4 Material und Umwelt
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- 4 Material und Umwelt (162)
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- 4.4 Thermochemische Reststoffbehandlung und Wertstoffrückgewinnung (24)
- 4.3 Schadstofftransfer und Umwelttechnologien (10)
- 6 Materialchemie (7)
- 6.2 Material- und Oberflächentechnologien (5)
- 1 Analytische Chemie; Referenzmaterialien (4)
Eingeladener Vortrag
- nein (73)
Our research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo) as well as other medieval Jewish and Armenian communities.
The presentation shows the panorama of historic inks and our attempt to follow up the transition of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age.
While studying the socio-geographic history of inks, division 4.5 of the Bundesanstalt für Materialforschung und Prüfung (BAM) together with the Centre for the Study of Manuscript Cultures (CSMC) in Hamburg has developed a non-invasive protocol for ink analysis. It consists of a primary reflectographic screening to determine the type of the ink (soot, tannin or iron-gall) and a subsequent in-depth analysis using several spectroscopic techniques: X-ray fluorescence (XRF), Infrared and Raman spectroscopies. The first of them, XRF elemental analysis aims at establishing the unique fingerprints of inks containing metals or trace elements in carbon inks. In addition, we use Raman analysis to identify so-called mixed inks, an ink category that received little attention so far. Finally, with the help of IR spectroscopy we obtain information about the ink binders.
Our experimental knowledge about the inks of antiquity and late antiquity rarely goes beyond their visual description. In rare cases, inks typology has been determined by means of microscopy and reflectography, i.e. using their physical and optical properties, respectively. Since carbon, plant and iron gall inks belong to different classes of compounds they could be easily distinguished had only pure inks been used. Even these crude observations suggest that the inks used differed greatly in their composition.
Reconstruction of the ink recipes with the help of advanced non-destructive analytical techniques could serve as a powerful accessory for in the studies of ancient papyri.
The proposed paper will present a short survey of the methods of material analysis and the challenges offered by ancient inks. The examples of the ink studies from the collections of the Israel Museum in Jerusalem and Egyptian Museum in Berlin will conclude the paper.
The initial focus of this research was on the development of a general workflow for the documentation and monitoring of historical stained glass windows using structured light scanning.
Therefore windows from different churches, time periods and with different corrosion and damage phenomena were scanned before and after conservation measures.
The initial focus of this research was on the development of a general workflow for the documentation and monitoring of historical stained glass windows using structured light scanning. Therefore windows from different churches, time periods and with different corrosion and damage phenomena were scanned before and after conservation measures. To evaluate the execution of the restoration measures the data was compared using 3D inspection software to examine the differences in geometry between the two scans. Various problems had to be solved, for example, how to deal with heavily reflective surfaces and the extreme contrast between light and dark surfaces, as seen in the borders between ‘Schwarzlot’ painting and plain glass. The application of materials for matting the surfaces, such as Cyclododecane spray, was impossible due to the high accuracy of the surface measurement required for 3D inspection. Regarding the contrast differences of the surfaces, the creation of exposure fusions and the use of polarization filters to reduce reflections were tested. In addition to the general problems encountered when recording translucent surfaces, the historical glasses caused additional problems in calculating surface comparisons. For example, the windows have to be moved and turned around several times, both during the conservation process and while scanning, causing deformations of the geometry due to the flexible lead rods allowing a certain degree of movement.
OECD test guideline on particle size and size distribution: Comparability of measurement results
(2019)
OECD-Prüfrichtlinien werden weltweit für regulatorische Zwecke angewandt, da sie eine harmonisierte und über internationale Ringversuche validierte Vorschrift zur Analyse vorgeben. Die bestehende Prüfrichtlinie TG 110 zur Größencharakterisierung von Partikeln und Fasern ist für viele Methoden und Materialklassen nicht geeignet, weswegen es Bedarf an einer Neuentwicklung gibt. Im Fokus der neuen TG steht die reproduzierbare und vergleichbare Anwendung von Methoden zur Bestimmung von Partikelgröße sowie Größenverteilung annährend sphärischer und faserförmiger Nanomaterialien im Bereich 1-1000 nm. Berücksichtigt werden die häufig angewandten Methoden zur Größencharakterisierung mit ihren unterschiedlichen physikalisch-technischen Limitierungen und die Bestimmung unterschiedlicher Durchmesser (hydrodynamischer, Feret…). Weiterhin sind materialspezifische Einflüsse durch die Partikel sowie das Messmedium zu berücksichtigen. Jede der Methoden soll unter Berücksichtigung von ISO-Standards und den materialspezifischen Limitierungen in der neuen Prüfrichtlinie beschrieben und über einen Ringversuch validiert werden.
Questions:
Biocides are in contact with soils through direct application and passive leaching from protected materials. Consequently, soil microorganisms are exposed to toxic 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).
Methods:
In laboratory evolution experiments we culture selected model soil microorganism with representative biocides followed by antibiotic cross-resistance determination and genome sequencing. Moreover, we investigate if the selected biocides affect the HGT frequency of plasmids that carry resistance genes among soil microorganism and the consequences for survival of the affected populations.
Results:
Our initial results show only small increases of biocide resistance during serial transfers in the presence of biocides. One reason for this might be the narrow selective window for biocide resistance due to steep dose-response relationships. Furthermore, we will present results from ongoing experiments on the effects of material preservatives on HGT frequencies facilitating microbial community adaptation to stress.
Conclusions:
The results will enable future risk assessment regarding resistance evolution for biocides used as material preservatives.
Question:
Biocides are in contact with soils through direct application and passive leaching from protected materials. Consequently, soil microorganisms are exposed to toxic 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).
Methods:
In laboratory evolution experiments we culture selected model soil microorganism with representative biocides followed by antibiotic cross-resistance determination and genome sequencing. Moreover, we investigate if the selected biocides affect the HGT frequency of plasmids that carry resistance genes among soil microorganism and the consequences for survival of the affected populations.
Results:
Our initial results show only small increases of biocide resistance during serial transfers in the presence of biocides. One reason for this might be the narrow selective window for biocide resistance due to steep dose-response relationships. Furthermore, we will present results from ongoing experiments on the effects of material preservatives on HGT frequencies facilitating microbial community adaptation to stress.
Conclusions:
The results will enable future risk assessment regarding resistance evolution for biocides used as material preservatives.
Question:
Biocides are in contact with soils through direct application and passive leaching from protected materials. Consequently, soil microorganisms are exposed to toxic 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).
Methods:
In laboratory evolution experiments we culture selected model soil microorganism with representative biocides followed by antibiotic cross-resistance determination and genome sequencing. Moreover, we investigate if the selected biocides affect the HGT frequency of plasmids that carry resistance genes among soil microorganism and the consequences for survival of the affected populations.
Results:
Our initial results show only small increases of biocide resistance during serial transfers in the presence of biocides. One reason for this might be the narrow selective window for biocide resistance due to steep dose-response relationships. Furthermore, we will present results from ongoing experiments on the effects of material preservatives on HGT frequencies facilitating microbial community adaptation to stress.
Conclusions:
The results will enable future risk assessment regarding resistance evolution for biocides used as material preservatives.
