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Eingeladener Vortrag
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In Vorbereitung einer Restaurierung erfolgten naturwissenschaftliche Untersuchungen zu Schadensphänomenen und Glaszusammensetzungen an mittelalterlichen Gläsern aus der Dorfkirche in Koszewko (Polen)im Environmental Scanning Electron Microscope (ESEM) mit EDX. Die Ergebnisse zeigen, dass die Glasverwitterung schon sehr stark vorangeschritten ist und ein zukünftiger Schutz der mittelalterlichen Glasmalereifelder vor Umwelteinflüssen unbedingt notwendig ist. Es wurde ein Schutzverglasungsystem entwickelt, das speziell auf den langfristigen Erhalt der einzelnen mittelalterlichen Glasmalereifelder ausgelegt ist.
Microbiologically influence corrosion (MIC) has become a big concern due the increased usage of different metals by our society. Microorganisms can use metal as an electron donor, causing unpredictable but serious damages. Nowadays it is known that besides sulfate reducing bacteria (SRB), other microorganisms including acetogens, iron oxidizers and methanogens can also induce MIC. Current studies related to methanogen-induced MIC (MI-MIC) mainly focused on environmental isolates from the oil and gas industry (e.g. Methanococcus maripaludis) with industrial materials e.g. iron. However, MI-MIC can occur in many other environments as well, including the oral cavity. Methanobrevibacter oralis is a methanogen isolated from the human oral cavity and was found more frequently in patients suffering from peri-implantitis/periodontitis. Titanium-implants removed from those patients have also showed clear signs of corrosion. The aim of our study is to establish and analyze corrosion potentials of dental metals (e.g. titanium) by oral methanogens. Periodontal pockets samples from patients suffering from periodontitis/peri-implantitis were taken for methanogenic and SRB enrichments. Stainless steel, pure titanium or Ti-6Al-4V alloy was used for corrosion studies. Corrosion rates and methane production were measured using weight-loss method and gas chromatography, respectively. Metal surfaces were visualized with scanning electron microscopy. Microbial communities in the dental pockets of healthy people and patients will be compared using 16S rRNA amplicon sequencing. Overall, this is the first study investigating the susceptibility of different dental implant materials to corrosion using human-related Archaea. The outcomes of this study can be further explored for a variety of clinical applications.
The first documentation of fuel biodeterioration dates back to the late 19th century. However, extensive studies concerning the microbial fuel contamination started in 1980’s. Polymeric fuel storage tanks containing diesel and biodiesel provide environmental conditions for microbial growth. Several studies demonstrated that bacteria, which were found in contaminated fuel systems, can use fuels as macronutrient; but such bacteria can also cause microbiologically influenced corrosion and fouling.
The aim of this study is to investigate the initial attachment behavior of bacteria, isolated from a diesel contamination, on neat and photooxidized high-density polyethylene (PE-HD). Two common PE-HD’s, less- and biodiesel-stabilized, were radiated to UV light representing a tank exposed to sunlight. The effect of photooxidiation on PE-HD’s surface were characterized chemically by Fourier-transform infrared spectroscopy (FTIR). The attached bacteria Pseudomonas aeruginosa and Bacillus subtilis on the polymer surface were evaluated by fluorescence microscopy and colony-forming unit tests (CFU).
We demonstrate a 2D platform based on high contrast wetting patterns suitable for miniaturized microbiological assays.
In principal, superhydrophilic spots are surrounded by a superhydrophobic surface area. The special structure of the superhydrophilic functional surface ensures that liquids, e.g. bacterial suspensions or biocide solutions, spread immediately and evenly on this surface without passing the wetting boundary. This feature allows a homogenous distribution of bacteria or chemical substances on well defined lateral dimensions. The superhydrophilic spots may also serve as substrate for bacterial biofilms. Due to the high wetting contrast and the fabrication process, it is possible to minimize the test areas as well as their distance to each other.
We demonstrate the fabrication process of the high wetting contrast platform and also present a microbiological assay as an application example. Advantages of this platform are the use of low volumes and its potential of automated analysis.
