR) distribution in species from different ecological niches was analysed. The genomes of black [dihydroxynaphthalene (DHN) melanin-containing] fungi from phyllosphere and exposed solid surfaces contain multiple photoreceptors (PRs). The plant pathogen Botrytis cinerea (Leotiomycetes) has a highly sophisticated photosensory and signalling system that helps to avoid light and to locate susceptible hosts. Rock-inhabiting Dothideomycetes and Eurotiomycetes including Knufia petricola possess equal numbers ofPRs along with the same set of protective pigments. This similarity between black fungi from plant and rock surfaces suggests that photoperception and -regulation are important for fungi that receive nutrients through cooperation with phototrophs. Genetic tools for manipulating K. petricola exist and will be used to test this idea.
In many bacteria, the biofilm-promoting second messenger c-di-GMP is produced and degraded by multiple diguanylate cyclases (DGC) and phosphodiesterases (PDE), respectively. High target specificity of some of these enzymes has led to theoretical concepts of "local" c-di-GMP signaling. In Escherichia coli K-12, which has 12 DGCs and 13 PDEs, a single DGC, DgcC, is specifically required for the biosynthesis of the biofilm exopolysaccharide pEtN-cellulose without affecting the cellular c-di-GMP pool, but the mechanistic basis of this target specificity has remained obscure. DGC activity of membrane-associated DgcC, which is demonstrated in vitro in nanodiscs, is shown to be necessary and sufficient to specifically activate cellulose biosynthesis in vivo. DgcC and a particular PDE, PdeK (encoded right next to the cellulose operon), directly interact with cellulose synthase subunit BcsB and with each other, thus establishing physical proximity between cellulose synthase and a local source and sink of c-di-GMP. This arrangement provides a localized, yet open source of c-di-GMP right next to cellulose synthase subunit BcsA, which needs allosteric activation by c-di-GMP. Through mathematical modeling and simulation, we demonstrate that BcsA binding from the low cytosolic c-di-GMP pool in E. coli is negligible, whereas a single c-di-GMP molecule that is produced and released in direct proximity to cellulose synthase increases the probability of c-di-GMP binding to BcsA several hundred-fold. This local c-di-GMP signaling could provide a blueprint for target-specific second messenger signaling also in other bacteria where multiple second messenger producing and degrading enzymes exist.
Dihydroxynaphthalene (DHN) melanin is produced by different Ascomycetes via slightly differing biosynthetic routes. The polyketide synthases (PKS) release the heptaketide YWA1, the hexaketide AT4HN or the pentaketide T4HN. The first two products are deacetylated by ‘yellowish-green’ hydrolases to T4HN, and T4HN is further converted by a core set of enzymes to DHN. Final polymerization steps are accomplished by multicopper oxidases. DHN melanogenesis is often regulated in a spatial and temporal fashion resulting e.g. in melanized reproduction, survival and/or infection structures. Remarkable is the regulation of the DHN melanogenesis in the foliar plant pathogen Botrytis cinerea: it involves two differently expressed PKSs providing the precursor in conidia and sclerotia, respectively (Schumacher 2016, Mol Microbiol). In contrast, a polyphyletic group of Ascomycetes (microcolonial fungi/ black yeast) dwelling in hostile habitats such as bare rock surfaces in hot and cold deserts, exhibits constitutive melanogenesis. Here, DHN melanin builds a protective layer around all vegetative cells thus contributing to the survival of diverse environmental stresses even without specialized reproduction structures. As part of our continuing research on microcolonial rock-inhabiting fungi, we chose the genetically amenable Knufia petricola strain A95 (Nai et al. 2013, Fungal Genet Biol; Noack-Schönmann et al. 2014, AMB Express) for detailed studies. DHN-deficient mutants generated by targeted mutation of biosynthetic genes were studied with regard to the architecture of the cell wall and the EPS (extracellular polymeric substances) matrix, attachment to and weathering of olivine, as well as the tolerance to abiotic and biotic stresses. We will discuss the critical role of the outer cell surface (DHN melanin and EPS) in adhesion to the substrate and subsequent damage of the colonized surface.
Municipal solid waste incineration (MSWI) is one of the leading technologies for municipal solid waste (MSW) treatment in Europe. Incineration bottom ash (IBA) is the main solid residue from MSWI, and its annual European production is about 20 million tons. The composition of IBA depends on the composition of the incinerated waste; therefore, it may contain significant amounts of ferrous and non-ferrous (NFe) metals as well as glass that can be recovered. Technologies for NFe metals recovery have emerged in IBA treatment since the 1990s and became common practice in many developed countries. Although the principles and used apparatus are nearly the same in all treatment trains, the differences in technological approaches to recovery of valuable components from IBA – with a special focus on NFe metals recovery – are summarized in this paper.
Morphologically simple and microbially dominated ecosystems termed “biofilms” have existed on Earth for a long period of biosphere evolution. A model biofilm combining one heterotroph and one phototroph component was used in a laboratory experiment to simulate biogenic weathering with two different specimens of basic rock samples from the soil profiles. The rocks fragments from the regions of cold environments of Eurasia,where abiotic physical processes, including rock disintegration initiated by freezing–thawing cycles, represent the most probable Scenario of rock weathering, were subjected to biological colonization. The rock Fragments were represented by dolerite and metagabbro amphibolites. Polished sections of the rock samples were inoculated with the model microbiological consortium of the oligotrophic fungus and the phototrophic cyanobacteria (biofilm). After 3 month runtime of the experiment the progress of rock weathering was derived from the growth of the biofilm on the rock surfaces. The model biofilm visualization on the rock surface of polished sections illustrated their stronger development namely on dolerite in comparison with metagabbro amphibolite. The findings confirmed the higher sensitivity of dolerite to biogenic weathering due to (i) mineral association, in which quartz was absent and (ii) porosity providing higher specific surface area for biotic—abiotic interaction influenced by the occurrence of micro-porosity in the rock.