Tricalcium-silicate (C3S) or Alite is the most important mineral in Portland cement. Since pure tricalcium-silicate is only stable above temperatures of 1250 °C, its decomposition has to be prevented technically by fast cooling after the sintering process. At room temperature, the decomposition velocity is very slow so that metastable tricalcium-silicate is obtained.
Although the mechanisms of clinker phase formation during burning process of Portland cement in a rotary kiln were solved and improved over the years, in view of possible economic and ecological benefits current projects aim to produce clinker phases from metallurgical slags. Recent studies discovered that the mineral phase which remained after a reducing treatment and separation of formed metallic iron from molten Linz-Donawitz (LD-) slags contained about 60 wt.% Alite despite it was cooled slowly. Because the results could be verified using slags from different origins and varying cooling velocities a chemical stabilisation of the Alite can be assumed. First tests in mortars indicate that workability, hardening and solid state properties are comparable with an ordinary Portland cement. An application of the observed phenomenon in cement production requires enhanced knowledge about formation and stabilisation conditions of Alite during crystallisation from melts in contrast to the sintering reactions in conventional Portland cement production. Therefore, this study focuses on the stabilisation mechanisms of Alite in consolidating melts. Samples from different melting experiments are analysed to determine stabilising factors.
Background:
One cornerstone to prevent the spread of antibiotic resistant bacteria in clinical settings is the application of disinfectants. However, bacteria can evolve resistance to disinfectants, which in turn can confer cross-resistance to antibiotics. Additionally, clonal bacterial populations can display phenotypic heterogeneity with respect to the tolerance of antibiotic stress leading to a prolonged survival of a sub-population; this phenomenon is termed persistence. Persistence to antibiotics is an evolvable trait and can serve as a stepping stone for the evolution of genetically encoded resistance. Until now, there is a lack of systematic studies that investigate if bacterial populations establish persister subpopulations that tolerate disinfectant stress longer than most of the population.
Objectives:
Our objective is to investigate if persistence is a bacterial survival strategy against disinfectants. Furthermore, we investigate the mechanisms of disinfectant persistence and if persistence can evolve in the face of fluctuating exposure to disinfectants. Lastly, we test if the evolved mechanisms of disinfectant tolerance lead to disinfectant resistance and if they confer cross-tolerance and cross-resistance against antibiotics.
Methods:
We use time-kill assays in the presence of disinfectants and experimental evolution combined to whole-genome sequencing in the model organism E. coli.
Results:
We find persister sub-populations against chlorhexidine and quaternary ammonium compounds, but not to alcohols, aldehydes and oxidative compounds. We will present the relationship of mechanisms known to underlie antibiotic persister formation to the formation of persisters against disinfectants. In addition, we will present data from an ongoing evolution experiment for persistence against disinfectants.
Question:
One cornerstone to prevent the spread of bacteria in clinical and industrial settings is the application of biocides including disinfectants and preservatives. However, bacteria can evolve resistance to biocides, which in turn can confer cross-resistance to antibiotics. Additionally, clonal bacterial populations can display phenotypic heterogeneity with respect to the tolerance of antibiotic stress leading to a prolonged survival of a sub-population; this phenomenon is termed persistence. Persistence to antibiotics is an evolvable trait and can serve as a stepping stone for the evolution of genetically encoded resistance. Until now, there is a lack of systematic studies that investigate if bacterial populations establish persister subpopulations that tolerate disinfectant stress longer than most of the population. Our objective is to investigate if persistence is a bacterial survival strategy against biocides. Furthermore, we investigate the mechanisms of biocide persistence and if persistence can evolve in the face of fluctuating exposure to biocides. Lastly, we test if the evolved mechanisms of biocide tolerance lead to biocide resistance and if they confer cross-tolerance and cross-resistance against antibiotics.
Methods:
We use time-kill assays in the presence of biocides and experimental evolution combined to whole-genome sequencing in the model organism E. coli.
Results:
We find persister sub-populations against chlorhexidine and quaternary ammonium compounds, but not to alcohols, aldehydes and oxidative compounds. We will present the relationship of mechanisms known to underlie antibiotic persister formation to the formation of persisters against biocides. In addition, we will present data from an ongoing evolution experiment for persistence against biocides.
Conclusion
There is a link between antibiotic and biocide persistence with possible implications for antibiotic resistance evolution and spread.
A fundamental question in ecology is how biodiversity affects ecosystem function. Biodiversity is commonly estimated based on genetic variation. We investigated a new approach that defines and measures biodiversity in complex microbial communities. We used the variation in multiple functionally-relevant, phenotypic traits measured in parallel in single cells as a metric for microbial phenotypic diversity. We studied phenotypic diversity and ecosystem functioning throughout different photosynthetic layers dominated by divergent microbial communities in the gradient of Lago di Cadagno. We determined genetic diversity by 16S and 18S amplicon sequencing and bulk ecosystem functioning (photosynthesis). In addition, we determined phenotypic diversity using single-cell technologies such as nanometer-scale secondary ion mass spectrometry (NanoSIMS) correlated with confocal laser scanning microscopy (CLSM) and scanning flow-cytometry. We measured functional trait variation between individuals in 13CO2 fixation, 15NH4+ uptake, and variation in physio-morphological cell traits, such as cell size, shape, and auto-fluorescence for various pigments related to photosynthesis. We used the distances between individuals in a multidimensional trait space to derive phenotypic trait-based diversity indices, such as trait richness, trait evenness, and trait divergence. We find that phenotypic trait divergence associates with ecosystem functioning, whereas genetic diversity does not. Including activity-based, single-cell phenotypic measurements with NanoSIMS provided an additional accuracy to the trait-based diversity assessment and allowed us to formulate hypotheses on the mechanisms that shape the correlation between phenotypic diversity and eco-system function. Together, our results show that phenotypic diversity is a meaningful concept to measure microbial biodiversity and associate it with ecosystem functioning.
A fundamental question in ecology is how biodiversity affects ecosystem function. Biodiversity is commonly estimated based on genetic variation. We investigated a new approach that defines and measures biodiversity in complex microbial communities. We used the variation in multiple functionally-relevant, phenotypic traits measured in parallel in single cells as a metric for microbial phenotypic diversity. We studied phenotypic diversity and ecosystem functioning throughout different photosynthetic layers dominated by divergent microbial communities in the gradient of Lago di Cadagno. We determined genetic diversity by 16S and 18S amplicon sequencing and bulk ecosystem functioning (photosynthesis). In addition, we determined phenotypic diversity using single-cell technologies such as nanometer-scale secondary ion mass spectrometry (NanoSIMS) correlated with confocal laser scanning microscopy (CLSM) and scanning flow-cytometry. We measured functional trait variation between individuals in 13CO2 fixation, 15NH4+ uptake, and variation in physio-morphological cell traits, such as cell size, shape, and auto-fluorescence for various pigments related to photosynthesis. We used the distances between individuals in a multidimensional trait space to derive phenotypic trait-based diversity indices, such as trait richness, trait evenness, and trait divergence. We find that phenotypic trait divergence associates with ecosystem functioning, whereas genetic diversity does not. Including activity-based, single-cell phenotypic measurements with NanoSIMS provided an additional accuracy to the trait-based diversity assessment and allowed us to formulate hypotheses on the mechanisms that shape the correlation between phenotypic diversity and eco-system function. Together, our results show that phenotypic diversity is a meaningful concept to measure microbial biodiversity and associate it with ecosystem functioning.