The manuscript Codex germanicus 1 (Cod. germ. 1) of the Staats- und Universitätsbibliothek Hamburg is a fifteenth-century German-language manuscript. It comprises two codicological units and has an especially complex developmental history. To trace this developmental history, neglected until now in the research literature, the manuscript was investigated, for the first time not solely with classical codicological and palaeographical methods, but also with the aid of X-ray fluorescence spectroscopy, in order to determine the composition of the writing materials. These methods made it possible, first, to support and check palaeographic findings and, second, to gain information about the stratigraphy of the manuscript where palaeographic methods find their limits – in regard to short entries, rubrications, and non-alphabetical signs.
It is well documented that throughout Antiquity, ancient Egyptians used mostly carbon inks as a writing material. In Late Antiquity, some metals started to be added to carbon based inks. We have records of five manuscripts from the Dead Sea Scrolls collection whose carbon inks were found to contain copper Also, lead was recently found as an additive in carbon inks on a charred fragment from Herculaneum. Furthermore, the earliest evidence of iron-gall ink was found in the Book of Proverbs (Codex Ms. Berol. orient. oct. 987) dating to the third fourth centuries ce. It has been suggested that along with carbon and iron-gall inks, there is no reason to think that purely tannin inks were not also in use in Egypt. However, so far, we just have evidence of a copper-tannin ink identified in a number of documents from Egypt in the first third centuries bce. In an attempt to fill this gap in this extremely fragmented scenario during our studies of the socio-geographic history of inks, we arrived at the conclusion that the continuous production of Coptic manuscripts from Late Antiquity to the Middle Ages offers a unique opportunity for the historical study of inks across a large geographic area.
Advanced codicological studies of Cod. germ. 6 (Hamburg, Staats- und Universitätsbibliothek): Part 2
(2018)
The work presented here follows the article Combining Codicology and X-Ray Spectrometry to Unveil the History of Production of Codex germanicus 6 (Staats- und Universitätsbibliothek Hamburg), published in 2014.1 It confirms the main result of the previous article: the Artusnotiz, the fourth text in the bound manuscript, must have been introduced as the last one. This paper offers further details of the codex production, based on the composition of the black and red inks collected in four measurement campaigns. Furthermore, using imaging μ-XRF, we succeeded in understanding the strong variation of the composition of the red inks in the initials of all the texts except for Parzival and Jeanne d’Arc.
Auslaugversuche wurden mit verschiedenen Bauprodukten durchgeführt, die unter Anwendungsbe-dingungen mit Niederschlägen in Kontakt kommen können. In das Testprogramm wurden Lacke für Außenanwendungen, Wärmedämmverbundsysteme, Dachziegel und polymere Dachfolien einbezogen.
Mit diesen Produkten wurden der von CEN TC 351 entwickelte dynamische Oberflächenauslaugtest (DSLT) und Immersionstests nach EN 16105 durchgeführt. Emissionsverläufe wurden sowohl für an-organische Komponenten als auch für organische Substanzen in den Eluaten ermittelt. Auslaugbare organische Substanzen wurden zuvor in Screeningtests identifiziert.
Um die mögliche Freisetzung von Stoffen aus Bauprodukten beurteilen zu können, ist es erforderlich, Emissionsverläufe zu beschreiben. Dazu sind die verwendeten Testverfahren geeignet. Um Baupro-dukte mit einem Blauen Engel als „Produkte mit geringer Auslaugung“ auszuloben, müssen die aus-laugbaren Substanzen komplett bekannt sein. Für organische Verbindungen ist das noch eine Heraus-forderung. Außerdem erfordert die Bewertung der Testergebnisse sowohl Übertragungsmodelle, die Vorhersagen über freisetzbare Stoffmengen unter Anwendungsbedingungen ermöglichen, als auch Vorgaben zu tolerierbaren Umweltkonzentrationen. Hier besteht noch Handlungsbedarf.
The quest for the mixed inks
(2018)
In this article, we would like to share our observations concerning the inks produced by intentionally mixing soot or charcoal with tannin extracts or iron-gall ink. Aside from Zerdoun’s mention in her outstanding review of written sources, “Les encres noires au Moyen-Âge”, this ink category has received little if any attention from scholars and scientists. And yet, if analytically attested, the use of such inks could serve as an additional category to classify and distinguish the writing inks on the historical socio-geographic map of the writing inks we are trying to build.
