4 Material und Umwelt
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Organisationseinheit der BAM
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Paper des Monats
- ja (19)
Bee populations have declined significantly in recent years and this is thought to be attributable at least in part to the (re-)emergence of viruses. These viruses are predominantly positive single stranded (+ss) RNA viruses belonging to the Picornavirales. Managed honeybees are often infested with the invasive mite, Varroa destructor, which vectors RNA viruses including Deformed wing virus (DWV, family Iflaviridae): a leading culprit of colony losses. Many bee viruses have been sequenced and structural features are now available for viruses such as DWV. DWV consists of at least 3 distinct genotypes, two of which have been shown to be differentially virulent in honeybees. Molecular studies have demonstrated that DWV has a mean evolutionary rate of 1.35 x 10-3 per site per year. For such viruses – in contrast to their eukaryotic hosts – ecological and evolutionary timescales significantly overlap. This rapid evolution allows RNA viruses to adapt quickly to novel host environments with recombination representing an additional key source of genetic variation. Interestingly, recombination between genotypes of DWV has recently been shown to be a common occurrence in honeybees. A challenge has been to develop bioinformatics tools that can accurately reconstruct viral haplotypes – including recombinants – from heterogenous high-throughput sequence data.
The impact of blood-to-blood Varroa destructor transmission on virus evolution represents an important question in bee virus research. Due to the nature of the V. destructor life cycle, predictions can be made about the potential impact of the mite on virus virulence evolution. Specifically, the developing honeybee host pupa should remain alive until close to the completion of metamorphosis to provide sufficient time for successful mite reproduction, including offspring mating. For optimal transmission, any virus found in a mature and mated daughter mite will hold a significant selective advantage over a virus found in an immature or unmated daughter mite – placing a cost on virus virulence that impacts honeybee pupae before mites can mate. On the other side, viruses replicating too slowly and with delayed virulence effects will hold a selective handicap because fewer transmission units will be found in mated mites. I have hypothesized that the evolution of virus virulence shifted following the arrival of V. destructor, with viruses, including recombinants and/or specific viral genotypes being selected for a level of virulence in pupae (and likely also in adults) that maximises R0, which represents the basic reproductive number of the virus in the host population. R0 is defined by the number of subsequent infections caused by a single infection and it must be greater than 1 for an infection to spread in a population. It is enhanced by maximising the number of transmission units passed to uninfected susceptible vectors, and ultimately hosts (Figure 1).
Honeybee viruses are also shared with sympatric wild bees and viral prevalence and sequence data indicate frequent virus transmission between managed and wild bee species. In addition to infecting the western honeybee (Apis mellifera), DWV can infect other Asian honeybee species such as Apis ceranae. Outside of honeybees, DWV has been found widely in bumblebees, including solitary bees and wasps and there is evidence that it can actively replicate in several Bombus and solitary bee species. Whether the arrival of the V. destructor mite in A. mellifera has driven viral emergence in non-Apis bees is a target of ongoing research.
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 in electrical contact with the metal. Methanogenic archaea can also cause MIC by directly withdrawing electrons from the iron surface for methanogenesis. However, the mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite, a by-product of methanogenesis, (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.
A new sewage sludge ordinance was set in force in Germany in 2017 that makes phosphorus recovery from sewage sludge mandatory. The technological possibilities for P-recovery from waste water, sewage sludge and sewage sludge ash were presented.
The Cairo Geniza is an “archive” discovered in the 19th century in Ben Ezra Synagogue in Fustat, a district in Old Cairo (Egypt). The collection of mostly Jewish documents that vary in genres, languages and writing supports contains a large number of early medieval Hebrew manuscripts.
The Geniza provides sources for the literary, linguistic, historical studies of the various aspects Jewish life. As the documents attest, at least two Jewish communities co-existed in Fustat up to 11th century: a so-called Babylonian and Palestinian. These communities had different leaders, different traditions and lived independently. The differences seem to manifest themselves also in the paleographical, codicological and some material properties of the manuscripts produced by each community.
The aim of this project is to compare the inks used in the Jewish documents depending on different variables: support (paper, parchment), purpose of the manuscript (legal, private, religious), provenance of the scribe. For the determination of the inks type and composition we had to choose non-invasive, non-destructive and portable techniques to analyze the corpus directly on-situ.
The analyses were carried out with a micro-X-ray spectrometer ArtTAX® (Bruker GmbH) and a digital stereomicroscope features built-in LED illumination at 395 nm and 940nm, Dino Lite.
We would like to stress that though the methods of material analysis listed above have been successfully employed in the field of cultural heritage and conservation including ancient and medieval manuscripts they have not yet been used to study fragments from the Cairo Genizah. Therefore, we believe that this research project is a pioneering study that will provide new insights into the history of Hebrew writing materials, their production techniques and materials and, thus, contribute new data to the field of Hebrew paleography.
The technique of painting on the reverse side of a glass panel was rediscovered by German artists at the beginning of the 20th century. They appreciated the impressive gloss, luminosity, and depth of colours in this genre. Compared to stained glass, the distinctive properties of this technique are: (1) the paint is applied “cold”, hence, it doesn’t involve a firing step, (2) reverse paintings on glass are framed and always viewed in reflected light and (3) the reverse paint stratigraphy is different from canvas paintings, starting with the front most layer and ending with the backing layer. In 1908 several artists, including Gabriele Münter, Wassily Kandinsky, Heinrich Campendonk, August Macke and Franz Marc of the “Der Blaue Reiter” (the Blue Rider) collective took an interest in this technique and started to share their interest with other colleagues in Europe. Our pioneering project is tracing this transfer of knowledge by a multidisciplinary approach in terms of art history, paint technology and material science. More than 100 artists and >1000 reverse paintings on glass were identified during the project. This high number of objects clearly points out that this technique was by far more important for modern art than previously assumed. In-situ, non-invasive measurements (XRF, Raman, VIS, DRIFTS) on a well-considered selection of 67 paintings reveal the broad palette of colorants ranging from traditional to experimental. Special attention is paid to the impact of synthetic organic pigments (SOP) in artists palette. Demonstrative examples by W. Kandinsky, L. G. Buchheim and F. Jespers are used to discuss analytical challenges and highlights.
Near-ambient pressure XPS makes it possible to characterise samples not compatible to ultra-high vacuum, and enables the study of liquid-solid, gas-liquid and gas-solid interfaces. NAP-XPS meas-urements of biofilms, suspended nanoparticles and metal-organic frameworks were performed with EnviroESCA developed by SPECS.
An interesting application is surface characterisation of biofilms, which are bacterial communities embedded in a self-produced polysaccharide matrix. Various model systems ranging from pure polysaccharides of alginate to biofilms harvested directly from the growth medium have been char-acterised in humid conditions[1].
NAP-XPS also makes it possible to characterise nanoparticles in solution. Silver nanoparticles in aqueous solution were characterised and the Ag 3d-spectrum compared to spectra obtained of dried nanoparticles in UHV-conditions[2]. The binding energy of the Ag 3d-core level peak was shifted by 0,6 eV towards higher binding energy for suspended nanoparticles compared to the dried sample measured in UHV. This can be assigned to a change in surface potential at the water-nanoparticle interface.
Metal-organic frameworks (MOFs) are suitable materials for gas storage of small molecules due to their nanoporous, crystalline structure. However, instability in humidity remains an issue for many types of MOFs. XPS-measurements of the MOF-structure HKUST-1 were performed in various NAP-conditions to assess the stability of the sample and its interaction with the gas molecules as water, methanol and pyridine.
Tantalum and niobium are essential for the development of electronics towards a more and more compact design, but without reducing their performance today. Especially in smart phones and tablets, tantalum and niobium capacitors with high charge densities have already become almost indispensable. However, tantalum as a critical raw material is still a problem for the sustainable production of electronics. Due to this fact, the existence of efficient recycling processes especially in Europe is becoming even more important nowadays.
The Bundesanstalt für Materialforschung und -prüfung (BAM) is currently working on the optimisation of an existing pyrometallurgical tantalum recycling process. Optimisation of this industrial process is carried out in a small-scale electric arc furnace (480 kVA, capacity approx. 150 kg/h) at BAM using a new and innovative equipment for on-line analysis of high temperature processes.
The aim of this project is to identify the best timing for an optimum slag tapping, when the slag is lower than minimum targeted tantalum concentration. Hence, LIBS (Laser induced breakdown spectroscopy) is used to identify the chemical composition of the slag layer and during slag tapping. The on-line-LIBS prototype of BAM enables an in-situ measurement of the element distribution in the melt after calibration on the slag system.
First results of this joint research project will be presented including LIBS-measurements and thermodynamic and kinetic aspects of the process.