Microorganisms perform multiple metabolic functions that shape the global cycling of elements, health and disease of their host organisms, and biotechnological processes. The rates, at which different metabolic activities are performed by individual cells, can vary between genetically identical cells within clonal populations. While the molecular mechanisms that result in such metabolic heterogeneity have attracted considerable interest, the environmental conditions that shape heterogeneity and its consequences have received attention only in recent years. Here, we review the environmental drivers that lead to metabolic heterogeneity with a focus on nutrient limitation, temporal fluctuations and spatial structure, and the functional consequences of such heterogeneity. We highlight studies using single-cell methods that allow direct investigation of metabolic heterogeneity and discuss the relevance of metabolic heterogeneity in complex microbial communities.
Fungi that share light-flooded habitats with phototrophs may profit from excess photosynthetic products. But to cope with sunlight-associated 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 fungi from phyllosphere and exposed solid surfaces contain multiple photoreceptors (PRs). The filamentous foliar 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 Dothideo- and Eurotiomycetes including Knufia petricola possess equal numbers of PRs along with the same set of protective pigments. This similarity between black fungi from plant and rock surfaces suggests that photoperception and photoregulation are important for fungi that avoid loss of energy and nutrients through cooperation with phototrophs.
Black yeasts form a polyphyletic group of Ascomycota that colonize bare surfaces like rocks, facades of buildings, and solar panels. Their protective adaptations enable an adequate response to fluctuating and diverse temperature, water and UV radiation stresses. Together with bacteria and algae they form sub-aerial biofilms (SAB) this way discoloring and weathering the surfaces they grow on. Strain A95 of Knufia petricola (Eurotiomycetes, Chaetothyriales) displays both typical yeast-like cell growth and constitutive dihydroxynaphthalene (DHN) melanogenesis. Along with the cyanobacterium Nostoc punctiforme as photobiont, it is already used in a model system for studying SAB formation and bio-weathering. Applying the recently developed tools for the generation of deletion mutants will allow to define gene functions and to identify genes critical for abiotic and biotic interactions. We present a chromosome-level genome assembly and annotation for K. petricola A95. The genome was assembled with MaSuRCA using a hybrid assembly approach of Illumina MiSeq and PacBio SMRT sequencing data. The resulting assembly consists of 17 contigs including the complete mitochondrial genome and five complete chromosomes. It shows indication of repeat-induced point mutations (RIP). Supported by RNA sequencing data from eight different growth conditions, 10,994 genes were predicted with the BRAKER2 pipeline. Functional annotation of genes was obtained from general functional annotation databases and the fungal specific database FungiPath. Comparative analyses are in progress to identify genes specific to black yeasts, that may facilitate the survival on exposed surfaces. In sum, the genome sequence of K. petricola is a valuable resource to gain insight into the protein inventory and functional pathways of extremotolerant and symbiosis-capable fungi.
Fungi that share light-flooded habitats with phototrophs may profit from excess photosynthetic products. But to cope with sunlight-associated 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 fungi from phyllosphere and exposed solid surfaces contain multiple photoreceptors (PRs). The filamentous foliar 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 Dothideo- and Eurotiomycetes including Knufia petricola possess equal numbers of PRs along with the same set of protective pigments. This similarity between black fungi from plant and rock surfaces suggests that photoperception and photoregulation are important for fungi that avoid loss of energy and nutrients through cooperation with phototrophs.
Sunlight, the major source of energy, drives life but in excess it provokes UV-induced DNA damage, accumulation of reactive oxygen species, desiccation, osmotic stresses and so on. Biological strategies to survive excess light include protection, avoidance and active utilisation. Phototrophic organisms including cyanobacteria, green algae and plants use all three strategies. Fungi occupying phototrophic niches may profit from the surplus photosynthetic products which also obliges them to cope with the same light-induced stresses. One way of handling these stresses would be to use similar signalling pathways to sense the presence and to interact with their phototrophic partners. Obviously, the levels of adaptation and responses to light will depend on the environment as well as fungal genotype and phylogenetic position. Black fungi – a polyphyletic group – accumulate the dark pigment DHN melanin in their cell walls and often occupy light-flooded habitats from phyllosphere to rock surfaces. Here we compare two sequenced melanised fungi of different lifestyles in their response to light.
The Leotiomycete Botrytis cinerea is an aggressive pathogen that primarily infects the above-ground parts of plants. It possesses large numbers of photoreceptors that respond to a broad spectrum of light. As a consequence, light controls morphogenesis in which it induces conidiation for disease spreading and represses sclerotial development for survival and/or sexual recombination. Cellular components involved in photo-perception and regulation of morphogenesis, stress responses and virulence have been identified and appear to regulate propagation, survival and infection. These include phytochromes, a group of photoreceptors which are particularly enriched in the Leotiomycetes and that mediate coordinated responses to light and elevated temperatures. Assuming that photo-regulation may be equally important for fungi that live in mutualistic relationships with phototrophs either by forming composite organisms or biofilms, we investigate the role of light in the rock-inhabiting Eurotiomycete Knufia petricola. Like other black yeasts, K. petricola grows slowly, does not form specialised reproductive structures and constitutively produces DHN melanin as well as carotenoids. Combining K. petricola with the cyanobacterium Nostoc punctiforme, we developed a model system for studying biofilm formation and bio-weathering. A genetic toolbox to manipulate this model system is being developed. K. petricola strain A95 possesses ten putative photoreceptors, more than found in filamentous Eurotiomycetes suggesting that light plays an important role for abiotic and biotic interactions in extremo-tolerant and symbiosis-capable fungi.
In this study, femtosecond laser-induced sub-micrometer structures are generated to modify polyethylene (PE) surface topographies. These surfaces were subjected to bacterial colonization studies with Escherichia coli and Staphylococcus aureus as test strains. The results reveal that the nanostructures do not influence S. aureus coverage, while the adhesion of E. coli is reduced.
The OECD test guidelines (TGs) for testing chemicals have been widely used for regulatory purposes all over the world since the establishment of the Mutual Acceptance of Data (MAD) principle in 1984. This MAD principle ensures that, if a chemical is tested under the Good Laboratory Practice (GLP) conditions accordingly to an OECD TG, the data should be accepted in all OECD countries. The TGs have been developed, harmonized, internationally validated (round robin tests) and adopted by OECD countries to be used for the physical-chemical characterisation, fate estimation, and hazard identification for risk assessment of various chemicals. In addition to the TGs, OECD Guidance Documents (GDs) usually provide guidance on how to use TGs and how to interpret the results. These GDs do not have to be fully experimentally validated, and hence they are not under MAD, but they are based on relevant published scientific research.
But are the existing TGs and the related GDs applicable and adequate for the regulatory testing of nanomaterials? In general, for nanomaterials it is accepted that most of the "endpoints" or more precisely measurement variables are applicable. However, for some endpoints new or amended TGs are needed. In addition, several GDs are needed to give more precise advice on the test performance in order to gain regulatory relevant data on nanomaterials.