Today glass is broadly used in modern architecture. For applications indoor it is possible to produce decor glass by using enamel colors and glass painting techniques without any problems. However, this is more limited for applications outdoor. Humidity and environmental pollution attack the surface of the coating and damage it strongly. There are only few colors on the market which are resistant towards acids and bases until now. Additionally, most of those colors are opaque. In order to extend the color palette, chemically resistant colored glasses are being developed which are transparent, relatively low melting and intensively toned even in thin coat thickness. To achieve such ambitious aim, many parameters have to match which act in complex manner. Metal oxides were used to color the glasses. A lead-free glass composition was developed to avoid an exposition of heavy metals to the environment. The glasses were characterized, in particular in terms of their thermal properties, their crystallization and corrosion behavior as well as their chemical and environmental durability. Different practical applications will be shown.
This paper reports the outcome of an interdisciplinary team’s application of multispectral imaging techniques and material analysis to a music fragment from the first decades of the fifteenth century: Atri, Archivio Capitolare, Museo della Basilica Cattedrale, Biblioteca del Capitolo della Cattedrale, Frammento 17. This important parchment leaf has rarely been investigated since its discovery 45 years ago. Thanks to the applied techniques and methods (such as the evaluation of the data using the fingerprint model), it is now possible to discuss new evidence supporting conclusions regarding the fragment’s origin and afterlife.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons (Fe → Fe²⁺ + 2e⁻ ; E° = 0.47 V) in electrical contact through surface attachment. Also methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO₃⁻ + 5H⁺ → 4FeCO₃ + CH₄ + 3H₂O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO₃ precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
To investigate the corrosive potential of methanogens, we studied strains isolated from marine sediments (Methanococcus maripaludis 14266, 2067, Methanobacterium-affiliated strain IM1), crude oil tanks (Methanococcus maripaludis Mic1c10, KA1) and the oral cavity (Methanobrevibacter oralis) in a closed (batch) culture, and in a sand-packed flow-through cell with pH control and simulation of a fluctuating environment. Results indicate that the rates of iron corrosion due to coupled methanogenesis (up to 0.3 mm/yr) are comparable to that caused by SRM. Surface analyses of the metal showed severe pitting. Such knowledge and deeper understanding also from an electrokinetic point of view may not only provide further models in microbial electrophysiology, but also contribute to mitigation strategies in MIC.
Microbiologically influenced corrosion (MIC) is the deterioration of metals due to the metabolic activities of microorganisms. Microorganisms can take electrons directly from the metal surface (EMIC) thereby causing corrosion. Well known culprits of EMIC are: sulfate-reducing bacteria (SRB), acetogens and methanogens.
This application note presents how EnviroESCA can be used to analyze E. coli biofilms on silicon under near ambient pressure conditions in various states of hydration. Such investigations of the outer bacterial cell surface in their hydrated state are essential for studying biological interfaces at work.
Wastewater contains a diverse array of organic and inorganic compounds and its complex composition strongly depends on the location and the connected dischargers. However, municipal wastewater as a carrier of feces and urine generally contains considerable amounts of the main nutrients nitrogen and phosphorus. The latter is in the focus of the discussions about the recovery potential of wastewater due to the relatively high mass flows of phosphorus in wastewater and the finite nature and decreasing quality of phosphate rock reserves. But due to the presence of the whole periodic table of elements, wastewater might contain further valuable components of interest for recovery including those defined as critical raw materials by the European Commission. Phosphorus and most of the other critical raw materials are fixed in the sewage sludge and after incineration in the sewage sludge ash (SSA). This is accompanied by high concentration factors from wastewater via sludge to ash. However, the mass fractions of the majority of elements in sewage sludge are comparable to those of the earth crust, indicating no relative enrichment. Nevertheless, enrichment factors of 100 or higher are given for phosphorus, copper, zinc, cadmium, silver, tin, lead and the platinum group elements indicating an anthropogenic input. An economic value of sewage sludge was estimated to $460,-/t calculated on the basis of the respective market prices for high purity elements – a theoretical value. A German survey of sewage sludge ashes showed that the mass fractions and the mass flows of most of the elements present in SSA are probably too low for an economic recovery. In most cases the mass flows are rather small compared to the imports and the chemical forms are not suitable for recovery. An exception is phosphorus that is present in high mass fractions up to 13% and that bears a high substitution potential. If the application of P-recovery technologies lead to a further concentration of valuable elements e.g. as by-products in side streams of the process, it would probably make also the recovery of other elements of economic interest.