Dem Fachbeirat Bodenuntersuchungen des BMBF/UBA wurden die abschließenden Ergebnisse zum UFOPLAN-Forschungsvorhaben „Monitoring zur Verwertung von Bodenmaterial“ vorgestellt. Die potentielle Auswirkung der neuen Regularien in der geplanten Novelle der BBodSchV (4. Referentenentwurf der Mantelverordnung) auf die Erweiterung der Verwertungsmöglichkeiten von Bodenmaterialien wurden aufgezeigt.
Mit der Novellierung der Bundes-Bodenschutz- und Altlastenverordnung (BBodSchV) (am 6.11.2020 im Bundesratsverfahren beschlossen) werden Regelungen zum Auf- und Einbringen von Bodenmaterial außerhalb der durchwurzelbaren Bodenschicht aufgenommen (sogenannte Verfüllungen). Ziel des Vorhabens war es, durch die Auswertung vorhandener und durchzuführender Untersuchungen eine Einstufung von Bodenmaterialien (jährlich fallen weit über 100 Mio. Tonnen davon an) für bestimmte Verwertungswege vornehmen zu können. Es sollte herausgefunden werden, ob Veränderungen hinsichtlich des Verwertungspotentials nachgewiesen werden können.
Basis für die Durchführung und Bewertung waren die neuen Regelungen (hier insbesondere die Untersuchung mit einem Wasser/Feststoffverhältnis von 2:1, neue nationale und europäische Elutions- und Untersuchungsverfahren) der novellierten BBodSchV. Der Fokus lag dabei auf den polyzyklischen aromatischen Kohlenwasserstoffen (PAK) sowie ausgewählte anorganische Stoffe (Schwermetalle und Anionen) unter der Berücksichtigung unterschiedlicher Bodenmaterialien zur Verwertung.
Dabei handelte es sich um:
- Böden aus urban geprägten Gebieten,
- Oberböden aus dem Straßenrandbereich in Form von Bankettschälgut,
- Baggergut aus Gewässern mit Verdacht auf eine Kontamination,
- Bergematerial (Mischung von Abraum- und Bodenmaterial),
- Auenböden mit vermuteten Verunreinigungen aus Industrie und Gewerbe.
Anhand der vorgelegten Ergebnisse kann nun eine Versachlichung der Diskussion um Ressorcenschutz vs. Schadlosigkeit der Verwertung erfolgen. Sie zeigen für die untersuchten Stoffe, dass bei einer Einführung der §§ 6-8 Novelle BBodSchV mit einer Erhöhung der Verwertungsquote für Bodenmaterial gerechnet werden kann. Eine Erhöhung des Deponievolumens ist somit nicht zu befürchten. Neben den ermittelten Daten konnten Grundlagen für die Überarbeitung verschiedener DIN-Normen für Bodenuntersuchungen erarbeitet werden.
Monodisperse iron oxide nanoparticles as reference material candidate for particle size measurements
(2020)
In order to utilize and rationally design materials at the nanoscale the reliable characterization of their physico-chemical properties is highly important, especially with respect to the assessment of their environmental or biological impact. Furthermore, the European Commission’s REACH Regulations require the registration of nanomaterials traded in quantities of at least 1 ton. Powders or dispersions where 50% (number distribution) of the constituent particles have sizes ≤ 100 nm in at least one dimension are defined as nanomaterials. This creates a need for industrial manufacturers and research or analytical service facilities to reliably characterize potential nanomaterials. Currently, BAM is developing reference nanoparticles, which shall expand the scarce list of worldwide available nano reference materials certified for particle size distribution and will also target other key parameters like shape, structure, porosity or functional properties. In this respect, materials like iron oxide or titanium dioxide are considered as candidates to complement the already available silica, Au, Ag, and polystyrene reference nanoparticles.
The thermal decomposition of iron oleate precursors in high boiling organic solvents can provide large quantities of iron oxide nanoparticles that can be varied in size and shape.[1, 2] The presence of oleic acid or other hydrophobic ligands as capping agents ensures stable dispersion in nonpolar solvents. Such monodisperse, spherical particles were synthesized at BAM and pre-characterized by electron microscopy (TEM, SEM including the transmission mode STEM-in-SEM) and dynamic light scattering comparing cumulants analysis and frequency power spectrum.
1. REACH regulations and nanosafety concerns create a strong need for nano reference materials with diverse properties.
2. Iron oxide nanoparticles are under development as new candidate reference material at BAM.
3. Narrow particle size distribution confirmed by light scattering and electron microscopy.
Museumsvitrinen sollen Kunst- und Kulturgut „ins rechte Licht“ setzen und vor Diebstahl oder Vandalismus schützen. Vergleicht man historische Schauvitrinen, die zumeist aus einfachen Glasscheiben in Holzrahmungen bestehen, mit heutigen Konstruktionen, lässt sich eine Entwicklung zu hochtechnisierten Gebilden ablesen, die deutlich mehr Ansprüchen genügen müssen als in der Vergangenheit.
Zahlreiche Beispiele verdeutlichen, dass Kunstwerke nicht nur außerhalb, sondern auch innerhalb von Museen oder Archiven ungünstigen Umwelteinflüssen ausgesetzt sind. So können Einbauten bzw. Dekorationen in Ausstellungsräumen, Aufbewahrungsbehältnisse in Depoträumen oder Ausstellungsvitrinen flüchtige Substanzen, sogenannte VOCs (Volatile Organic Compounds) freisetzen, die zu irreversiblen Veränderungen an den Objekten führen und diese schädigen. Hierzu zählen organische Säuren, wie Ameisen- oder Essigsäure, aber auch Verbindungen, die Sulfide enthalten. Hier wird die an der BAM entwickelte BEMMA-Bewertungsmethode vorgestellt, die von Museen verwendet werden kann Materialien mit einem geringeren Emissionspotential auszusuchen.