Microbiologically induced corrosion due to bacterial biofilms causes several problems in industrial systems, technical applications and in medicine. Prior to the formation of a biofilm on a substrate, planktonic cells attach on the surface. Hence, the properties of the surface play a key role in biofilm formation and are of great importance for the development of strategies to prevent bacterial attachment and biofilm formation.
This project aims at clarifying to which extent surface micro-/nanostructuring and chemical functionalization affects bacterial attachment and whether a synergistic combination of the two can be used to control bacterial adhesion. To answer these questions, model surfaces with regular patterns of 5-10 micrometers in size have been prepared, which provide distinct zones differing in terms of their chemistry or nano-roughness. This was achieved by micro contact printing of self-assembled monolayers with different functional groups and deposition of patterned ZnO nanorod arrays for studying the effect of surface chemistry and morphology, respectively. Typical contrasts studied were combinations of positively/negatively charged, hydrophobic/hydrophilic or flat/rough.
The attachment behavior of bacteria on tailored surfaces were studied in a flow chamber as a function of time. The strain Pseudomonas fluorescens SBW25 was chosen as a model organism. DNA-intercalating dyes such as Syto9 have a high affinity to adsorb on ZnO nanorods. To overcome this limitation a genetic modification was performed by introducing a gene which expresses a green fluorescent protein in P. fluorescens SBW25 enabling the quantitative evaluation of the flow chamber studies by means of fluorescence microscopy. Further analysis of the attachment behavior was performed by means of scanning electron microscopy.
The presentation will summarize the results of our systematic study on the role of individual parameters on bacterial attachment and highlight synergistic combinations, showing an inhibition or enhancing effect. As the investigations with model substrates enable a precise control of the surface parameters, this approach can be applied to different microorganisms and material systems to achieve a correlative description of bacterial adhesion on solid surfaces.
The miraculously preserved 2000-year-old Dead Sea Scrolls, ancient texts of invaluable historical significance, were discovered in the mid-20th century in the caves of the Judean desert. The texts were mainly written on parchment and exhibit vast diversity in their states of preservation. One particular scroll, the 8-m-long Temple Scroll is especially notable because of its exceptional thinness and bright ivory color. The parchment has a layered structure, consisting of a collagenous base material and an atypical inorganic overlayer. We analyzed the chemistry of the inorganic layer using x-ray and Raman spectroscopies and discovered a variety of evaporitic sulfate salts. This points toward a unique ancient production technology in which the parchment was modified through the addition of the inorganic layer as a writing surface. Furthermore, understanding the properties of these minerals is particularly critical for the development of suitable conservation methods for the preservation of these invaluable historical documents.
Measurements of aerosol particles are vital for enforcing EU air quality regulations to protect human health, and for research on climate change effects. Although metrics such as PM10 and PM2.5 are currently in use, the level of uncertainty of aerosol metrics is too high and the traceability is insufficient. The project AEROMET, which has been started in June 2017 aims at implementing improvements in a) the uncertainty of particle mass, size and number concentration measurements and b) in the characterization of regulated components in airborne particles. Both are demanded by existing networks within the EU as well as by global atmospheric research.
On-site measurement campaigns
One of the objects is the application of mobile x-ray spectroscopy techniques combined with aerosol sampling techniques for quantifying particle compositions in the field for real time analysis. During two in-field measurement campaigns in Budapest, Hungary in May 2018 and Cassino, Italy in September 2018 the size dependent mass concentrations of specific elements in ambient aerosols were monitored under dynamic conditions.
Typically, airborne particles are sampled on filter substrates. During this project new sampling methods with specially designed substrate holders for an in-situ TXRF analysis were developed and applied for the first time. This approach allows a direct time and size resolved analysis without laborious digestion steps and a reduced risk of contamination.
Aerosol particles were sampled in a 13-stage DLPI impactor - size range from 0,03 µm to 10 µm - which was equipped with special adapters for acrylic discs of 30 mm diameter, serving as substrates. TXRF analysis was performed on site with the transportable spectrometer S2 PICOFOX (Bruker Nano GmbH) equipped with a Mo X-ray tube and a 30 mm² Silicon Drift Detector (SDD). Excitation conditions were 50 kV, 600 µA, measurement time 1000 s. Quantification was based on internal standardization using 50 ng of Y in solution, which was pipetted into the centre of the discs prior to sampling.
At moderate air pollution levels, i.e. PM10 ~ 20 µg/m³, sampling times of less than 2 hours were enough for the detection of elements in different particle size bins. The in-situ approach and the high sensitivity of TXRF enables the observation of rather quick changes in the quantity and distribution of elements in an ambient aerosol on the day of sampling, as the below example from the Cassino field campaign on 11 Sept. 2018 shows: The analysis of the morning and afternoon sampling shifts reveals the occurrence of the elements Fe, Ca and Si in different size bins as well as their significant temporal change in respective mass concentrations over the day while the distributions of several other elements in the aerosol remain unchanged.
The validation of these results by backup measurements is planned.
A mobile Bruker S2 Picofox TXRF spectrometer has been used in two field campaigns within the EMPIR env07 AEROMET project for the on-site analysis of cascade impactor aerosol samples.The results show that even at moderate air pollution levels – i.e.PM10 fairly below 20 μg/m³ - element mass concentrations in air in the range of 100 pg/m³could be measured in up to 13 size bins after sampling times of less than only 0.5 days.
Today glass is broadly used in modern architecture. For indoor applications it is possible to produce decorated glass by using enamel colours and glass painting techniques without any problems. However, this is more limited for applications out of doors. Humidity and environmental pollution attack the surface of the coating and can damage it. There are only a few colours on the market which are resistant towards acids and bases until now. Additionally, most of those colours are opaque. To extend the colour palette, chemically resistant low melting coloured glasses are being developed which are transparent and intensively toned even in thin coating thicknesses. To achieve such an ambitious aim, many parameters have to combine and act in a complex manner. New compositions of lead borosilicate, zinc borosilicate and lead-zinc borosilicate glasses were produced and milled as powder. The thermal properties as well as the environmental stability were analysed. The influence of PbO and ZnO on the thermal properties and the environmental stability were investigated. Evaluation of the fusing results shows that the production and mixture of transparent vitreous enamels for the exterior side of glasses is possible. The tests made it clear that the original materials for making the vitreous enamels must be excellently ground and prepared to achieve a satisfactory result. The method to produce durable vitreous enamels for exterior application also seems to allow the production of glass colours.
Since it was realized that sites contaminated with metals and radionuclides needed treatment, various remediation methods have been and are being developed. Depending on the size of the contaminated site and urgency of intervention, conventional or recently introduced techniques have been used. Conventional techniques include excavation and removal for treatment of soil and contaminants, or the so-called “pump-and-treat” method, in which contaminated groundwater is removed from the ground by pumping and treated in a treatment plant on the surface. It has the advantage of using proven techniques and is easy to control, and the treated groundwater can be reinjected into the ground or discharged in rivers or lakes. Novel methods include permeable reactive barriers, biomineralization, and electrokinetic remediation.
Waste, Evaluation Methods
(2019)
It is difficult to decide which waste management system fulfills best predefined sustainability goals such as maximum materials and energy recovery, least environmental impact, and lowest societal cost. Such decisions are based on many parameters. However, several evaluation methods exist with different scope and output, and the application of one or more evaluation methods provides an objective comparison of alternatives.