Z02 is one of the three technically supporting projects at the Centre for the Study of Manuscript Cultures (CSMC). In collaboration with the other two service projects, Z01 and Z03, it aims at bridging the gap between humanities and natural sciences and technology. To that purpose, we set up a laboratory with a range of high-end instruments, most of them mobile, allowing thorough non-destructive analysis of manuscripts. In addition to working on constantly improving the laboratory and the methods of analysis, a substantial part of our activities is dedicated to service, by supporting different research projects conducted at the centre. In this talk, we will present our equipment and the possibilities offered by the different techniques available regarding the different kinds of missions: typology and classification of inks, provenance studies, recovery of faded inscriptions and palimpsests, reconstruction of the history of manuscripts, authentication and dating. We will give a brief overview of our past and ongoing activities in the frame of the second phase of the CSMC. Finally, a selection of projects will be presented in greater detail to highlight the possibilities of our laboratory and the diversity of missions which can be carried out.
In addition to previously reported results on the simulated aging of polystyrene samples (PS) containing 1 wt. % hexabromocyclododecane (HBCD), we present the first results of our investigations of polypropylene (PP)-samples containing 0.1 wt. % BDE-209. All studied polymer samples were exposed to a defined weathering schedule in a climate chamber in accordance to regulation EN ISO 4892-3:2006.For the determination of BDE-209 in the collected rain water samples derived from the used climate chamber, the samples were prepared in accordance with a validated protocol. Before the analyses, each sample was spiked with 2 µL of isotopically labeled BDE-209 (13C10-BDE-209) to serve as internal standard (ISTD) in the performed stable isotope dilution analysis. Subsequently the samples were extracted with isooctane, the obtained aliquots of the extracts were concentrated to 200 µL and 2 µL of the resulting solution were injected to the GC/MS for quantification.
Additionally, the total bromine contents are monitored for the aged and untreated samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as well as X-ray fluorescence analysis (XRF) as non-destructive and rapid method. Furthermore, results from surface analysis using environmental scanning electron microscopy (ESEM) for morphological characterization of the aged and untreated samples were presented and discussed. In general, the resulting data from the accelerated aging will be compared to those from the natural weathering experiments (“atmospheric exposure”, in soil).
The atmospheric exposure was performed by placing the samples on a weathering rack, which is aligned in SW direction (in a 45° angle to the horizon). The weathering data were regularly recorded by Deutscher Wetterdienst at this site. The surfaces of the test specimens (aged and stored references) were analyzed by ESEM as well as by LA-ICP-MS and by XRF. The surface of PS and PP specimens aged outdoors present the aging under real conditions and allow the comparison to the accelerated aged specimens by means of the weathering chamber. This way, we explore the efficiency of the accelerated aging procedure, which provides the advantage of well-defined and reproducible conditions compared to natural weathering, as a tool for testing different plastic materials.
Additionally “in soil” experiments were conducted in-door in a well characterized testing soil. The soil (boulder-clay, sand with 12 % loam, particle size in total 0.2-4 mm) is filled in a free-draining concrete basin inside of an air-conditioned room. In this manner, TOC, water capacity and humidity are recorded parameters. To assure a washing out process from the samples by the raining water, the target water content is calculated to 8%. The actual humidity is measured by a tensiometer, assuring the duration of the raining period. The water content is additionally monitored by weight of the basin, capturing water from raining periods. The correct humidity is a fundamental parameter for biological activity. Samples of PS resp. PP were of dimension 10x1cm and 5 specimens were placed up to the half in the soil per basin. Microbial activity of the soil, monitored by the reference polyurethane, sets HBCD resp. BDE-209 of the samples free and will be leached from the samples by raining water. Thereafter these will be captured by passive samplers placed in a distinct distance to the samples in the soil. The “in soil” experiments are complementary to the weathering experiments due to the biological activity in the soil. These experiments simulate the fate of the brominated flame retardants in the biosphere.
Environmental sustainability and –stability of Materials concerning the Migration of pollutants
(2018)
MaUS is an acronym for ”Material und Umweltsimulationen“. Plastics are in the focus of environmental politics due to their long-term behaviour and therefore to their persistence. Not only that they appear as visible contaminants in the sea and on the beach, but their unknown behaviour concerning their additives as well as the related transformation products are anxious. Therefore, we wish to establish a certified reference method to provide a method for testing plastics.
Aim of this project is the development of fast motion standard reference methods for testing plastics regarding to their environmental compatibility. To establish these testing methods, we use polystyrene (PS) and polypropylene (PP) with environmental relevant brominated flame retardants, known for their persistent bioaccumulative and toxic (PBT) properties. In case of PS the material contains 1 wt% of 1,2,5,6,9,10-hexabromocyclododecan (HBCD) and in case of PP 0.1 wt% bromodiphenylether (BDE-209), which is known as a substance of very high concern (SVHC). Furthermore, we use polycarbonate (PC), which is still used as material in baby flasks and releases Bisphenol A (BPA), an estrogenic active substance.
As an additional material PTFE is used for its importance as a source for two ubiquitous environmental substances (PFOS and PFOA), whose toxicological effects are still incompletely known.
The focus in this current work is set on the transfer of potential pollutants out of applied materials mentioned above into environmental compartments like water or soil. Here an accelerated aging concept should be developed to shortened time consuming natural processes. For these resulting simulations we use a programmable weathering chamber with dry and wet periods and with high and low temperatures. These programmes run for several weeks and according to a defined sampling schedule we take water samples, run a clean-up procedure by SPE (Molecular imprinted polymers (MiPs) resp. polymer-based cartridges (Waters Oasis HLB)) and analyse them by HPLC-UV resp. LC-MS/MS. Of most interest in case of flame retardants are photocatalytic transformation products. Therefore, we conduct a non-target-screening resp. a suspected target-screening by LC-MS/MS and HRMS.
Synchrotron XPS in the soft-X-ray regime is suitable for the detection of light elements commonly found in biological samples. Various model systems of biofilms have been developed and characterised at synchrotron- and lab-based facilities. By obtaining the chemical composition at various information depths, the vertical distribution of iodine in an artificial biofilm have been determined.
ABSTRACT: A collection of thioimidazolium salts were synthesized and used as a new class of nonvolatile alkylating agents. Their nonvolatility prevents exposure during use or handling and are thus drastically safer than conventional alkylating agents. We discovered that thioimidazolium Iodide salts cannot release volatile compounds in the solid state, but instead only decompose when molten. Since decomposition proceeds via alkyl iodide elimination, SN2 of iodide on the thioimidazolium cation is constrained in the solid state, and instead can occur only upon melting when ions are mobile. By smart design of these alkylators, the melting point and thus the decomposition temperature of these salts can be increased from 106 to 169 °C and release negligible volatile organic compounds prior to melting. Thioimidazolium-bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids act as a completely nonvolatile and air-stable TFSI-based alkylating agent and can be used for high-throughput Synthesis of TFSI ionic liquids without solvent. Alkyl groups from methyl to dodecyl can be transferred to a nucleophile and the product purified by sublimation of the thione byproduct, which can then be recycled. We also found that thioimidazolium salts with a dodecyl chain are bactericidal, yet can hydrolyze in water to form benign neutral products, and thus wont accumulate in the environment. These results demonstrate that thioimidazolium salts are a designable platform for the pursuit of safer and more environmentally friendly alkylating and antiseptic agents.
Microbial activity and functioning in soils are strongly limited by carbon (C) availability, of which a great proportion is released by living roots. Rhizodeposition and especially root exudates stimulate microbial activity and growth, and may shift the stoichiometric balance between C, N, and P. Thereby, exudates heighten microbial nutrient demand and acquisition of N and P from organic matter, leading to an increase in enzyme production. Aim of this study was to determine environmental controls of extracellular enzyme production, and hence on potential enzyme activities (Vmax) and substrate affinities (Km). To determine the controlling factors, we worked on four spatial scales from the microscale (i.e. rhizosphere) through the mesoscale (i.e. soil depth) and landscape scale (relief positions), and finally to the continental scale (1200 km transect within the Coastal Cordillera of Chile). Kinetics of seven hydrolyzing enzymes of the C, N, and P cycles (cellobiohydrolase, β‑glucosidase, β‑xylosidase, β‑N‑acetylglucosaminidase, leucine‑aminopeptidase, tyrosine‑aminopeptidase, and acid phosphatase) were related to soil texture, C and N contents, pH, and soil moisture via redundancy analysis (RDA). Potential activities of C, N, and P acquiring enzymes increased up to 7-times on the continental scale with rising humidity of sites and C and N contents, while substrate affinities simultaneously declined. On the landscape scale, neither Vmax nor Km of any enzyme differed between north and south slopes. From top- to subsoil (down to 120 cm depth) potential activities decreased (strongest of aminopeptidases under humid temperate conditions with up to 90%). Substrate affinities, however, increased with soil depth only for N and P acquiring enzymes. Affinities of cellobiohydrolase and β‑xylosidase, on the contrary, were 1.5- to 3-times higher in top- than in subsoil. Potential activities of N and P acquiring enzymes and β‑glucosidase increased form bulk to roots. Simultaneously, substrate affinities of N and P acquiring enzymes declined, whereas affinities of β‑glucosidase increased. These trends of activities and affinities in the rhizosphere were significant only for acid phosphatase. The RDA displayed a strong relation of potential activities of C and P acquiring enzymes and β‑N‑acetylglucosaminidase to C and N contents in soil as well as to the silt and clay contents. Aminopeptidase activity was mainly dependent on soil moisture and pH. We conclude that substrate availability for microorganisms mainly determined enzyme activity patterns on the continental scale by the humidity gradient. Patterns on the meso- and microscale are primarily controlled by nutrient limitation, which is induced by a shift of the stoichiometric balance due to input of easily available C by roots in the rhizosphere.