This thesis addresses the development of a methodological approach for the non-invasive identification of colourants and for the classification of binding media in reverse glass paintings from the early 20th century. For this purpose, mobile and miniaturized devices were used to measure the paintings in situ. The methodology includes X-ray fluorescence (XRF), VIS spectroscopy (VIS), Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). In a first step the capabilities of DRIFTS for binding media classification and pigment identification were tested.
DRIFTS enables, besides Raman spectroscopy, the collection of molecular information of a substance that can be used as characteristic fingerprint spectrum. However, the simultaneous collection of both specular (surface) and diffuse (volume) reflection leads to complicated mixed DRIFT spectra, that can vary strongly for one substance depending on the dominant fraction of reflected light. Specular reflection causes several spectral distortions like inverted bands, band shifts and derivative-like features whereas pure diffuse reflections leads to an intensity enhancement of combination bands and overtones. Both specular and diffuse reflection cannot be optically separated, and their proportion depends on material properties like the absorption coefficient and the refractive index as well as on Parameters like surface roughness, porosity, grain size and angle of incidence and detection. A direct comparison of DRIFT spectra with IR spectra of other methods (e.g. transmission, ATR) is not possible, hence the creation of DRIFTS databases was needed. The next step was the complimentary utilization of Raman spectroscopy and DRIFTS for the dentification of synthetic organic colourants. Such colourants are in the further chapters called synthetic organic pigments (SOP) even when it’s not always entirely clear if they are soluble dyes or pigments that are practically insoluble in the medium in which they are incorporated. Raman spectroscopy is generally the method of choice when dealing with SOP, but fluorescence can hamper the Raman spectrum severely, inhibiting the proper identification of the pigment.
DRIFTS was successfully applied and several SOP like synthetic alizarin (PR83), the yellow azo pigments (e.g. PY1) or the red and orange β-naphthol pigments (e.g. PR3) could be identified in the paintings solely by means of DRIFTS. The holistic methodological sequence was defined after the successful establishment of DRIFTS as serious analytical alternative. As the time is always the most limiting factor for in situ measurement campaigns in museums, the 9
sequence needs to be time saving but also efficient. The methodology starts with quick measurements by XRF and VIS to get a first idea of the pigment composition, followed by the validation of the results with the vibrational spectroscopies for selected points.
Measurements of reverse glass paintings by Carlo Mense and Wassily Kandinsky were conducted to test the entire procedure. A high number of pigments could be identified, including several rare ones like strontium white (SrSO4), PR60 and PB52. The binding media were classified using the previously recorded references. The results were set in the art historian context and were discussed in a multidisciplinary way. The influence of Asian art, especially of Chinese reverse glass paintings as source of inspiration for artists of the “Blauer Reiter” collective (e.g. Wassily Kandinsky, Gabriele Münter, Franz Marc und Heinrich Campendonk) is shown. Non-invasive measurements of two Chinese reverse glass paintings from the late 19th and early 20th century were conducted, enabling a comparison of the palettes of Chinese and European painters. The Chinese palette includes heavy use of red lead and orpiment, pigments that were hardly sed in Europe anymore. More modern pigments like zinc white, cadmium yellow, viridian, chromates, cobalt blues or SOP were not found at all in the Chinese paintings.
Timber is constantly exposed to environmental influences under outdoor conditions which limits its Lifetime and usability. In order to counteract the damaging processes caused by insects, we have developed a novel and more environmentally friendly method to protect wood materials via covalent modification by organic insecticides. Starting with an important class of synthetic insecticides which are derived from the natural insecticide nicotine, various new carboxylic acid derivatives of imidacloprid were made accessible. These activated neonicotinoids were utilized for the chemical modification of wood hydroxy groups. In contrast to conventional wood preservation methods in which biocides are only physically bound to the surface for a limited time, the covalent fixation of the preservative guarantees a permanent effect against wood pests, demonstrated in standardized biological tests. Additionally, the environmental interaction caused by non-bound neonicotinoids is significantly reduced, since both, a smaller application rate is required and leaching of the active ingredient is prevented. By minimizing the pest infestation, the lifetime of the material increases while preserving the natural appearance of the material.
Der Verwertung von Bodenmaterialien wird auf Grund des Volumens dieses Stoffstromes eine hohe umweltpolitische Bedeutung beigemessen. Dabei ist unter Gewährleistung des Vorsorge- und Nachhaltigkeitsprinzips eine möglichst hochwertige Verwertung anzustreben, um natürliche Ressourcen zu schonen und die Beseitigung von Abfällen weitestgehend zu vermeiden.
Die vorgesehene Novelle der BBodSchV enthält in den Paragraphen 6 bis 8 neue Vorgaben hinsichtlich des Auf- und Einbringens von Bodenmaterialien unterhalb oder außerhalb einer durchwurzelbaren Bodenschicht. So soll die Möglichkeit eingeräumt werden, Bodenmaterialien mit Feststoffgehalten von regulierten Stoffen zwischen dem einfachen und doppelten Vorsorgewert einer weiteren Verwertung zuzuführen unter der Voraussetzung, dass die Eluatwerte eingehalten werden.
Im Rahmen eines Forschungsvorhabens des Umweltbundesamtes (FKZ: 3716 74 203 0) wurden unterschiedliche Bodenmaterialien (Baggergut, Bankettschälgut, Stadt- und Auenböden, Bergematerial), die unter diese Kriterien fallen, mit besonderem Fokus auf PAK hinsichtlich ihres Verwertungspotentials untersucht.