In the transition to the Circular Economy (CE) model, where the added value of products is kept as long as possible and waste is eliminated, the sustainable management of raw materials plays a key role. In above CE model, especial attention is paid to CRMs which are economically and strategically important for the European economy, but have a high-risk associated with their supply.
One of the most important element which can not be replaced and is an essential element for human nutrition, yet limited resource is phosphorus (P). An importance of issues related to sustainable P management results from EU legislation, which indicated P as a Critical Raw Material (CRM).
The sustainable management of P-resources is especially important for the Baltic region. A consequence of waterborne loads passing into the sea, mainly as wastewater with a high P content is the eutrophication of the Baltic Sea environment. Due to the largest inputs of P (37%) into the Baltic Sea originate from Poland, the development of sustainable solutions aimed at more rational P management for this country is externally important.
Due to the vital importance of phosphorus (P) and its increasing scarcity as a natural resource, phosphorus recovery has recently gained significant scientific and technical interest. An interesting sources of phosphorus are sewage sludge (SS) and sewage sludge ash (SSA) due to the major part of the phosphate from P rich wastewater is transferred to the sludge (approx. 90%). Despite the fact that the raw materials base is large (PURE report indicates that in 2020 the amount of sewage sludge generated in Poland will reach 180% of the dry matter of sewage sludge produced in 2010), at present recycling of phosphorus is not a commonly used practice in Poland.
Phosphorus (P) recycling from sewage sludge for agricultural needs has to meet requirements for agricultural implementation, such as short and long-term P-plant-availability under field conditions. Field experiments often bring no evaluable results, because agricultural soils got a high potential of P-supply even if they are classified as low in P-supply according to the CAL extraction method. The present study presents a possible way to investigate the P-plant-availability of P-recycling-fertilizers under field-like conditions. The plant experiments are firstly performed in small Mitscherlich pots in growth chambers and subsequently in containers with a high soil volume of 170 kg under greenhouse conditions, in which plants can grow until ripening. The tested P-recycling fertilizers were produced from sewage sludge in a large-scale thermal process. It was a two-step treatment process performed with a pyrolysis of sewage sludge at 550°C (SSC-550) and a subsequent thermochemical post-treatment at 950°C with Na2SO4 (SSA-Na) and HCl + Na2SO4 (SSA-HCl/Na) as additives. The results show, that the P-recycling-products from pyrolysis got an adequate long-term but a 65% lower short-term P-plant-availability compared to triple superphosphate. SSA-Na and SSA-HCl/Na show both a high short and longterm P-plant-availability comparable to triple-superphosphate. This can be explained by their highly plant-available P-compound CaNaPO4.
This work addresses the identification of synthetic organic pigments (SOP) in ten modern reverse paintings on glass (1912-1946) by means of an in-situ multi-analytical approach. The combination of the complimentary properties of mobile Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) enabled the detection of sixteen SOP even in complex mixtures with inorganic compounds and binders. For the β-naphthol pigments, both Raman and DRIFTS yield appropriate results. DRIFTS was the preferred method for the detection of synthetic alizarin (PR83). Its diagnostic band pattern even allows its detection in complex mixtures with mineral pigments, binders and fillers. Raman spectroscopy yielded distinctive spectra for the triaryl carbonium pigments (PG1, PV2, PR81) and the two-yellow azo SOP (PY3, PY12), whereas DRIFT spectra were affected by extensive band overlapping. This may also occur in Raman spectra, but in less problematic amounts. Fluorescence is the major problem with Raman and it significantly hampers the SOP spectra even with the 785 nm laser. On the one hand the big spot size of DRIFTS (10 mm) limits the technique to rather large sampling areas, whereas the use of a 50× objective for in-situ Raman measurements permits a focus on small spots and aggregated SOP flakes. Moreover, “environmental” factors like temperature changes, artificial light, limited space and vibrations when people pass by need to be considered for in-situ measurements in museums.
Finally, the results show the experimental use of SOP in modern reverse glass paintings. Among several rare SOP (e.g. PB52, PR81), two of them (PG1, PV2) have never been reported before in any artwork.
First insights into Chinese reverse glass paintings gained by non invasive spectroscopic analysis
(2019)
A non-invasive methodological approach (X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Raman spectroscopy) has been carried out to identify the pigments and classify the binding media in two Chinese reverse glass paintings (The Archer, Yingying and Hongniang) from the late 19th and early 20th centuries. The results reveal a combined use of traditional Chinese and imported European materials. Several pigments like cinnabar, lead white, orpiment, carbon black and copper-arsenic green (probably emerald green) were found in both paintings; red lead, artificial ultramarine blue, Prussian blue and ochre appear in at least one of the paintings.
The presence of portlandite (Ca(OH)2) along calcite (CaCO3) in the fine-grained, white backing layer of Yingying and Hongniang indicates the presence of limewash. In Chinese tradition, limewash was produced from clamshells, and was then sold as clamshell white. In contrast to the Japanese pigment, Chinese clamshell white was made of finely grounded shells, which were heated over a low fire. The residue (CaO) forms portlandite (Ca(OH)2) when water is continuously added. This water-rich mixture is applied on the painting. Portlandite reacts with atmospheric CO2 during drying and forms fine-grained calcite (CaCO3) [1,2].
The identification of emerald green (The Archer) suggests an earliest manufacturing date in the 1830s [3] and promotes the sinological dating of the painting. Drying oil was classified as a binding media in most areas of both paintings. However, the orange background of The Archer yielded prominent bands of both proteinaceous and fatty binder.
A non-invasive methodological approach has been carried out to identify the pigments and classify the binding media of the reverse painting on glass Kreuzabnahme (1914/15) by Carlo Mense.
Mense was a member of the group Rhenish Expressionists around August Macke and got interested in the technique of painting on the reverse side of a glass panel. The studied painting indicates a remarkably painted reverse and front side, which creates a unique visual appearance of the glass. The applied noninvasive, spectroscopic approach includes X-ray fluorescence, VIS spectroscopy, Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy. The measurements revealed inorganic Pigments mixed with drying oil as binder. Together with common pigments, such as lead white, barium sulphate, bone black, cinnabar, chrome yellow, ochre, and viridian, an unusual additional material was found, Strontium white.
This work highlights the rediscovery of the technique of reverse glass painting by the artists of the “Blaue Reiter” collective in the early 20th-century and focusses particularly on the role of Wassily Kandinsky (1866–1944). Kandinsky created more than 70 reverse paintings on glass and showed several of them in exhibitions together with paintings on canvas and cardboard, implying a coequal importance of these techniques. Four of his early (1911–1914) reverse glass paintings (Auferstehung, Allerheiligen II, Rudern, Apokalyptischer Reiter II) were selected for investigation and their iconography, painting techniques and painting materials were examined. Two paintings were executed on so-called cathedral glass, revealing a “hammered surface”, whereas Kandinsky used a corrugated glass panel for Rudern. A multi-analytical, non-invasive approach [X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), VIS spectroscopy (VIS), Raman spectroscopy] was taken to identify the pigments and classify the binding media. The results reveal a broad palette of materials. Several pigments like lead white, zinc white, Strontium yellow, Prussian blue, viridian, cadmium yellow, ultramarine blue, cinnabar and carbon black were found in most of the four paintings. The use of the rare synthetic organic pigments PR60 and PB52 is discussed. In two works of art, cadmium carbonate is associated with cadmium yellow. The identification of aluminium foil along with tin foils in Rudern indicates an early use of this material for reverse glass paintings.