In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is −0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (−2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (−0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.
Phosphorus (P) plays an essential role in the global food security. However, the global P reservoirs have a statistic lifetime of about 385 years only. Due to the scarcity of P and the increasing world population an efficient and sustainable recycling management is required. A few biogenic waste materials are high in P contents such as sewage sludge and meat and bone meal. Thus, they are suitable for P recycling and fertilizer production. But besides the high P content sewage sludge is often highly contaminated with organic pollutants and toxic heavy metals which have to be eliminated before agricultural field application. In this presentation we show the potential of sewage sludge as secondary resource for fertilizers. This includes our developments in thermochemical processes for the production of novel P-fertilizers from recycled materials. Furthermore, for these novel P-fertilizers common extraction tests to determine the plant-available P are often unusable. Therefore, we successfully applied the Diffusive gradients in thin-films (DGT) techniques to analyse the plant-availability of P-fertilizers from recycled materials.
The particle size distribution is considered the most relevant information for nanoscale property identification and material characterization. The current OECD test guideline on particle size and size distribution (TG 110) is not applicable to ‘nano-sized’ objects. In this project we thus develop a new OECD test guideline for the measurement of the size and size distribution of particles and fibers with at least one dimension in the range of 1 - 1000 nm. A fiber is defined as an object having an aspect ratio of length/diameter l/d >3. The width and length of each fiber should be measured concurrently.
In order to measure the particle size distributions, many techniques are available. 9 methods for particles and 2 methods for fibres have been tested in a prevalidation study and appropriate methods will be compared in an interlaboratory round robin test starting in February 2019.
The particle size distribution is considered the most relevant information for nanoscale property identification and material characterization. The current OECD test guideline on particle size and size distribution (TG 110) is not applicable to ‘nano-sized’ objects. In this project we thus develop a new OECD test guideline for the measurement of the size and size distribution of particles and fibers with at least one dimension in the range of 1 - 1000 nm. A fiber is defined as an object having an aspect ratio of length/diameter l/d >3. The width and length of each fiber should be measured concurrently.
In order to measure the particle size distributions, many techniques are available. 9 methods for particles and 2 methods for fibres have been tested in a prevalidation study and appropriate methods will be compared in an interlaboratory round robin test starting in February 2019.
Transformation of carbendazim, diuron, octylisothiazolinone and terbutryn was investigated in two paints containing either white titanium dioxide or a red iron oxide pigment.
Test specimens of these coatings on glass were exposed to water contact and UVA-radiation under laboratory conditions. Panels of birch plywood were coated and exposed to natural weather conditions in a field experiment. Concentrations of biocides and transformation products were analysed in leachates from laboratory tests, runoff samples and remaining coatings. Water contact, UVA radiation as well as pigments in the paints affected the pattern and amount of transformation products.
In Denmark, increasing amounts of woody biomass are being used for the production of renewable energy, resulting in more wood ashes being generated. While these materials have been mainly landfilled, wood ashes may also be utilised for fertilizing and liming purposes on top of soils. Pre-treatments involving hardening or granulation may be carried out prior to soil application. In this study, two Danish wood ash samples were hardened and/or granulated. Lab-hardening induced rapid changes in the shape of the acid neutralisation capacity curve of the ashes. Up-flow column tests, assuming local equilibrium conditions, were employed to investigate the leaching from pre-treated ashes. Granules and loose ashes demonstrated similar leaching behaviours, indicating that similar geochemical processes were governing their leaching. In comparison with untreated fresh ashes, the hardened ashes demonstrated reduced leaching of Ca, Ba, Pb and Zn with concentration levels generally below or close to the analytical limits of quantification; to the contrary, the leaching of As, P, Sb, Si, V and Mg was enhanced in the hardened ashes. The release of alkalinity was reduced by hardening. In general, all granules were barely breakable by finger-pinching and they could withstand one month of continuous leaching, preserving their overall shape. The solubility of phosphorous in neutral ammonium citrate indicated that about 30–51% of the total P content in the ash samples was released, suggesting that the ashes could be potentially valuable as P-fertiliser if applied onto soil.
Selection of resistance in bacteria grown on antimicrobial surfaces in a multidrug environment
(2018)
Bacterial biofilms are regarded as the most common cause of chronic infections and are often associated with medical devices, such as implants and catheters. Bacteria growing in biofilms produce a protective, extracellular matrix, which enables them to tolerate much higher antimicrobial concentrations than free-living bacteria and survive long enough to acquire antimicrobial resistance. Preventive and therapeutic strategies against biofilm infections in clinical settings commonly involve the application of multiple antimicrobials: antimicrobial coatings on the biomaterials and systemically administered antibiotics. This frequent practice harbors the risk of the development of cross-resistance via shared resistance mechanisms between antimicrobials used in material coatings and administered antibiotics.
Our goal is to determine how population dynamics within biofilms affect the transmission of resistance mutations. Specifically, we want to identify antimicrobial-antibiotic-combinations that select for and against antibiotic resistance in biofilms by following the population dynamics of resistant and susceptible strains in competition assays. Gaining a better understanding about resistance development and spread in persistent biofilm infections will enable us to provide clinical recommendations for improved administration of antibiotics/antimicrobials in combination with medical device materials to mitigate against biofilm associated antimicrobial resistance.
Here, we will discuss our first findings on the effects of combinations of the carbapenem drug meropenem and various antimicrobials.
The SCALE Project is a Horizon2020 Project (GA°730105) that aims to develope a secure supply chain for Scandium in Europe. To achieve that, the whole value chain is investigated and new methodologies and techniques are being developed. In BAM we are characterizing potential Scandium-bearing industrial by-products.
Background Bacterial biofilms are regarded as the most common cause of chronic infections and are often associated with medical devices, such as implants and catheters. Bacteria growing in biofilms produce a protective, extracellular matrix, which enables them to tolerate much higher antimicrobial concentrations than free-living bacteria and survive long enough to acquire antimicrobial resistance. Preventive and therapeutic strategies against biofilm infections in clinical settings commonly involve the application of multiple antimicrobials: biocidal coatings on the biomaterials and systemically administered antibiotics. This frequent practice harbors the risk of the development of cross-resistance via shared resistance mechanisms between antimicrobials used in material coatings and administered antibiotics.
Aim Our goal is to determine how bacteria adapt to antimicrobials during biofilm formation on surfaces coated with antimicrobials and how population dynamics within biofilms affect the transmission of resistance mutations. Specifically, we want to identify antimicrobial-antibiotic-combinations that select for and against antibiotic resistance in biofilms by following the population dynamics of resistant and susceptible strains in competition assays on a single cell level.
Methodology To study the effect of antimicrobial-antibiotic exposure on resistance development and population dynamics on bacterial biofilms in a multidrug environment, we will grow Pseudomonas aeruginosa on glass surfaces with and without antimicrobial coatings and expose them to antibiotics. First, we will screen in vitro for combinations of antibiotics and antimicrobials that select for and against antibiotic resistance. Second, effective combinations will be chosen for in-depth investigations during bacterial adhesion and of mature biofilms of resistant and susceptible genotypes. Third, based on the outcome of the screen and the obtained mechanistic understanding we will choose a clinical example in which we study the relevance of our findings in biofilms grown in vivo.
Relevance Studying the biointerfacial interactions between bacterial biofilms and medical devices in terms of population dynamics as well as on single cell level during multidrug selection will help us understand how drug resistance develops and spreads in persistent biofilm infections. Based on our findings we aim to provide clinical recommendations for improved administration of antibiotics/antimicrobials in combination with medical device materials in order to mitigate against biofilm associated antimicrobial resistance.