There is a need for an assessment of the emission properties of volatile organic compounds (VOCs) from consumer products. A method comparison was carried out to evaluate adapted and cost-effective procedures for such items. Smaller and automated emission chambers de-picted similar kinetics compared to a 203 L standard chamber. Toy samples made of PVC (Polyvinyl chloride) emitted more VOCs compared to other tested polymeric products. The emissions from 2 selected samples were studied to allow an evaluation of the resulting room concentration and external exposure of a child. Obtained concentrations were not of concern.
Eine entscheidende Problematik nach Inkrafttreten der neuen
Klärschlammverordnung ist, wie Phosphor nicht nur rückgewonnen,
sondern in den Markt eingeschleust und letztlich auch
in den Kreislauf zurückgeführt werden kann. Die Wege hierzu
sind noch weitgehend ungeklärt. Die DWA-Arbeitsgruppe KEK-
1.1 hat aus diesem Grund einen Workshop durchgeführt, um
rechtliche Anforderungen an Rezyklate, Aspekte der Rezyklatqualität
und -beschaffenheit sowie den aktuellen Markt für Rezyklate
zu diskutieren. Auf Basis dieses Workshops wurde ein
Arbeitsbericht erstellt, der sich schwerpunktmäßig mit dem Einsatz
von Rezyklaten zu Düngezwecken beschäftigt. Hierzu liegen
bereits Erkenntnisse vor, und es sind bereits Praxisbeispiele in
der Umsetzung.
The challenge of the project ASHES is focused on the recycling of nutrients from residues of thermochemical processing of by-products of sugar cane industry (bagasse/straw) in Brazil to increase the energy efficiency of thermal conversion and to enable the recycling of process ashes as fertilisers. Dry lignocellulosic biomass (straw, bagasse) are combusted, gasified and subsequently combined with post-thermochemical treatment in the AshDec process to increase the plant availability of phosphorus. Different fertilizer formulations are granulated/pelletized and tested regarding their storage/handling characteristics.
There is a need for an assessment of the emission properties of volatile organic compounds (VOCs) from consumer products. A method comparison was carried out to evaluate adapted and cost-effective procedures for such items. Smaller and automated emission chambers depicted similar kinetics compared to a 203 L standard chamber. Toy samples made of PVC (Polyvinyl chloride) emitted more VOCs compared to other tested polymeric products. The emissions from 2 selected samples were studied to allow an evaluation of the resulting room concentration and external exposure of a child. Obtained concentrations were not of concern.
Fluorometric sensing is a versatile approach for trace analysis outside of the laboratory, requiring suitable sensor materials and their integration into sensing devices. The versatility of fluorophores as probes, especially in terms of the possibility to tailor their optical as well as their recognition properties by synthetic modifications in a wide range, renders them as superior active component for the preparation of optical sensing devices. Recent works at BAM in this field include, for example, the detection of nerve gas agents, illustrating impressively the aforementioned benefits of fluorophores in optical sensing applications.
In the interdisciplinary project presented here, we target hazardous gases such as ammonia, benzene, and hydrogen sulfide, next to others, which pose a major threat to human health and environmental safety and for which the availability of a sensitive and reliable detection method is highly desirable. The dyes presented follow a “turn-on” fluorescence schematic, which allows for the selective and sensitive detection of the respective gaseous analyte. The immobilization of the probe in polymeric matrices is then the next step toward the fabrication of a prototype device for molecular sensing. Further steps in the project include the assembly of instruments for test-atmosphere generation, the referencing of the sensor system, development and implementation of an optical setup, and the testing of the prototype device under laboratory conditions and in the field.
In this presentation, we give an overview over the recent developments on this topic in our groups. Highlights are hydrogen sulfide sensitive, BODIPY based transition metal complexes, which allow for a sensitive as well as selective detection of the toxic gas. In addition, we present a novel class of highly substituted BODIPY derivatives – pocket-BODIPYs – which are of a synthetically high versatility and can readily be modified to create pockets in the periphery of the molecule of defined geometries. This is illustrated on the successful encapsulation of benzene by a pocket-BODIPY derivative, confirmed by X-ray crystallographic analysis as well as by further spectroscopic and analytical methods.