Dabei wurden auch die Auswirkungen der Umstellung des Elutionsverfahrens von einem Wasser-Feststoffverhältnis (W/F) von 10 l/kg auf ein W/F von 2 l/kg auf die Einstufung von Bodenmaterialien betrachtet.
Insbesondere für die Stoffgruppe der PAK konnte gezeigt werden, dass sich mit Verabschiedung der neuen Regelungen zusätzliche Verwertungsmöglichkeiten von Bodenmaterialien außerhalb der durchwurzelbaren Bodenschicht eröffnen und deren Deponierung teilweise vermieden werden kann.
Abstract: Since it is unknown for many applications, which PFASs are used and how they enter the environment, target analysis-based methods reach their limits. The two most frequently used sum parameters are the adsorbable organically bound fluorine (AOF) and the extractable organically bound fluorine (EOF). Both can be quantified using either combustion ion chromatography (CIC) or high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Here we provide an insight on the advantageous and disadvantageous of both sum parameters and both detection methods. Our study is based on the analysis of surface water samples. Next to total fluorine (TF) analysis, AOF and EOF were determined as well as CIC and HR-CS-GFMAS are compared and results are comparatively discussed. Fluorine mass balancing revealed that, the AOF/TF proportion was higher than the EOF/TF proportion. The AOF made up 0.14–0.81% of TF and the EOF 0.04–0.28% of TF. Although, organically bound fluorine represents only a small portion of TF, PFASs are of worldwide concern, because of their extreme persistence and their bioaccumulation potential. The EOF-HR-CS-GFMAS method turned out to be more precise and sensitive than the AOF-CIC method and is a promising tool for future monitoring studies/routine analysis of PFASs in the environment.
Das Element Phosphor ist für Pflanzen, Tiere und Menschen essenziell. Um die Phosphorversorgung für Pflanzen in der Landwirtschaft zu gewährleisten, werden Phosphordünger eingesetzt. Die Nährstoffe werden hauptsächlich durch Wirtschaftsdünger (Gülle, Jauche, Stallmist) zurückgeführt. Zusätzlich werden in der konventionellen Landwirtschaft mineralische Phosphordünger eingesetzt, die vorwiegend aus dem fossilen Rohstoff Phosphorit gewonnen werden. Um die Abhängigkeit von fossilen Rohstoffen zu reduzieren, sollen nährstoffhaltige Rest- und Abfallstoffe zur Phosphordünger aufbereitet werden. In Abwasserkläranlagen fällt phosphorreicher Klärschlamm als Abfallstoff an. Der größte Anteil des Klärschlammes wird in Steinkohlekraftwerken, Zementwerken oder in Monoklärschlammverbrennungsanlagen verbrannt. Die Klärschlammaschen aus den Monoverbrennungsanlagen enthalten bis zu 12 Gew.-% Phosphor und sind daher für die Düngerherstellung geeignet.
Ein geeignetes Verfahren zur Aufbereitung der Klärschlammaschen ist die thermochemische Behandlung im Drehrohrofen. Mit dem sogenannten AshDec®-Prozess, kann ein Phosphordünger hergestellt werden. Aktuell wird eine großtechnische Anlage in Altenstadt (Bayern) geplant, die im Jahr 2023 den Betrieb aufnehmen soll. Der zentrale Bestandteil ist die Phasenumwandlung von schlecht pflanzenverfügbaren Phosphaten in der Klärschlammasche (vorwiegend das Calciumphosphat Whitlockit und Aluminiumphosphat) zu gut pflanzenverfügbaren Calciumalkaliphosphaten im Produkt. Um dies zu erzielen, werden die Aschen mit Natrium- und/oder Kalium-Verbindungen gemischt und einer thermochemischen Behandlung bei 800-1000 °C zugeführt. Um die Pflanzenverfügbarkeit und Düngewirkung von Phosphaten abschätzen zu können, ist die chemische Extraktionsmethode mit neutraler Ammoniumcitratlösung geeignet.
In der Dissertation werden die (Phosphor-)Phasenreaktionen und die Prozessbedingungen des thermochemischen Verfahrens untersucht, um das Verfahren gezielt zu modifizieren und die Wirtschaftlichkeit zu steigern. Die Zielphasen der thermochemischen Behandlung sind die Calciumalkaliphosphate CaNaPO4 und CaKPO4, und deren Mischphasen Ca(Na,K)PO4, welche in der Publikation 3.1 synthetisiert wurden. Für diese Calciumalkaliphosphate wurden die thermodynamischen Daten der Standardbildungsenthalpie, Standardentropie, Wärmekapazität und die Wärmemenge der Phasenumwandlung bestimmt (Publikation 3.1).
Bei der thermochemischen Behandlung von Klärschlammaschen wurden als Additive Natrium- und Kaliumsulfat bei verschiedenen Temperaturen getestet. Der Einsatz von Kaliumadditiven ist erwünscht, um den Marktwert des Produktes durch die Produktion eines Phosphor-Kalium-Düngers zu erhöhen. Zusätzlich wird eine möglichst geringe Prozesstemperatur angestrebt, bei der die erwünschten Calciumalkaliphosphate gebildet werden.