This work presents a technical investigation of two Chinese reverse glass paintings from the late 19th and early 20th centuries. A multi-analytical, non-invasive approach (X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Raman spectroscopy) was used to identify the pigments and classify the binding media. The results reveal a combined use of traditional Chinese and imported European materials. Several pigments like cinnabar, lead white, orpiment, carbon black and copper-arsenic green (probably emerald green) were found in both paintings; red lead, artificial ultramarine blue, Prussian blue and ochre appear in at least one of the paintings. The proof of limewash (calcite and small amounts of portlandite) as a backing layer in Yingying and Hongniang indicates that clamshell white was also used for reverse glass paintings. Drying oil was classified as a binding media in most areas of both paintings. However, the orange background of The Archer yielded prominent bands of both proteinaceous and fatty binder.
This work addresses the identification of synthetic organic pigments (SOP) in eight modern reverse paintings on glass (1913–1946) by means of an in-situ multi-analytical approach. We combined the complementary properties of mobile Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to overcome the main disadvantages of each method: extensive band overlapping in DRIFT spectra and fluorescence problems in Raman spectra. A collection of DRIFTS reference spectra enables a precise pigment identification by DRIFTS and establishes this method as a serious non-destructive alternative for the identification of SOP. The group of β-naphthol pigments yielded valuable results for both methods, whereas synthetic alizarin (PR83) was preferentially detected by DRIFTS. Finally, uncommon triaryl carbonium pigments and two azo group-based yellows were identified in the paintings by means of Raman spectroscopy.
An understanding of the interactions of 2D nanomaterials with pathogens is of vital importance to developing and controlling their antimicrobial properties. In this work, the interaction of functionalized graphene with tunable hydrophobicity and bacteria is investigated. Poly-(ethylene glycol)-block-(poly-N-isopropylacrylamide) copolymer (PEG-b-PNIPAM) with the triazine joint point was attached to the graphene Surface by a nitrene [2 + 1] cycloaddition reaction. By thermally switching between hydrophobic and hydrophilic states, functionalized graphene sheets were able to bind to bacteria. Bacteria were eventually disrupted when the functionality was switched to the hydrophobic state. On the basis of measuring the different microscopy methods and a live/dead viability assay, it was found that Escherichia coli (E. coli) bacteria are more susceptible to hydrophobic interactions than B. cereus bacteria, under the same conditions. Our investigations confirm that hydrophobic interaction is one of the main driving forces at the presented graphene/bacteria interfaces and promotes the antibacterial activity of graphene derivatives significantly.
An existing pyrometallurgical process for tantalum and niobium recovery, mainly from low grade pyrometallurgical residues, was investigated. Series of melting experiments were carried out in a pilot-scale electric arc furnace to study how the amount, the grain size and the way of feeding affect the activity of carbon as a reducing agent. During the pyrometallurgical treatment refractory metals such as tantalum and niobium are reduced to their carbide form and enriched in the molten iron-based metal phase. The cooled down slag and metal phase were analysed to investigate thermodynamic and kinetic conditions of the carbide formation. FACT Sage simulations were also used to investigate the material system in state of thermodynamic equilibrium. Results show that mass transfer and kinetics may play an important role if compared to equilibrium analyses using FACT Sage.
An existing pyrometallurgical process for tantalum and niobium recovery, mainly from low grade pyrometallurgical residues, was investigated. Series of melting experiments were carried out in a pilot-scale electric arc furnace to study how the amount, the grain size and the way of feeding affect the activity of carbon as a reducing agent. During the pyrometallurgical treatment refractory metals such as tantalum and niobium are reduced to their carbide form and enriched in the molten iron-based metal phase. The cooled down slag and metal phase were analysed to investigate thermodynamic and kinetic conditions of the carbide formation. FACT Sage simulations were also used to investigate the material system in state of thermodynamic equilibrium. Results show that mass transfer and kinetics may play an important role if compared to equilibrium analyses using FACT Sage.
The church of Koszewko (Poland) is a brick building edified in the 15th century built on cobblestone foundations. There are five windows in the sanctuary. Three of them enclose heraldic panels from the Küssow’s family from the 15th century which are surrounded with Goethe glass from the 18th century to complete the windows. The colored heraldic panels are strongly damaged and corroded with massive paint layer losses, glass- and leadbreakages. Those medieval glass fragments have been shortly discovered and are of particular interest for Poland since only few medieval glazing have been conserved.
The damages as well as the glass compositions have been investigated with ESEM/EDX. Two categories of medieval glass compositions have been identified. The blue glass is particularly sensible to corrosion because of his high content in K2O. The colorless and the red glass samples belong to a stable glass type. Due to the thickness of the gel layer, it is easy to see that the degradation is strongly proceeded. The protection of those medieval stained-glass panels is absolute necessary.
The medieval panels have been restored and surrounded from a copper frame. Then they have been fixed on the wood frame in the church. The exterior glazing has been closed with a panel of Goethe glass. The gap between the Goethe- and the medieval glass is about 3 cm. The Goethe glass panel has been stabilized with a film based on polyester to protect the medieval glasses against any damages. In this way, a low cost protective glazing has been installed for a long-term conservation of each medieval stained-glass panels. The climate measurements over the period of one year on the restored windows are in process. The temperature and the relative humidity are recorded in the church interior, in the gap between the original and the Goethe glass and outdoors.
19th and 20th centuries glass paint layers consist of a colour body and a colourless lead silicate flux, in which borax or boric acid was added as further component to improve the paint ability and to reduce the firing temperature for multiple layers of paint. Model glasses were used in laboratory tests to investigate the stability of glass paints with additions of boron oxide. To determine boron in paint layers, a LIBS-system with pulsed NdYAG-laser was used.
Medieval stained-glass windows are protected by an outside gazing system in many churches.The interspace between the original and the protective glass is ventilated with air from the indoor or exterior environment, where dust and particles can move.Cascade impactor measurements and SEM/EDX analyses of sampled dust were carried to determine the dust composition. The effect of particles on model glass samples was investigated in climate chambers under accelerated weathering conditions. The results from in situ measurements and laboratory tests were combined to evaluate the potential effect of particulate matter on historic stained-glass Windows.
RNA virus populations are composed of highly diverse individuals that form a cloud of related sequences commonly referred to as a ‘quasispecies’1–3. This diversity arises as a consequence of low-fidelity genome replication4,5. By contrast, DNA Virus populations contain more uniform individuals with similar fitness6.