The characteristics of different molecules chosen as representatives for specific functionalities in conditioning layers play an important role on attachment behavior and later biofilm formation of bacteria. The chemical composition is a major component influencing the attachment but there is a conglomerate of influences.
Background Bacterial biofilms are regarded as the most common cause of chronic infections and are often associated with medical devices, such as implants and catheters. Bacteria growing in biofilms produce a protective, extracellular matrix, which enables them to tolerate much higher antimicrobial concentrations than free-living bacteria and survive long enough to acquire antimicrobial resistance. Preventive and therapeutic strategies against biofilm infections in clinical settings commonly involve the application of multiple antimicrobials: biocidal coatings on the biomaterials and systemically administered antibiotics. This frequent practice harbors the risk of the development of cross-resistance via shared resistance mechanisms between antimicrobials used in material coatings and administered antibiotics.
Aim Our goal is to determine how bacteria adapt to antimicrobials during biofilm formation on surfaces coated with antimicrobials, how antimicrobial resistance mutations are acquired and evolve within mature biofilms, and how population dynamics within biofilms affect the transmission of resistance mutations. Specifically, we want to identify antimicrobial-antibiotic-combinations that select for and against antibiotic resistance in biofilms by following the population dynamics of resistant and susceptible strains in competition assays.
Methodology We will grow biofilms of Pseudomonas aeruginosa on glass surfaces with and without antimicrobial coatings and expose them to antibiotics. Then we will track their physiological properties, evolutionary adaptations, and population dynamics. First, we will screen in vitro for combinations of antibiotics and antimicrobials that select for and against antibiotic resistance. Second, effective combinations will be chosen for in-depth investigations during bacterial adhesion and of mature biofilms of resistant and susceptible genotypes. Third, based on the outcome of the screen and the obtained mechanistic understanding we will choose a clinical example in which we study the relevance of our findings in biofilms grown in vivo.
Relevance Studying the biointerfacial interactions between bacterial biofilms and medical devices in terms of population dynamics as well as on single cell level during multidrug selection will help us understand how drug resistance develops and spreads in persistent biofilm infections. Based on our findings we aim to provide clinical recommendations for improved administration of antibiotics/antimicrobials in combination with medical device materials in order to mitigate against biofilm associated antimicrobial resistance.
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 in electrical contact with the metal. 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.
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 in electrical contact with the metal. 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.
Biofilm formation on materials leads to high costs in industrial processes, as well as in medical applications. This fact has stimulated interest in the development of new materials with improved surfaces to reduce bacterial adhesion.
We present a flow chamber system to test and quantify bacterial adhesion on materials that are part of antifouling concepts. The adhesion process is standardized and can be adapted to different bacteria in subaquatic of subaerial environments. It is combined with a standardized evaluation procedure based on statistical evidence.
Without precaution, insects may cause serious damage to Museum collections. Quarantine of potentially infested objects can be logistically challenging. Anoxia under controlled nitrogen atmosphere is a most compatible but also time-consuming method to eradicate insect pests in all kinds of different materials. Treatment results are usually effected by duration, temperature, humidity and residual oxygen content. During a two-year research project, 34 relevant pest insect species of all developmental stages were tested in several different materials (wood, paper, wool) to monitor treatment success and to determine optimum treatment parameters. Duration of Treatment ranged from one to three weeks at temperatures of 20 - 27 °C.
As expected, results showed significant differences in mortality among tested species. Highest tolerance of hypoxic conditions was found in older larvae of Hylotrupes bajulus. However, this species is an unlikely museum pest. Anobiids and other wood boring beetles are more often an issue related to cultural heritage. Tested imbedding materials in general had no mortality lowering influence. A combination of three weeks exposure time at up to 0.5 % residual oxygen and at 24 °C and 50 % RH is recommended for infested artefacts.
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.
In nature, the cellular environment of DNA includes not only water and ions, but also other components and co-solutes, which can exert both stabilizing and destabilizing effects on particular oligonucleotide conformations. Among them, ectoine, known as an important osmoprotectant organic co-solute in a broad range of pharmaceutical products, turns out to be of particular relevance. In this article, we study the influence of ectoine on a short single-stranded DNA fragment and on double-stranded helical B-DNA in aqueous solution by means of atomistic molecular dynamics (MD) simulations in combination with molecular theories of solution. Our results demonstrate a conformation-dependent binding behavior of ectoine, which favors the unfolded state of DNA by a combination of electrostatic and dispersion interactions. In conjunction with the Kirkwood–Buff theory, we introduce a simple Framework to compute the influence of ectoine on the DNA melting temperature. Our findings reveal a significant linear decrease of the melting temperature with increasing ectoine concentration, which is found to be in qualitative agreement with results from denaturation experiments. The outcomes of our Computer simulations provide a detailed mechanistic rationale for the surprising destabilizing influence of ectoine on distinct DNA structures.
Emerging infectious diseases arise as a result of novel interactions between populations of hosts and pathogens, and can threaten the health and wellbeing of the entire spectrum of biodiversity. Bees andtheir viruses area case in point. However, detailed knowledge of the ecological factors and evolutionary forces that drive disease emergence in bees and other host–pathogen communities is surprisingly lacking. In this review, we build on the fundamental insight that viruses evolve and adapt over timescales that overlap with host ecology. At the same time, we integrate the role of host community ecology, including community structure and composition, biodiversity loss, and human driven disturbance, all of which represent significant factors in bee virus ecology. Both of these evolutionary and ecological perspectives represent major advances but, in most cases, it remains unclear how evolutionary forces actually operate across different biological scales (e.g., from cell to ecosystem). We present a molecule-to-ecology framework to help address these issues, emphasizing the role of molecular mechanisms as keybottom-up drivers of change at higher ecological scales. We consider the bee–virus system to be an ideal one in which to apply this framework. Unlike many other animal models, bees constitute a well characterized and accessible multispecies assemblage, whose populations and interspecific interactions can be experimentally manipulated and monitored in high resolution across space and time to provide robust tests of prevailing theory.
Social insects employ a range of behaviours to protect their colonies against disease, but little is known about how such collective behaviours are orchestrated. This is especially true for the social Blattodea (termites). We developed an experimental approach that allowed us to explore how the social response to disease is co-ordinated by multistep host-pathogen interactions. We infected the eastern subterranean termite Reticulitermes flavipes with the entomopathogenic fungus Metarhizium anisopliae, and then, at different stages of infection, reintroduced them to healthy nestmates and recorded behavioural responses. As expected, termites groomed pathogen-exposed individuals significantly more than controls; however, grooming was significantly elevated after fungal germination than before, demonstrating the importance of fungal status to hygienic behaviour. Significantly, we found that cannibalism became prevalent only after exposed termites became visibly ill, highlighting the importance of host condition as a cue for social hygienic behaviour. Our study reveals the presence of a coordinated social response to disease that depends on stage of infection. Specifically, we show how the host may play a key role in triggering its own sacrifice. Sacrificial self-flagging has been observed in other social insects: our results demonstrate that termites have independently evolved to both recognize and destructively respond to sickness.
Coastal oceans receive large amounts of anthropogenic fixed nitrogen (N), most of which is denitrified in the sediment before reaching the open ocean. Sandy sediments, which are common in coastal regions, seem to play an important role in catalysing this N‐loss. Permeable sediments are characterized by advective porewater transport, which supplies high fluxes of organic matter into the sediment, but also leads to fluctuations in oxygen and nitrate concentrations. Little is known about how the denitrifying communities in these sediments are adapted to such fluctuations. Our combined results indicate that denitrification in eutrophied sandy sediments from the world's largest tidal flat system, the Wadden Sea, is carried out by different groups of microorganisms. This segregation leads to the formation of N2O which is advectively transported to the overlying waters and thereby emitted to the atmosphere. At the same time, the production of N2O within the sediment supports a subset of Flavobacteriia which appear to be specialized on N2O reduction. If the mechanisms shown here are active in other coastal zones, then denitrification in eutrophied sandy sediments may substantially contribute to current marine N2O emissions.
Soil microbes are exposed to different environmental stressors originating from various sources. Biocides used as material preservatives can represent environmental stressors since they are in direct contact with the environment including soil. Microorganism in soils can adapt to stress by different mechanisms; for example, by the evolution of resistance by de novo mutations or acquisition of resistance genes via horizontal gene transfer (HGT). Here, we hypothesize that material preservatives could enhance the evolution of biocide resistance enabling the potential for cross-resistance to antibiotics. Furthermore, we hypothesize that material preservatives can cause increased frequencies of HGT (i.e. altered community permissiveness) facilitating microbial community adaptation to stress. We will culture soil microorganism with increasing concentrations of selected biocides followed by antibiotic susceptibility determination. Moreover, we will incubate soil mesocosms with selected biocides to investigate if these compounds promote HGT of plasmids that carry resistance genes in soil microbial communities. Together these results will elucidate the potential for the evolution of biocide resistance and cross-resistance to antibiotics as well as the effect of biocides on adaptation to environmental stressors in soil microbial communities.