In den Publikationen 3.2 und 3.3 wird gezeigt, dass für Klärschlammaschen eine komplette Phasenumwandlung zu Calciumnatriumphosphaten ab 875 °C in Laborversuchen (Korundtiegel) mit dem Additiv Natriumsulfat erzielt werden kann. Der Einsatz von Kaliumsulfat erforderte notwendige Reaktionstemperaturen von über 1100 °C. Diese
unterschiedlichen Reaktionstemperaturen hängen mit den Schmelzpunkten von Natriumsulfat (890 °C) und Kaliumsulfat (1070 °C) zusammen. Um Kaliumsulfat in den Prozess bei niedrigen Temperaturen zu integrieren, wurden Natriumsulfat und Kaliumsulfat vor der Behandlung gemischt. Dies führte zu einer Schmelzpunkterniedrigung und resultierte in Reaktionstemperaturen zwischen 900 °C bis 1000 °C für die untersuchten Mischungen von Natrium- und Kaliumsulfat (Publikation 3.3).
Die Zusammensetzung der Calciumalkaliphosphate Ca(Na,K)PO4 war anders als erwartet. Bei der Phasenanalytik stellte sich heraus, dass bei geringem und mittlerem Anteil von Kaliumsulfat im Alkali-Additiv nur Calciumnatriumphosphate mit sehr geringen Kaliumgehalten gebildet wurden. Erst bei einem hohen Anteil von Kaliumsulfat in der Mischung der Alkalisulfate konnten kaliumhaltige Calciumalkaliphosphate nachgewiesen werden (u.a. (Ca0.9Mg0.1)(Na0.6K0.4)PO4). Dieser geringere Einbau von Kalium in die Calciumalkaliphosphate hängt mit den zusätzlich stattfindenden Reaktionen zwischen den Alkalien und den Silikaten zusammen. Es ist bekannt, dass die zugegebenen Alkalisulfate zuerst mit Silikaten und anschließend mit den Phosphaten reagieren. Silikate bauen bevorzugt Kalium ein, deswegen konnten erst kaliumhaltige Phosphate gebildet werden, wenn die Reaktion mit den Silikaten abgeschlossen war. Dies führte zu einem geringeren Kaliumanteil in den gebildeten Phosphaten im Vergleich zum Kaliumanteil der verwendeten Alkaliadditive. Das in Silikaten gebundene Kalium ist wahrscheinlich schlecht für die Pflanzen verfügbar. Dies könnte den Einsatz der produzierten Phosphor-Kalium-Dünger einschränken. Der bevorzugte Kaliumeinbau in Silikaten konnte auch in Kalkulationen mit den thermodynamischen Daten aus der Publikation 3.1 gezeigt werden.
Mittels Phasenanalytik vor und nach der chemischen Extraktion, konnte die Zugehörigkeit zu verschiedenen Modifikationen der Calciumalkaliphosphaten sicher bestimmt werden und eine ungefähre Zusammensetzung dieser Calciumalkaliphosphate abgeschätzt werden. So konnte nachgewiesen werden, dass die Modifikation vom CaNaPO4 ungefähr 10 % Magnesium einbauen kann. Wenn mehr Magnesium eingebaut wird, bildet sich die Phase (Ca,Mg)NaPO4, die eine vergleichbare Struktur wie die bekannte Phase (Ca0.72Mg0.28)NaPO4 aufweist. Dieses magnesiumreiche Calciumnatriumphosphat entstand vermutlich, wenn entweder erhöhte Anteile an Kalium eingebaut wurden (Ca0.8Mg0.2)(Na0.85K0.15)PO4 (Publikation 3.3) oder die Phasenumwandlung vom Calciumphosphat Whitlockit zum Calciumalkaliphosphat CaNaPO4 noch nicht abgeschlossen war (Publikation 3.2). Wenn mehr Kalium eingebaut wird, dann entsteht eine Phase (u.a. (Ca0.9Mg0.1)(Na0.6K0.4)PO4) ähnlich zu den Mischphasen aus der Publikation 3.1.
In den Publikationen 3.4 und 3.5 wurden keine Klärschlammaschen untersucht, sondern Biokohlen aus Modellklärschlämmen (Publikation 3.5) und Biomasseaschen (Publikation 3.4) aus der Vergasung oder Verbrennung einer Mischung aus Zuckerrohrbagasse und Hühnertrockenkot. Die thermochemischen Produkte der Biokohlen bzw. Biomasseaschen enthielten das gewünschte CaNaPO4 und hatten eine hohe Düngewirkung in Pflanzenwachstumsversuchen mit Sojapflanzen bzw. Gräsern.
Das Element Phosphor ist für alle Lebewesen essenziell und wird beispielsweise von Pflanzen in Form von Phosphaten aufgenommen.
In der landwirtschaftlichen Produktion werden dem Boden die Phosphate durch Wachstum und Ernte der Pflanzen entzogen und müssen ihm in Form von Phosphatdüngemitteln wieder zugeführt werden, um die Nahrungsmittelproduktion zu sichern. Rohphosphat stellt die Grundlage unserer derzeitigen Phosphatdüngemittel dar, ist aber gleichzeitig ein endlicher Rohstoff.
Des Weiteren sind insbesondere sedimentäre Rohphosphate oftmals mit erheblichen Konzentrationen toxischer Schadstoffe wie Cadmium, Uran und Thorium belastet. Eine Kreislaufführung des Phosphats sollte erfolgen, um natürliche Rohstoffvorkommen zu schonen und den Eintrag von Schadstoffen auf unsere Böden zu unterbinden.
Es wurden erste Ergebnisse des Projekts extraWERT vorgestellt. Im Projekt werden monatlich Klärschlammproben von 10 kommunalen Kläranlagen untersucht, deren P-Gehalt im Grenzbereich der AbfKlärV liegt zwischen 1,7 und 2,3%. Die ersten Ergebnisse lagen zu fünf Kläranlagen vor, es wurden Daten zum TS-Gehalt, zur oTS und zu den Nährstoffgehalten präsentiert.