Genome diversity is often correlated with increased Fitness in RNA viruses, while DNA viruses are thought to require more faithful genome replication. During DNA replication, erroneously incorporated bases are removed by a 3′-5′ exonuclease, a highly conserved enzymatic function of replicative DNA but not RNA polymerases. This proofreading process enhances replication fidelity and ensures the genome integrity of DNA organisms, including large DNA viruses7. Here, we show that a herpesvirus can tolerate impaired exonucleolytic proofreading, resulting in DNA virus populations, which, as in RNA viruses8, are composed of highly diverse genotypes of variable individual fitness. This indicates that herpesvirus mutant diversity may compensate for individual Fitness loss. Notably, in vivo infection with diverse virus populations results in a marked increase in virulence compared to genetically homogenous parental virus. While we cannot exclude that the increase in virulence is caused by selection of and/or interactions between individual genotypes, our findings are consistent with quasispecies dynamics. Our results contrast with traditional views of DNA virus replication and evolution, and indicate that a substantial increase in population diversity can lead to higher virulence.
Leaching processes are responsible for the release of biocides from treated materials into the environment.
Adequate modeling of emission processes is required in order to predict emission values in the framework of the risk assessment of biocidal products intended for long-term service life. Regression approaches have been applied to data obtained from the long-term monitoring of biocide emissions in experiments involving semi-field conditions. Due to the complex interaction of different underlying mechanisms such as water and biocide diffusion and desorption, however, these attempts have proven to be of limited usefulness e at least, for the available biocide emission data. It seems that the behavior of the biocide emission curve depends to a considerable extent on whichever underlying mechanism is slowest at a given point in time, thus limiting the amount of biocide available for release. Building on results obtained in the past few years, the authors propose a criterion for determining which mechanism controls the leaching process at a given point in time based on the slope of the log-log emission curve. In addition, a first-order approximation of this slope value is presented which displays advantages both in terms of computability and interpretability. Finally, an algorithm for the determination of breakpoints in the slope of the log-log emission curve is presented for the demarcation of phases within which one mechanism acts as a limiting factor.
Biocides are commonly applied to construction materials such as facade renders and paints in order to protect them from microbial spoilage. These renders and paints are exposed to weathering conditions, e.g., sunlight and rain. Pigments are interacting intensively with the spectrum of the incoming light; thus, an effect of paint pigments on phototransformation rates and reaction pathways of the biocides is hypothesized.
In this study, the phototransformation of four commonly used biocides (carbendazim, diuron, octylisothiazolinone (OIT) and terbutryn) in four different paint formulations differing solely in pigments (red and black iron oxides, white titanium dioxide, and one pigment-free formulation) were investigated. Paints surfaces were irradiated under controlled conditions. The results show that biocides degrade most rapidly in the pigment-free formulation. The degradation in the pigment-free formulation followed a first-order kinetic model with the respective photolysis rate constants: kp,Diuron=0.0090 h−1, kp,OIT=0.1205 h−1, kp,Terbutryn=0.0079 h−1.
Carbendazim concentrations did not change significantly. The degradation was considerably lower in the pigment-containing paints. The determination of several phototransformation products of terbutryn and octylisothiazolinone showed different transformation product ratios dependent on the pigment. Consequently, pigments not only reflect the incoming light, but also interact with the biocide photodegradation.
Halomonas elongata is a halophilic γ-proteobacterium that synthesizes and accumulates the compatible solute ectoine to cope with osmotic stress in saline environments. Ectoine possesses protecting properties and stabilizes proteins as well as whole cells against stresses like ionizing radiation and cytotoxins. These properties make ectoine a highly demanded ingredient in cosmetics and pharmaceuticals. To date H. elongata is the industrial Producer strain of ectoine, but several metabolic factors for optimum ectoine production remain to be explored.
In this work, we used up to date Metabolic engineering approaches following the ‘Push, Pull, Block – strategy’ to examine targets that contribute to ectoine synthesis. Firstly, the basics of glucose catabolism were inspected to PUSH and enhance carbon flow towards ectoine synthesis. Secondly, lysine biosynthesis was targeted to BLOCK a pathway that is competing for precursors with ectoine synthesis. Thirdly, the mechanosensitive (MS) channels of H. elongata have been examined as possible excretion routes for ectoine. An overexpression of the ectoine excretion channels potentially could PULL out product at the end of ectoine synthesis and increase overall ectoine flux. For the interrogation of central metabolic pathways, we established the new molecular tool CRISPR-mediated interference (CRISPRi) for targeted modulation of gene expression.
PUSH Glucose catabolism through the Entner-Doudoroff (ED) and Emden-Meyerhof-Parnas (EMP) pathway was targeted with CRISPRi and examined on gene expression level for ist response to changing salinity and different carbon sources. Changing salinity did not influence gene expression levels of glucose catabolism but the carbon source glucose triggered glycolysis through the (ED) pathway. When gene expression of the ED pathway was downregulated with CRISPRi, the growth rates remained constant. The observations indicate a metabolic overflow mechanism for glycolysis, in which fluxes are constantly high - even at lower salinity when no resources are demanded for ectoine synthesis. The further analysis of glucose to product conversion rates will advise optimum conditions for future industrial cultivation processes.
BLOCK Lysine biosynthesis was downregulated with CRISPRi, which led to a significant increase in ectoine production. Hence, the blockage of lysine biosynthesis would be a valuable strategy for the optimization of the industrial producer strain in future studies.
PULL MS channels and ectoine regulation are inevitably connected in osmoadaptation. Therefore, ectoine excretion, growth performance and gene expression levels of the MS channels were monitored in steady state conditions and in response to osmotic shock in the wildtype strain and in a MS channel deletion mutant. We observed that the MS channels were essential for the survival of osmotic shock but surprisingly their presence reduced cell growth under high salinity. The MS channels were only partially responsible for ectoine excretion.
Thus, alternative ectoine excretion channels must exist and remain to be explored.
Specific co-fertilization of nutrients can enhance their plant-availability and thus the yield of plants. To investigate this effect, we performed a pot experiment with three different P-fertilizers and ammonium nitrate sulfate as a co-fertilizer, without and with a nitrification inhibitor (NI), and analyzed the form of nitrogen (N) in the soil via novel X-ray spectroscopic method. The application of NI with the N fertilizer led to a higher dry matter yield of maize. Novel N K-edge micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy identified that the application of a NI promotes the temporary formation of a non-exchangeable N in detectable hot-spots in the soil. The subsequent slow release and prolonged availability of N during plant growth leads to higher yield. It can be concluded that NIs lead to a temporary fixation of ammonium-N in a pool that can be accessed by plant roots. Those types of available nutrient pools meet the idea of so-called “next generation fertilizers” as plants have access to nutrients according to their current demand.