Soil microbes are exposed to different environmental stressors originating from various sources. Biocides used as material preservatives can represent environmental stressors since they are in direct contact with the environment including soil. Microorganism in soils can adapt to stress by different mechanisms; for example, by transferring mobile genetic elements via horizontal gene transfer (HGT). Here, we hypothesize that material preservatives can cause increased frequencies of HGT (i.e. altered community permissiveness) facilitating microbial community adaptation to stress. Furthermore, we hypothesize that soil microbial communities are primed by biocide exposure facilitating the response to different types of stresses. We will incubate soil mesocosms with selected biocides to investigate if these compounds promote HGT of plasmids that carry resistance genes in soil microbial communities. Subsequently, we will prime the soil microbial community with sub-inhibitory concentrations of biocides followed by exposure to toxic biocide concentrations or other types of common environmental stresses including metals, antibiotics, and salt. Using suitable control experiments, a shift in the functional response of the primed as compared to the non-primed community would indicate that biocides prime microbial communities via HGT. Together these results will elucidate the effect of biocides on HGT-mediated adaptation to environmental stressors in soil microbial communities.
Soil microbes are exposed to different environmental stressors originating from various sources. Biocides used as material preservatives can represent environmental stressors since they are in direct contact with the environment including soil. Microorganism in soils can adapt to stress by different mechanisms; for example, by transferring mobile genetic elements via horizontal gene transfer (HGT). Here, we hypothesize that material preservatives can cause increased frequencies of HGT (i.e. altered community permissiveness) facilitating microbial community adaptation to stress. Furthermore, we hypothesize that soil microbial communities are primed by biocide exposure facilitating the response to different types of stresses. We will incubate soil mesocosms with selected biocides to investigate if these compounds promote HGT of plasmids that carry resistance genes in soil microbial communities. Subsequently, we will prime the soil microbial community with sub-inhibitory concentrations of biocides followed by exposure to toxic biocide concentrations or other types of common environmental stresses including metals, antibiotics, and salt. Using suitable control experiments, a shift in the functional response of the primed as compared to the non-primed community would indicate that biocides prime microbial communities via HGT. Together these results will elucidate the effect of biocides on HGT-mediated adaptation to environmental stressors in soil microbial communities.
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.
Waste-to-energy (WtE) is one of the leading technologies for municipal solid waste (MSW) treatment in Europe. According to Eurostat data, in 2015, 27 % of MSW was utilized in WtE plants, which represents more than 80 million tons per year. Therefore, the European annual production of incineration bottom ash (IBA) is about 20 million tons, as it is about 25 wt% of input MSW. In the European List of Waste, IBA is listed as mirror entry (i.e. waste materials which should be classified as either non-hazardous or hazardous, depending on its hazardous properties and/or content of hazardous substances) under codes 19 01 11 and 19 01 12.
Recent trends indicate that WtE allows, apart from utilization of the energy content of waste, also the recovery of various valuable components. Hence, WtE can be included in the key technologies that can put the circular economy concept into practice. Secondary raw materials in the case of WtE are solid residues, especially IBA, as it is a secondary source, particularly of ferrous metals (Fe) and non-ferrous metals (NF) and glass. Moreover, the residual mineral fraction can be used for various applications in the construction industry, i.e. as aggregates substitute for bound or unbound applications, in cement manufacturing or, as indicated by recent research, also in more sophisticated applications, e.g. for ceramics production. Recovery of these metals can also cause huge greenhouse gas savings. Alone in Europe, metal recovery from IBA reduces greenhouse gas emissions by approximately 3.2 million tonnes of CO2 equivalent.
Small grain size fractions of municipal solid waste incineration (MSWI) bottom ash (BA) contain elemental and chemically bonded metals in appreciable amounts, especially copper. Investigations with a centrifugal concentrator were carried out using samples, which had been treated with different impact devices. Partly the impacts of single devices were visible in outlines, but mostly the surfaces of the metals were still covered with mineral residues. To generate copper rich fractions, parameters of the separation process should ensure mass yields <2%, best between 0.5 and 1%. The density of the concentrates is then generally >3.2 g/cm3. Best results were achieved with material from a special treatment train which is adapted to grain sizes <2 mm. Reliable copper contents between 20 and 40% (single runs >50%) could be realised.
However, considering the required mass yields, referred to this subset only 150–170 g copper would be recovered from 1 Mg MSWI BA. Furthermore, this copper is only in parts present in elemental form. A
dependable added value of such treatment step seems to be given only, if that enables a recycling of the mineral aggregates (tailings) in parallel to avoid landfill costs.
This study focuses on the analysis of a corpus of manuscripts found in Fustat (medieval Cairo, Egypt) in the biggest medieval “archive” found until now: the Cairo Geniza. The giant collection of mostly Jewish documents has been attracting scholars’ attention a lot but so far, the material aspects of these documents seem to have been mainly neglected.
Application of scientific methods of analysis, especially X-Ray fluorescence characterization, contributes to our understanding of the materials used for production of manuscripts during the Middle ages.
Our corpus of the 11th century manuscripts comprises manuscripts written by scribes belonging to three Jewish communities that co-existed in Cairo during this period: the Karaites, the so-called Jerusalemites (or Palestinian) and the so-called Babylonians (or Iraqi), three different communities with different traditions and different leaders. The differences manifest themselves also in the paleographical properties of the manuscripts produced within each community. Can we extend the differences detected by the paleographical analysis to differences in composition of the writing materials and especially the composition of the inks? Or can we relate the differences in the composition to the manuscript type (legal, private...), or to another criterion. In this presentation, we offer answers to some of the questions using statistical analysis of the measurements results.
X-ray photoelectron spectroscopy (XPS) provides elemental and chemical information from the outermost ~10 nm of the sample surface. This is in the same order of magnitude as the thickness of the outer bacterial membrane of gram-negative bacteria, as well as outer membrane molecules as exopolysaccharides and lipopolysaccharides, commonly attached to the cell surface. With the development of near-ambient pressure (NAP)-XPS, bacteria can be analysed with minimal sample preparation.
EnviroESCA is a laboratory based NAP-XPS instrument, equipped with a monochromated Al Kα radiation source and a differentially pumped energy analyser connected to an exchangeable sample environment. It allows for measurements in various gas-atmospheres, including water vapor, which makes it possible to characterise bacteria and other biological samples close to their natural, hydrated state. Artificial model-biofilms of exopolysaccharides, planktonic Pseudomonas Fluorescens and biofilms of Escherichia Coli have been characterised in hydrated and dried state.
High-resolution XPS-spectra from carbon, oxygen, nitrogen and phosphorous can be assigned to carbohydrates, lipids and proteins in general agreement with literature. Especially the carbon 1s peak is of interest. A series of measurements of an E. coli biofilm from 11 mbar in humid environment to 1 mbar air reveal changes in the C1s peak, which suggests that the bacterial surface undergo substantial Change.
The halophilic bacterium Halomonas elongata can tolerate salt concentrations above 10% NaCl and uses the accumulation of the compatible solute ectoine as a major osmoregulatory mechanism. Ectoine can be accumalted inside the cell through import from the medium or de novo synthesis and establishes an osmotic equilibrium with the surrounding1. Ectoine also protects proteins from the effects of freezing, drying and high temperatures4 and DNA from ionizing radiation2. These features make ectoine a valuable compound for cosmetics and medical devices.
H. elongata was originally isolated from a solar salt facility, where it thrives under high salt concentrations. It was found that marine prokaryotes, which are exposed to high oxidative stress in their environment, vary glycolytic strategies5. A variation in the use of the glucose metabolic pathways is also assumed for H. elongata.
The halophilic bacterium Halomonas elongata can tolerate salt concentrations above 10% NaCl and uses the accumulation of the compatible solute ectoine as a major osmoregulatory mechanism. Ectoine can be accumalted inside the cell through import from the medium or de novo synthesis and establishes an osmotic equilibrium with the surrounding1. Ectoine also protects proteins from the effects of freezing, drying and high temperatures4 and DNA from ionizing radiation2. These features make ectoine a valuable compound for cosmetics and medical devices.
H. elongata was originally isolated from a solar salt facility, where it thrives under high salt concentrations. It was found that marine prokaryotes, which are exposed to high oxidative stress in their environment, vary glycolytic strategies5. A variation in the use of the glucose metabolic pathways is also assumed for H. elongata.