In the present study, a simple approach was used to investigate the effect of UV-exposure on two high density Polyethylene materials (PE-HD), commonly used for storage tanks, on fuel sorption behavior and colonization by microorganisms. The aim was to investigate whether the sorption behavior of the fuels (diesel/biodiesel) and the colonization by microorganisms, frequently occurring in the fuel, is affected and may lead to undesirable or safety-relevant material changes. We showed that the UV-irradiation leads to significant changes of the sorption behavior due to chemi-crystallization and crosslinking. The fuel Sorption is affected by the UV-induced formation of polar carbonyl and hydroxyl groups predominantly occurring at the surface. With respect to microbial colonization behavior for Bacillus subtilis and Pseudomonas aeruginosa, isolated from a contaminated diesel sample, differences of the initial adhesion could be shown depending on the initial type of polyethylene as well as on the degree of UV-induced degradation.
Growing awareness of the impact of monoterpenes on climate, atmospheric chemistry, and indoor air quality has necessitated the development of measurement standards to globally monitor and control their emissions. For National Metrology Institutes to develop such standards, it is essential that they demonstrate measurement equivalence for assigned values at the highest levels of accuracy. This report describes the results of a pilot comparison for 4 key monoterpene species: α-pinene, 3-carene, R-limonene and 1,8-cineole, at a nominal amount-of-substance fraction of 2.5 nmol mol-1. The objective of this comparison is to evaluate participant capabilities to measure trace-level monoterpenes using their own calibration techniques.
Potential use of incineration bottom ash in construction – Evaluation of the environmental impact
(2020)
Knowledge of the long-term leaching behavior of potentially harmful substances is crucial for the assessment of the environmental compatibility of reusing municipal solid-waste incineration bottom ash (MSWI BA) in construction, i.e., as a road base layer.
BA fractions obtained from wet-processing aiming at the improvement of environmental quality were used to investigate the mobility of relevant substances. Eluates from laboratory-scaled leaching procedures (column percolation and lysimeters) were analyzed to learn about the long-term release of substances. Unsaturated conditions and artificial rainwater (AR) were used in the lysimeter tests to simulate field conditions. In addition, batch test eluates were generated at usual liquid-to-solid ratios (L/S) for compliance testing purposes. A variety of cations and anions was measured in the eluates.
The wet treatment reduces the leaching of chloride and particularly sulfate by more than 60%. The release of typical contaminants for the treated MSWI BA such as the heavy metals Cu and Cr was well below 1% in the conducted leaching tests.
An increase in the Sb concentration observed in the lysimeter experiments starting at L/S 0.75 L/kg and in the column experiment at L/S 4 L/kg is assumed to be related to decreasing concentrations of Ca and thus to the dissolution of sparingly soluble calcium antimonate. The same leaching mechanism applies with V, but the concentration levels observed are less critical regarding relevant limit values. However, on the long term the behavior of Sb could be problematic for the application of MSWI BA in construction.
In Bayern wird Klärschlamm aus der kommunalen Abwasserreinigung weitgehend verbrannt. Monoverbrennungsanlagen - ausschließlich für kommunalen Klärschlamm - gibt es in Altenstadt, München, Gendorf, Straubing, Neu-Ulm und zukünftig auch in Augsburg. Die Anlage in Altenstadt verbrennt jährlich ca. 55.000 t Klärschlamm-Trockensubstanz und produziert dabei rund 15.000 t phosphatreiche Aschen.
Die Asche aus Altenstadt wird zurzeit überwiegend direkt landwirtschaftlich genutzt. Aufgrund der niedrigen Schadstoffgehalte ist diese Nutzung nach den düngemittelrechtlichen Regelungen gesetzlich zulässig. Um der Intention der neuen Düngeverordnung (26. Mai 2017) nach hocheffizienten, d.h. gut pflanzenverfügbaren Düngemitteln zu entsprechen, ist eine Aufbereitung der Klärschlammasche geplant. Im Rahmen des R-Rhenania Projektes errichten der Betreiber der Klärschlammverbrennungsanlage Altenstadt in Bayern Emter GmbH - und der Düngemittelhersteller sePura GmbH gemeinsam eine AshDec®-Demonstrationsanlage, die im Jahr 2023 den Betrieb aufnehmen soll. Das angewandte AshDec®-Verfahren schließt die Phosphate in der Klärschlammasche thermisch im Drehrohrofen auf und macht diese für Pflanzen vollständig verfügbar. Gleichzeitig werden Schadstoffe wie Arsen, Blei und Cadmium entfernt. Den thermischen Aufschluss kennt man bereits vom erfolgreichen, aber nicht mehr produzierten Düngemittel „Rhenania-Phosphat“, das auf der Basis von Rohphosphaten hergestellt wurde.
Die geplante Anlage wird neben den Aschen aus Altenstadt zusätzlich die Aschen aus weiteren bayerischen Verbrennungsanlagen verwerten und für eine Kapazität von 30.000 Jahrestonnen Asche ausgelegt sein. Der Projektpartner sePura plant den produzierten Dünger vollständig in Bayern zu verwerten. Dies verringert die Umweltbelastung durch lange Transportwege und fördert die Regionalität des Vorhabens.
Da das Recycling von tantalhaltigen Post-Consumer-Abfällen praktisch nicht existiert, stellen metallurgische Reststoffe eine äußerst wichtige Rohstoffquelle für das Tantalrecycling dar. Die meisten Zinnerze enthalten von Natur aus erhebliche Mengen an Refraktärmetallen. Diese Elemente werden in den Schlacken der pyrometallurgischen Primärzinngewinnung angereichert. Aufgrund ihrer vergleichsweise hohen Wertstoffkonzentration und ihrer Funktion als zusätzlicher Schlackenbildner stellen diese Schlacken einen wertvollen Rohstoff für die Verhüttung tantalhaltiger Reststoffe dar. In der vorliegenden Arbeit wird ein existierendes Verfahren zur Tantalrückgewinnung diskutiert, dem hauptsächlich pyrometallurgische Rückstände geringer Wertstoffkonzentration als Einsatzstoff dienen. Mit Hilfe des Verfahrens sollte dasoxidisch vorliegende Tantal vollständig reduziert und in der Metallphase angereichert werden. Weiterhin sollte vermieden werden, dass unerwünschte Elemente wie Titan in die Metallphase überführt werden. Ziel der Untersuchung war es, die ablaufenden Reduktionsprozesse besser zu verstehen, um so Ansätze für die Prozessoptimierung identifizieren zu können.