Previous research shows that analytical methods based on Diffusive Gradients in Thin films (DGT) provide very good correlations to the amount of bioavailable nutrients and pollutants in the environmental samples. However, these DGT results do not identify which compound of the specific element has the high bioavailability. Using various spectroscopic techniques (infrared, XANES and NMR spectroscopy) to analyze the dried DGT binding layers after deployment could allow us to determine the specific elements or compounds. Nutrients such as phosphorus and nitrogen are often, together with other elements, present as molecules in the environment. These ions are detectable and distinguishable by infrared and NMR spectroscopy, respectively. In addition, XANES spectroscopy allows for the specification of nutrients and pollutants (e.g. chromium) on the DGT binding layer. Furthermore, microspectroscopic techniques make it also possible to analyze compounds on the DGT binding layer with a lateral resolution down to 5 µm2. Therefore, species of elements and compounds of e.g. a spatial soil segment can be mapped and analyzed, providing valuable insight to understand the dynamics of nutrients and pollutants in the environment. Here we will present the advantages and limitations of this novel combination of techniques.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizer can also contain toxic pollutants e.g. chromium (Cr) in the hexavalent state (Cr(VI)), which is regulated with low limit values in agricultural products (German fertilizer ordinance limit: 2 mg/kg Cr(VI)). The determination of Cr(VI) in these novel fertilizer matrices can be hampered by redox processes that lead to false results with the standard wet chemical extraction method (German norm DIN EN 15192). Therefore, we analyzed Cr(VI) in various P-fertilizers with the DGT technique. DGT devices equipped with a APA (polyacrylamide) diffusion layer and Cr(VI) selective N-methyl-D-glucamine (NMDG) binding layer were used for the study. After a 24 h conditioning period of the fertilizer at 60% of the water holding capacity (WHC), the fertilizers were brought to 100% WHC, transferred onto the DGT devices and deployed for 24 h at 25°C. The extraction of Cr from the DGT binding layer was carried out with 1 M HNO3 for 24 h. The Cr-concentrations of the extract were determined by means of ICP-MS. We found a good correlation between the standard wet chemical extraction and the DGT method for the whole range of P-fertilizers. However, partly soluble Cr(VI) compounds cannot be detected in full extent by the DGT method that is best suited for mobile Cr(VI). Furthermore, Cr K-edge XANES spectroscopy showed that the Cr(VI)-selective DGT binding layer also adsorbs mobile Cr(III) compounds from acid treatment of phosphates which can therefore cause an overestimation of Cr(VI). The DGT method was very sensitive and in most cases selective for the analysis of Cr(VI) in P-fertilizers made from recycled materials. However, the results of certain types of P-fertilizers containing mobile Cr(III) or partly immobile Cr(VI) show that still some optimization of the method is required to avoid over- or underestimation of Cr(VI).
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 a lower plant-availability compared to commercial P-fertilizers but are expected to play an increasingly important role into the future (Kratz et al. 2019). One promising way to increase the plant-availability of the fertilizer P is a co-fertilization with specific nitrogen (N) forms which can enhance the P uptake and make P-fertilizers from recycled material more competitive to commercial phosphate rock-based P-fertilizers (Rahmatullah et al. 2006; Vogel et al. 2018). To investigate this effect, we performed a pot experiment with three different P-fertilizers (sewage sludge-based, phosphate rock and triple superphosphate) and ammonium nitrate sulfate as a co-fertilizer, without and with a nitrification inhibitor (NI), and analyzed the form of N and P in soil via a suite of chemical and novel X-ray spectroscopic methods. The application of NI with the P and N fertilizers led to a higher dry matter yield and a higher P uptake of maize. Novel N K-edge micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy identified that the application of a NI promotes the temporary formation of a non-exchangeable N in detectable hot-spots in the soil. The subsequent slow release and prolonged availability of N during plant growth leads to higher yield and nutrient uptake. It can be concluded that NIs lead to a temporary fixation of ammonium-N in a pool that can be accessed by plant roots. Those types of available nutrient pools meet the idea of so-called “next generation fertilizers” as plants have access to nutrients according to their current demand.
A wide range of methods are used to estimate the plant-availability of soil phosphorus (P). Published research has shown that the diffusive gradients in thin films (DGT) technique has a superior correlation to plant-available P in soils compared to standard chemical extraction tests. In order to identify the plantavailable soil P species, we combined DGT with infrared and P K- and L2,3-edge X-ray adsorption near edge structure (XANES) spectroscopy. This was achieved by spectroscopically investigating the dried binding layer of DGT devices after soil deployment. All three spectroscopic methods were able to distinguish between different kinds of phosphates (poly-, trimeta-, pyro- and orthophosphate) on the DGT binding layer. However, infrared spectroscopy was most sensitive to distinguish between different types of adsorbed inorganic and organic phosphates. Furthermore, intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed.
The use of secondary building materials can meet the requirements of sustainability in several ways: the extended time availability of primary raw materials and, thereby, the protection of natural ressources as well as the conservation of landfill sites. Regarding the predicted decrease of gypsum supply in Germany, particularly the recycling of gypsum (calcium sulfate) is of growing importance. Currently, the gypsum demand is fulfilled (at least 60%) by gypsum as side product from coal-fired power plants (FGD Gypsum). Germany’s natural gypsum deposits fulfil the remaining gypsum demand. Due to national climate protection goals the gypsum supply from coal power plants will decrease significantly in the future.
In addition, the content of sulfates in other secondary building materials, in particular in recycled concrete aggregates, should be minimized for quality reasons. Separated gypsum can be used in gypsum production if the high quality requirements for recycled gypsum are met. Accordingly, there have been significant advancements in the processing of gypsum residues in the last years. Since almost all processing steps in the recycling process are associated with environmental impacts, an evironmental evaluation of the use of recycled gypsum as a substitute in gypsum production has to be carefully conducted.
The presentation focusses on the techniques for generating recycled gypsum from gypsum plaster boards, the related quality requirements and a comprehensive environmental evaluation of the complete process.
The chemical emissions from products are tested by means of emission test chambers under defined conditions (climate, loading, air change rate). The standard method for the determination of volatile organic compounds (VOC) is the sampling onto Tenax-tubes followed by thermal desorption (TDS) and gas chromatography-mass spectrometry (GC-MS) analysis. The EU-LCI list includes some very volatile organic compounds (VVOC) and some VOC for which there are limitations when using the standard method. For VVOC additional sampling is required using stronger absorbers like Carbotrap or multi-bed adsorption tubes. The analysis of VVOC also requires a different GC oven program and a different column for the separation. For the determination of formaldehyde and other low boiling aldehydes (e.g. acetaldehyde, acetone, propanal, propenal) DNPH-cartridges are used which are extracted with acetonitrile followed by liquid chromatography (HPLC-UV) analysis. The derivatisation of propenal and other unsaturated aldehydes (e.g. 2-butenal) with DNPH might lead to lower findings due to incomplete derivatization and forming of by-products. For a better quantification of acetic acid the use of ion chromatography (IC) is recommended because the analysis of acetic acid with the standard method (TDS) leads to lower findings due to break through during sampling. The use of ion chromatography for the analysis of organic acids requires a third sampling technique. The acids are adsorbed onto silica-gel and extracted with water.
The container of high-level radioactive waste (HLRW) being in deep geological disposal, the backfill material is needed to serve as the second defense for HLRW and the highly compacted bentonite is generally selected. As the time goes, the underground water will infiltrate the backfill, causing the corrosion of materials for the building of containers in the formed electrolyte. Carbon steel, titanium and its alloy are the potential candidate materials for the fabrication of HLRW containers.
The current investigation aims at assessing the safety of HLRW container in deep geological disposal for hundreds of thousands of years and facilitating the material selection for future Container fabrication by estimating their corrosion behavior in compacted bentonite with a series of moisture content at different temperatures through electrochemical methods including open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curve (PC) measurements. The corrosion rates were estimated for a carbon steel, a pure titanium and a titanium alloy in compacted Gaomiaozi Bentonite infiltrated with simulated underground water in Beishan area of China over an expected disposal period up to 106 years respectively, showing that titanium and its alloy are more reliable materials for building HLRW containers than carbon steel.