The technique of painting on the reverse side of a glass panel was rediscovered by German artists at the beginning of the 20th century. In contrast to other paint techniques (e.g. panel and mural painting), the paint layers are applied in reverse succession starting with the foremost paint layer and ending with the primer (backmost layer). The paintings are viewed in reflected light, thus revealing an impressive gloss, luminosity and depth of colour. The artist group “Der Blaue Reiter” (the Blue Rider) around W. Kandinsky and F. Marc got in touch with this technique in the summers of 1908 and 1909 and spread their knowledge in different regions. Our pioneering project is tracing this transfer of knowledge by a multidisciplinary approach in terms of art history, painting technology and material science. More than 100 artists and >1000 reverse paintings on glass (1905-1955) were identified during the project. This numbers clearly point out that this technique was by far more important for modern art than previously assumed. In-situ, non-invasive measurements (XRF, Raman, VIS, DRIFTS) on a well-considered selection of 67 paintings reveal the broad palette of colorants ranging from traditional to experimental materials. Special attention is paid on artists who are strongly connected to Berlin. Demonstrative examples by W. Dexel, G. Muche and L. Hildebrandt are used to discuss analytical challenges and highlights.
This study focuses on the analysis of a corpus of manuscripts found in Fustat (medieval Cairo, Egypt) in the biggest medieval “archive” found until now: the Cairo Geniza. The giant collection of mostly Jewish documents has been attracting scholars’ attention a lot but so far, the material aspects of these documents seem to have been mainly neglected.
Application of scientific methods of analysis, especially X-Ray fluorescence characterization, contributes to our understanding of the materials used for production of manuscripts during the Middle ages.
Our corpus of the 11th century manuscripts comprises manuscripts written by scribes belonging to three Jewish communities that co-existed in Cairo during this period: the Karaites, the so-called Jerusalemites (or Palestinian) and the so-called Babylonians (or Iraqi), three different communities with different traditions and different leaders. The differences manifest themselves also in the paleographical properties of the manuscripts produced within each community. Can we extend the differences detected by the paleographical analysis to differences in composition of the writing materials and especially the composition of the inks? Or can we relate the differences in the composition to the manuscript type (legal, private...), or to another criterion. In this presentation, we offer answers to some of the questions using statistical analysis of the measurements results.
The Cairo Geniza is an “archive” discovered in the 19th century in Ben Ezra Synagogue in Fustat, a district in Old Cairo (Egypt), located south of the center of modern Cairo. The giant collection of mostly Jewish documents that vary in genres, languages and writing supports contains a large number of early medieval Hebrew manuscripts, mostly in fragmentary form. The larger part of the Cairo Geniza is stored today in the Cambridge University Library (CUL).
The Geniza provides sources for the literary, linguistic, historical studies of the various aspects Jewish life. As the documents attest, at least two Jewish communities co-existed in Fustat up to 11th century: a so-called Babylonian and Palestinian. These communities had different leaders, different traditions and lived independently. The differences seem to manifest themselves also in the paleographical, codicological and some material properties of the manuscripts produced by each community.
The aim of this project is to compare the inks used in the Jewish documents depending on different variables: support (paper, parchment), purpose of the manuscript (legal, private, religious), provenance of the scribe. For the determination of the inks type and composition we had to choose non-invasive, non-destructive and portable techniques to analyse the corpus directly in the CUL.
The analyses were carried out with a mobile energy dispersive micro-X-ray spectrometer ArtTAX® (Bruker GmbH, Berlin, Germany), which consists of an air-cooled, low-power molybdenum tube, polycapillary X-ray optics (measuring spot size 70 µm in diameter), an electrothermally cooled Xflash detector, and a CCD camera for sample positioning (Bronk et al 2001, Hahn et al. 2010). All measurements are executed using a 30 W low-power Mo tube, 50 kV, 600 µA Mo tube, and with an acquisition time of 15 s (live time) to minimize the risk of damage (Fig. 1, 2).
Fig. 1: XRF spectrometer probe above a manuscript fragment
Fig. 2: Typical element profile of a XRF linescan
The Dino Lite digital stereomicroscope (Fig. 3) features built-in LED illumination at 395 nm and 940 nm and a customized external white light source. During use, the microscope is fastened to a small tripod or mounted on a Plexiglas ring holder that incorporates a white light source.
Fig. 3: Dino Lite digital stereomicroscope
Fig. 4: Details of one fragment (T-S 16.124) observed with the Dino microscope (x20). On the left, when illuminated with NIR (Near-Infrared, 940 nm) light, the ink fades, indicating iron-gall ink. On the right, the image under NIR light does not change. It is carbon ink.
On example of these studies is the manuscript T-S 16.124 (Cambridge University Library, Fig. 5) whom belongs to the third corpus. It is a deed, written in Hebrew, dated from 1328 (= 1017 CE) and witnessed by a very high number of people (6) comparing to the standard of similar documents (between 2 and 3), from at least two different Jewish communities in Fustat (trans congregational). The verso is written in Arabic (Bareket 1999).
Fig. 5: Manuscript T-S 16.124 (Cambridge University Library)
To compare the inks, we used the fingerprint model. This method relies on the determination of characteristic elemental compositions and represents the amount of a minor constituent relative to the main component, iron in iron gall ink (Malzer et al. 2004, Hahn et al. 2004, Rabin et al 2014). However, a calculation of a fingerprint based on XRF measurements is not possible in the case of carbon ink since carbon, its main component, cannot be detected with this technique.
Fig. 6: Ink fingerprint T-S 16-124 (recto) normalized to iron (Fe)
Conclusion
We show that using reflectography and XRF analysis it is possible to sort the inks according to their type. In the case of the iron-gall inks, use of the ink fingerprint, i.e. amount of the vitriol components normalized to iron we can make direct comparisons of the ink composition.
We would like also to stress that though the methods of material analysis listed above have been successfully employed in the field of cultural heritage and conservation including ancient and medieval manuscripts they have not yet been used to study fragments from the Cairo Genizah. Therefore, we believe that this research project is a pioneering study that will provide new insights into the history of Hebrew writing materials, their production techniques and materials and, thus, contribute new data to the field of Hebrew paleography.
The Cairo Genizah is a well-known “archive” discovered in the 19th century in Ben Ezra Synagogue in Fustat, a district in Old Cairo (Egypt), located south of the center of modern Cairo. The giant collection of mostly Jewish documents that vary in genres, languages and writing supports contains a large number of early medieval Hebrew manuscripts, mostly in fragmentary form. The larger part of the Cairo Genizah is stored today in the Cambridge University Library, containing about 200,000 fragments.
The Genizah provides sources for the literary, linguistic, historical studies of the various aspects Jewish and non-Jewish life. As the documents attest, at least two Jewish communities co-existed in Fustat up to 11th century: a so-called Babylonian and Palestinian. These communities had different leaders, different traditions and lived independently. The differences manifest themselves also in the paleographical properties of the manuscripts produced by each community.
Although Genizah manuscripts have attracted a great deal of scholarly attention, the material aspects of these documents seem to have been largely neglected. The current study aims to obtain information on the composition of the writing supports and the inks used, in order to obtain insights on trade, local production techniques and social structures.
Can we extend the differences detected by the paleographical analysis to differences in composition of the writing materials ? Can we relate the differences in the composition to a community, to the manuscript type (legal, private...), or to another criterion?
While studying the socio-geographic history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques. The XRF elemental analysis aims primarily at understanding the fingerprints of inks containing metals, making it possible to distinguish among different inks.
Our own research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo). During many years of study, we concluded that the continuous production of Coptic manuscripts from late Antiquity to the Middle Ages offers a unique opportunity for historical study of the ink in a large geographic area. Thanks to the collaboration with the ERC project “PAThs” (www.paths.uniroma1.it), based at the University of Rome La Sapienza, and within the activities of a PhD research dedicated to this topic, we therefore created a new branch of our project focused entirely on the analysis of Coptic inks, pigments, and dyes. This pioneering systematic study of writing materials coming from a specific area and time frame (5th-10th century) aims not only at a better understanding of the complex Coptic multicultural and plurilingual society, but also and mainly at clarifying the links among the Coptic and other societies between the ancient and medieval eras. Finally, it will cast light on the history of the technological development of inks in the eastern world, from Antiquity to the middle ages.
While studying the socio-geographic history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink and a subsequent in-depth analysis using several spectroscopic techniques: XRF, FTIR, and Raman. In most cases, we can obtain satisfactory results using a non-invasive protocol. However, mixed inks that contain no metals evade such a protocol. These inks constitute a heterogeneous group of media used especially in the Middle East and the Islamicate world since at least the 10th century; they are characterized by blending carbon ink and tannins, with or without the addition of vitriol.