Weltweit werden etwa 80–85 % aller abgebauten Rohphosphate für die Produktion von Düngemitteln verwendet. Bei noch steigendem Bedarf an Phosphor (P) geht man derzeit davon aus, dass die weltweiten P-Reserven noch über 200 Jahre ausreichen. Um den P-Vorrat langfristig abzusichern, sollte der in Reststoffen enthaltene Phosphor möglichst umfänglich genutzt werden. Dieser Forderung trägt das von der Bundesregierung 2012 erstmals beschlossene Deutsche Ressourceneffizienzprogramm ProgRess Rechnung. Rohphosphat wird auch seitens der Europäischen Kommission aufgrundseiner ökonomischen Bedeutung und des unsicheren Angebots als „kritischer Rohstoff“ eingestuft. Vor diesem Hintergrund hat die Bundesregierung in der Verordnung zur Neuordnung der Klärschlammverwertung vom 27. September 2017 in Deutschland eine verpflichtende technische Rückgewinnung von Phosphor für Abwasserbehandlungsanlagen ab einer Ausbaugröße von 100.000 Einwohnerwerten (12 Jahre nach Inkrafttreten der Verordnung) bzw. ab einer Ausbaugröße von über 50.000 Einwohnerwerten (15 Jahre nach Inkrafttreten der Verordnung) vorgeschrieben. Die Verordnung enthält keine Vorgaben hinsichtlich der anzuwendenden Technologie bei der Phosphorrückgewinnung. Ausgenommen von der Rückgewinnungspflicht sind Klärschlämme mit niedrigen Phosphorgehalten (weniger als 20 Gramm Phosphor je Kilogramm Klärschlamm-Trockenmasse). Auch die im Jahre 2017 verabschiedeten neuen Rechtsvorschriften für die Düngung verlangen zukünftig einen nachhaltigen und ressourceneffizienten Umgang mit Nährstoffen bei der landwirtschaftlichen Erzeugung und schränken die P-Zufuhr insbesondere auf hoch versorgten Böden ein (Düngeverordnung vom 26. Mai 2017). Dies wird zu einem mehr am Pflanzenbedarf orientierten und ggf. vermehrt überbetrieblichen Einsatz von wirtschaftseigenen Düngern führen. Um den politischen und gesetzlichen Anforderungen gerecht zu werden, müssen einerseits wirksame und kosteneffiziente technische Verfahren zum P-Recycling (weiter)entwickelt werden. Andererseits müssen die Recyclingprodukte die Anforderungen für eine direkte Verwendung in der Landwirtschaft oder als Rohstoff für die Herstellung von Düngemitteln erfüllen. In dem vorliegenden Standpunkt wird zunächst der potenzielle Beitrag von Reststoffen zur Deckung des P-Bedarfs in der deutschen Pflanzenproduktion geschätzt. Für die wichtigsten Reststoffe werden technische Verfahren zur P-Rückgewinnung bzw. Aufarbeitung skizziert. Auf Basis der Anforderungen der Landwirtschaft bzw. der Düngemittelindustrie
an die P-Recyclingprodukte werden deren Herstellungsverfahren bewertet. Schließlich wird der Regelungs- und Forschungsbedarf formuliert.
Over the past two decades, per- and polyfluoroalkyl substances (PFASs) have emerged as worldwide environmental contaminants, calling out for sophisticated treatment, decomposition and remediation strategies. In order to mineralize PFAS pollutants, the incineration of contaminated material is a state-of-the-art process, but more cost-effective and sustainable technologies are inevitable for the future. Within this review, various methods for the reductive defluorination of PFASs were inspected. In addition to this, the role of mechanochemistry is highlighted with regard to its major potential in reductive defluorination reactions and degradation of pollutants. In order to get a comprehensive understanding of the involved reactions, their mechanistic pathways are pointed out. Comparisons between existing PFAS decomposition reactions and reductive approaches are discussed in detail, regarding their applicability in possible remediation processes. This article provides a solid overview of the most recent research methods and offers guidelines for future research directions.
The physical and chemical analysis of aerosols using reliable and physically traceable methods is important for the thorough investigation of airborne particles to support a better understanding of their origin as well as their health and climate impacts. Within the European Metrology Research AeroMet project,the aim of hysikalisch–Technische Bundesanstalt’s (PTB) X-ray spectrometry group is to develop and establish traceable and reliable X-ray methods to measure the elemental mass deposition per unit area, the elemental composition,and the chemical binding state of particulate matter supported by a flat substrate. This approach can substantially contribute to support quantitative analytical methods during on-site measurement campaigns where portable Instrumentation is employed by qualifying suitable calibration samples for commercial analytical X-ray instruments and by investigating samples collected during the field campaign.
Wood protection technology in the marine environment has changed over the last decades and will continue to do so. New active ingredients, newer formulations, and novel wood-based materials including physically- and chemically-modified wood, together with increasing concerns over environmental impacts of wood preservatives, urgently demand a major revision of EN 275 “Wood preservatives – Determination of the Protective Effectiveness against Marine Borers”, dated from 1992. This IRG document reports on the technical work in CEN TC 38 regarding the revision of this standard. A Task Group within WG 24 of CEN TC 38 was formed consisting of experts from different field of competence (e.g. wood preservatives industry, wood scientists, marine biologists, archaeologists and cultural heritage conservators). Starting by e-mail correspondence in 2014, and continuing with four physical meetings (Berlin 2x, Florence, Venice) with experts from Germany, Italy, Sweden, and UK were held so far. Significant items for revision in EN 275 were identified as: number of replicates, duration of the test, dimension of specimens, number of test sites, number of reference species, reference material including reference preservative, re-immersion of specimens after non-destructive periodical evaluation for longer periods of time vs higher number of replicates for successive destructive examinations without re-immersion, utilization of X- ray apparatus and specific software to ease evaluation, etc.
Furthermore, the task group is working on a standardized lab test for time-saving evaluation of different wood qualities for their potential to resist attack by limnorids. The suitability of this lab test will be determined by round robin tests as soon as safe face-to-face collaboration permits. The outcome will be published as a CEN TR (Technical Report) document, with a view to eventual adoption within the revised standard.
This study investigated the adaptation of the state-of-the-art test procedure for the determination of emissions of volatile organic compounds (VOC) from materials into indoor air to test for the radon exhalation from stony construction products. A complete robustness validation including all relevant parameters showed that the procedure can be well applied by testing institutes already holding available the required VOC testing infrastructure that solely needs to be complemented by calibrated commercial radon measurement instrumentation. When measurements of the radon exhalation from construction materials become mandatory by law, test capacity can easily be applied. This work can serve as a recommendation for the European standardisation that still is on hold in this point.
Eine Vielzahl unterschiedlicher Materialien findet für die farbliche Gestaltung von Zeichnungen Verwendung. Einige Pigmente und Farbstoffe, d.h. Tinten, Stifte oder Kreiden, waren nur für den Gebrauch als Zeichenmittel vorgesehen – andere wiederum finden sich auch in der Tafel- oder Fassmalerei. Ausgehend von schwarzen Zeichenmaterialien soll zunächst eine allgemeine Typologie der Farbmittel entwickelt werden, um den Kosmos dieser Vielfältigkeit zu illustrieren. In einem zweiten Teil werden farbige Elemente am Beispiel von Rötel in Zeichnungen hinterfragt, deren Funktion und Bedeutung sich aus der Betrachtung heraus nicht unbedingt sofort erschließt. So diente die Farbe hier weder der naturgetreuen Nachahmung, noch wurde sie für eine nachträgliche Wertsteigerung eingesetzt. Der dritte Teil dieses Exkurses widmet sich schließlich solchen „farbigen“ Elementen, deren Konnotationen sich aus den Zeichnungen nicht ermitteln lassen und die daher zunächst irritieren. Diese vermeintliche Farbigkeit war aber ursprünglich vielleicht gar nicht intendiert, sondern ist vielmehr auf Alterungs- und Korrosionsprozesse zurückzuführen.
Antimicrobial touch surfaces have been introduced in healthcare settings with the aim of supporting existing hygiene procedures, and to help combat the increasing threat of antimicrobial resistance. However, concerns have been raised over the potential selection pressure exerted by such surfaces, which may drive the evolution and spread of antimicrobial resistance. This review highlights studies that indicate risks associated with resistance on antimicrobial surfaces by different processes, including evolution by de-novo mutation and horizontal gene transfer, and species sorting of inherently resistant bacteria dispersed on to antimicrobial surfaces. The review focuses on antimicrobial surfaces made of copper, silver and antimicrobial peptides because of the practical application of copper and silver, and the promising characteristics of antimicrobial peptides. The available data point to a potential for resistance selection and a subsequent increase in resistant strains via cross-resistance and co-resistance conferred by metal and antibiotic resistance traits. However, translational studies describing the development of resistance to antimicrobial touch surfaces in healthcare-related environments are rare, and will be needed to assess whether and how antimicrobial surfaces lead to resistance selection in These settings. Such studies will need to consider numerous variables, including the antimicrobial concentrations present in coatings, the occurrence of biofilms on surfaces, and the humidity relevant to dry-surface environments. On-site tests on the efficacy of antimicrobial Coatings should routinely evaluate the risk of selection associated with their use.
The polyphyletic group of black fungi within the Ascomycota (Arthoniomycetes, Dothideomycetes, and Eurotiomycetes) is ubiquitous in natural and anthropogenic habitats. Partly because of their dark, melanin-based pigmentation, black fungi are resistant to stresses including UV- and ionizing-radiation, heat and desiccation, toxic metals, and organic pollutants. Consequently, they are amongst the most stunning extremophiles and poly-extreme-tolerant organisms on Earth. Even though ca. 60 black fungal genomes have been sequenced to date, [mostly in the family Herpotrichiellaceae (Eurotiomycetes)], the class Dothideomycetes that hosts the largest majority of extremophiles has only been sparsely sampled. By sequencing up to 92 species that will become reference genomes, the “Shed light in The daRk lineagES of the fungal tree of life” (STRES) project will cover a broad collection of black fungal diversity spread throughout the Fungal Tree of Life. Interestingly, the STRES project will focus on mostly unsampled genera that display different ecologies and life-styles (e.g., ant- and lichen-associated fungi, rock-inhabiting fungi, etc.). With a resequencing strategy of 10- to 15-fold depth coverage of up to ~550 strains, numerous new reference genomes will be established. To identify metabolites and functional processes, these new genomic resources will be enriched with metabolomics analyses coupled with transcriptomics experiments on selected species under various stress conditions (salinity, dryness, UV radiation, oligotrophy). The data acquired will serve as a reference and foundation for establishing an encyclopedic database for fungal metagenomics as well as the biology, evolution, and ecology of the fungi in extreme environments.