Our own research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo). During many years of study, we concluded that the continuous production of Coptic manuscripts from late Antiquity to the Middle Ages offers a unique opportunity for historical study of the ink in a large geographic area. Thanks to the collaboration with the ERC project “PAThs” (www.paths.uniroma1.it), based at the University of Rome La Sapienza, and within the activities of a PhD research dedicated to this topic, we therefore created a new branch of our project focused entirely on the analysis of Coptic inks, pigments, and dyes. This pioneering systematic study of writing materials coming from a specific area and time frame (5th-10th century) aims not only at a better understanding of the complex Coptic multicultural and plurilingual society, but also and mainly at clarifying the links among the Coptic and other societies between the ancient and medieval eras. Finally, it will cast light on the history of the technological development of inks in the eastern world, from Antiquity to the middle ages.
Microbiologically influenced corrosion (MIC) is an expensive but unpredictable problem for the industries. The most well-known culprit for MIC is the sulfate-reducing microorganisms (SRM), such as members from the genus Desulfovibrio. It has been widely accepted that SRM can contribute significantly to MIC through the production of hydrogen sulfide (HS-) or in some cases a direct electron uptake from the metal surface. However, in a real environmental system, SRM is not exclusive and often involved with other microorganisms that may also contribute to MIC, such as methanogens.
Methanogenic archaea can produce methane (CH4) using H2+CO2, formate, methylated amines or acetate. Methanogens are highly abundant in the environment and many are found in very extreme conditions, such as high temperature and high salinity. Previous researches have demonstrated that methanogens are capable of MIC, though the specific mechanisms are still under investigation. In the oil and gas industry, methanogens are not considered as the main contributor for MIC since the corrosion rates are often too low. However, the tests for methanogen-induced MIC are usually performed at static conditions, which cannot represent the system accurately. Here, we developed a novel anaerobic system to evaluate the corrosion potential of methanogens under flow conditions. We will use the Methanococcus maripaludis KA1 strain, which was isolated from a crude oil tank, as the organism of interest. A separate system for Desulfovibrio alaskensis will be established for corrosion rate comparisons. Furthermore, we will study the synergistic effects of M. maripaludis and D. alaskensis on MIC under flow.
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.
Our aims
- Develop a novel flow system to study MIC by methanogens to mimic industrial Environments
- Investigate the inhibitory concentrations of biocides targeting SRB on corrosive methanogenic strains
- Investigate the inhibitory effects of corrosion inhibitors on methanogens
- Compare the inhibitory concentrations to SRB
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 plant-available soil P species, we combined DGT with infrared and P K- and L-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. Additionally, also intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed. Furthermore, infrared and XANES microspectroscopy make it also possible to analyze P compounds on the binding layer with a lateral resolution down to 1 µm2. Therefore, P species of a spatial soil segment (e.g. rhizosphere) can be mapped and analyzed.
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).
Bioinformatics meets virology: The European virus bioinformatics center's second annual meeting
(2018)
The Second Annual Meeting of the European Virus Bioinformatics Center (EVBC), held in Utrecht, Netherlands, focused on computational approaches in virology, with topics including (but not limited to) virus discovery, diagnostics, (meta-)genomics, modeling, epidemiology, molecular structure, evolution, and viral ecology. The goals of the Second Annual Meeting were threefold: (i) to bring together virologists and bioinformaticians from across the academic, industrial, professional, and training sectors to share best practice; (ii) to provide a meaningful and interactive scientific environment to promote discussion and collaboration between students, postdoctoral fellows, and both new and established investigators; (iii) to inspire and suggest new research directions and questions. Approximately 120 researchers from around the world attended the Second Annual Meeting of the EVBC this year, including 15 renowned international speakers. This report presents an overview of new developments and novel research findings that emerged during the meeting.
Despite the recognized excellence of virology and bioinformatics, these two communities have interacted surprisingly sporadically, aside from some pioneering work on HIV-1 and influenza. Bringing together the Expertise of bioinformaticians and virologists is crucial, since very specific but fundamental computational approaches are required for virus research, particularly in an era of big data. Collaboration between virologists and bioinformaticians is necessary to improve existing analytical tools, cloud-based systems, computational resources, data sharing approaches, new diagnostic tools, and bioinformatic training. Here, we highlight current progress and discuss potential avenues for future developments in this promising era of virus bioinformatics. We end by presenting an overview of current technologies, and by outlining some of the Major challenges and Advantages that bioinformatics will bring to the field of virology.
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.
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.
The importance of soldiers to termite Society defence has long been recognized, but the contribution of soldiers to other societal functions, such as colony immunity, is less well understood.
We explore this issue by examining the role of soldiers in protecting nestmates against pathogen infection. Even though they are unable to engage in grooming behaviour, we find that the presence of soldiers of the Darwin termite, Mastotermes darwiniensis, significantly improves the survival of nestmates following entomopathogenic infection.
We also show that the copious exocrine oral secretions produced by Darwin termite soldiers contain a high concentration of Proteins involved in digestion, chemical biosynthesis, and immunity. The oral secretions produced by soldiers are sufficient to protect nestmates against infection, and they have potent inhibitory activity against a broad spectrum of microbes. Our findings support the view that soldiers may play an important role in colony immunity, and broaden our understanding of the possible function of soldiers during the origin of soldier-first societies.
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.
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.
Comparison of Formaldehyde Concentrations in Emission Test Chambers Using EN 717-1 and EN 16516
(2018)
For more than 25 years EN 717-1 (Wood-based panels - Determination of formaldehyde re-lease - Part 1: Formaldehyde emission by the chamber method) is the standard for formalde-hyde emission testing of wooden boards. In 2017 EN 16516 (Construction products - Assess-ment of release of dangerous substances - Determination of emissions into indoor air) was published as a new harmonised standard for the emission testing of construction products. Because test chamber conditions are different, both standards give different concentrations for formaldehyde. To determine a conversion factor four test series were set up with different wooden boards. For a loading of 1 m²/m³ the conversion factor is 1.6. This means that the formaldehyde concentration measured under the conditions of EN 16516 is a factor of 1.6 higher compared to EN 717-1.
Comparison of Formaldehyde Concentrations in Emission Test Chambers Using EN 717-1 and EN 16516
(2018)
For many years EN 717-1 (Wood-based panels - Determination of formaldehyde release - Part 1: Formaldehyde emission by the chamber method) is the standard for formaldehyde emission testing of wooden boards. In 2017 EN 16516 (Construction products - Assessment of release of dangerous substances - Determination of emissions into indoor air) was published as a new harmonised standard for the emission testing of construction products. Because test chamber conditions are different, both standards give different concentrations for formaldehyde. For the determination of a conversion factor four test series were set up with different wooden boards.
Tantalum and niobium are essential for the development of electronics towards a more and more compact design, but without reducing their performance today. Especially in smart phones and tablets, tantalum and niobium capacitors with high charge densities have already become almost indispensable. However, tantalum as a critical raw material is still a problem for the sustainable production of electronics. Due to this fact, the existence of efficient recycling processes especially in Europe is becoming even more important nowadays.
The Bundesanstalt für Materialforschung und -prüfung (BAM) is currently working on the optimisation of an existing pyrometallurgical tantalum recycling process. Optimisation of this industrial process is carried out in a small-scale electric arc furnace (480 kVA, capacity approx. 150 kg/h) at BAM using a new and innovative equipment for on-line analysis of high temperature processes.
The aim of this project is to identify the best timing for an optimum slag tapping, when the slag is lower than minimum targeted tantalum concentration. Hence, LIBS (Laser induced breakdown spectroscopy) is used to identify the chemical composition of the slag layer and during slag tapping. The on-line-LIBS prototype of BAM enables an in-situ measurement of the element distribution in the melt after calibration on the slag system.
First results of this joint research project will be presented including on-line-LIBS-measurements and thermodynamic and kinetic aspects of the process.
Two new approaches towards an emission reference material for use in quality assurance measures for materials emissions testing were developed and intensively tested. The overall goal was to obtain solid materials with homogenous and reproducible (S)VOC release. Since the application in inter-laboratory comparisons is aimed at, it should furthermore be long-term stable to ensure safe shipment to the customer without sustaining compound losses. In the first approach, thermoplastic polyurethane (TPU) was impregnated with the VOC texanol under high-pressure with liquid CO2 as solvent. In the second, styrene (VOC) and the SVOC 2,6-diisopropylnaphthalene (DIPN) were spiked into vacuum grease (VG) and a mixture of paraf-fin/squalane (P/S). For the prediction of the emission rates a finite element model (FEM) was developed for the VG and P/S type materials. All requirements for reference materials were fulfilled, whereas the TPU samples need to be aged for about 10 days until repeatable and re-producible emission rates were obtained.
Two new approaches towards an emission reference material for use in quality assurance measures for materials emissions testing were developed and intensively tested. The overall goal was to obtain solid materials with homogenous and reproducible (S)VOC release. Since the application in inter-laboratory comparisons is aimed at, it should furthermore be long-term stable to ensure safe shipment to the customer without sustaining compound losses. In the first approach, thermoplastic polyurethane (TPU) was impregnated with the VOC texanol under high-pressure with liquid CO2 as solvent. In the second, styrene (VOC) and the SVOC 2,6-diisopropylnaphthalene (DIPN) were spiked into vacuum grease (VG) and a mixture of paraf-fin/squalane (P/S). For the prediction of the emission rates a finite element model (FEM) was developed for the VG and P/S type materials. All requirements for reference materials were fulfilled, whereas the TPU samples need to be aged for about 10 days until repeatable and reproducible emission rates were obtained.
In this work, we use a gas sensor system consisting of a commercially available gas sensor in temperature cycled operation. It is trained with an extensive gas profile for detection and quantification of hazardous volatile organic compounds (VOC) in the ppb range independent of a varying background of other, less harmful VOCs and inorganic interfering gases like humidity or hydrogen. This training was then validated using a different gas mixture generation apparatus at an independent lab providing analytical methods as reference. While the varying background impedes selective detection of benzene and naphthalene at the low concentrations supplied, both formaldehyde and total VOC can well be quantified, after calibration transfer, by models trained with data from one system and evaluated with data from the other system. The lowest achievable root mean squared errors of prediction were 49 ppb for formaldehyde (in a concentration range of 20–200 ppb) and 150 μg/m³ (in a concentration range of 25–450 μg/m³) for total VOC. The latter uncertainty improves to 13 μg/m³ with a more confined model range of 220–320 μg/m³. The data from the second lab indicate an interfering gas which cannot be detected analytically but strongly influences the sensor signal. This demonstrates the need to take into account all sensor relevant gases, like, e.g., hydrogen and carbon monoxide, in analytical reference measurements.
Sintered bioactive glass scaffolds of defined shape and porosity, e.g. made via additive manufacturing, must provide sufficient bioactivity and sinterability. As higher bioactivity is often linked to high corrosion and crystallization tendency, a certain compromise between sintering ability and bioactivity is therefore required. Groh et al. developed a fluoride-containing bioactive glass (F3), which allows fiber drawing and shows a bioactivity well comparable to that of Bioglass®45S5.
To study whether and to what extent the sinterability of F3 glass powder is controlled by particle size, coarse and fine F3 glass powders (300-310µm and 0-32µm) were prepared by crushing, sieving and milling. Sintering, degassing and phase transformation during heating were studied with heating microscopy, vacuum hot extraction (VHE), DTA, XRD, and SEM.
For the coarse glass powder, sintering proceeds slowly and is limited by surface crystallization of primary Na2CaSi2O6 crystals. Although the crystallization onset of Na2CaSi2O6 is shifted to lower temperature, full densification is attained for the fine powder. This finding indicate that certain porosity might be tuned via particle size variation. Above 900°C, intensive foaming is evident for the fine powder. VHE studies revealed that carbon species are the main foaming source.
Subaerial biofilms (SAB) are an important factor in weathering, biofouling, and biodeterioration of bare rocks, building materials, and solar panel surfaces. The realm of SAB is continually widened by modern materials, and the settlers on these exposed solid surfaces always include melanized, stress-tolerant microcolonial ascomycetes. After their first discovery on desert rock surfaces, these melanized chaetothyrialean and dothidealean ascomycetes have been found on Mediterranean monuments after biocidal treatments, Antarctic rocks and solar panels. New man-made modifications of surfaces (e.g., treatment with biocides or photocatalytically active layers) accommodate the exceptional stress-tolerance of microcolonial fungi and thus further select for this well-protected ecological group. Melanized fungal strains were isolated from a microbial community that developed on highly photocatalytic roof tiles after a long-term environmental exposure in a maritime-influenced region in northwestern Germany. Four of the isolated strains are described here as a novel species, Constantinomyces oldenburgensis, based on multilocus ITS, LSU, RPB2 gene phylogeny. Their closest relative is a still-unnamed rock-inhabiting strain TRN431, here described as C. patonensis. Both species cluster in Capnodiales, among typical melanized microcolonial rock fungi from different stress habitats, including Antarctica. These novel strains flourish in hostile conditions of highly oxidizing material surfaces, and shall be used in reference procedures in material testing.
A presentation held for the seminar "Ausgewählte analytische Methoden der Physik" hosted by Prof. Birgit Kanngießer at TU Berlin. The first part focus on depth-dependent XPS-measurements (XPS, synchrotron HAXPES) to obtain a concentration profile of iodine in an artificial biofilm. In the second part, NAP-XPS measurements of various bacterial samples are presented.
Z02 is one of the three technically supporting projects at the CSMC. In collaboration with Z01 and Z03, it aims at bridging the gap between humanities and natural sciences and technology. To that purpose, we set up a laboratory with a range of high-end instruments, most of them mobile, allowing thorough non-destructive analysis of manuscripts. In addition to working on constantly improving the laboratory and the methods of analysis, a substantial part of our activities is dedicated to service, by supporting different research projects conducted at the center.
In this talk, we will present our equipment and the possibilities offered by the different techniques available regarding the different kinds of missions: typology and classification of inks, provenance studies, recovery of faded inscriptions and palimpsests, reconstruction of the history of manuscripts, authentication and dating. We will give a brief overview of our past and ongoing activities in the frame of the second phase of the CSMC. Finally, a selection of three projects will be presented in greater detail to highlight the possibilities of our laboratory and the diversity of missions which can be carried out:
- Support of project C08 on East Frankish manuscripts containing collections of formulae
- Identifying color materials applied in Muhammad Juki's Shahnamah with non-invasive combined methods
- Checking for the presence of metals in the Herculaneum papyri
Recent studies have shown that host-microbiota interactions can lead to dramatic changes in host phenotype especially behaviour. We investigate the causal drivers of microbe-associated shifts in host phenotype by examining how feeding behaviour is modulated by a bacterial infection in an omnivorous cockroach: Blatta orientalis. We conducted food-choice experiments after challenging hosts with the common entomopathogenic soil bacterium Pseudomonas entomophila to understand the impact of bacterial pathogens on host macronutrient preference. We find that immune challenge by this bacterium drives a sharp decline in carbohydrate intake and results in a relative increase in the ratio of protein to carbohydrate consumed. Additionally, infected cockroaches reduce their overall nutrient intake. We show for the first time that cockroach feeding behaviour is dynamically modulated by a pathogen. In contrast to studies on Spodoptera moths, this modulation does not impact any of the immune parameters we measured: it does not affect the abundance of immune related proteins in the hemolymph, hemolymph antimicrobial activity, or survival. This leads to the possibility that as long-lived omnivorous species B. orientalis may be better adapted to unpredictable variation in food availability and quality. An illness-induced anorexia-like response which is thought to assist hosts in limiting nutritional resources available to pathogens is therefore the most likely cause of the observed phenotype. Reduction of carbohydrate intake by sick individuals would be consistent with such an explanation.
In another cockroach species Blatella germanica we also investigate whether in addition to pathogens, host microbiota especially gut commensals are causally responsible for shifts in host behavioural phenotype and immune competence. To address this, we conduct food-choice and immunechallenge experiments in germ-free cockroaches and naïve cockroaches.
Surface characterisation of Escherichia coli under various conditions by near-ambient pressure XPS
(2018)
Bacteria are inherently in a hydrated state and therefore not compatible to ultra-high vacuum techniques such as XPS without prior sample preparation involving freeze drying or fast freezing.
This has changed with the development of near-ambient pressure (NAP)-XPS, which makes it possible to characterise the bacterial surface with minimal sample preparation. This paper presents NAP-XPS measurements of Escherichia coli under various NAP conditions: at 11 mbar in a humid environment, at 2 mbar after drying in the chamber, pre-dried at 4 mbar, and at 1 mbar after overnight pumping at 10^−4 mbar. The high-resolution spectra of carbon, nitrogen, and oxygen are presented and found to be in general agreement with XPS measurements from freeze-dried and fast-frozen bacteria. However, it was found that the amount of carbon components associated with polysaccharides increases relative to aliphatic carbon during drying and increases further after overnight pumping. This implies that drying has an impact on the bacterial surface.
The technique of painting on the reverse side of glass was rediscovered by artists in the early 20th century. The artist group “Der Blaue Reiter” around Wassily Kandinsky and Franz Marc got in touch with this technique in 1908 and 1909. In the following years it gained great popularity, especially in Germany. Nevertheless, the technique has not received its due appreciation in art history. It was considered as stained glass. However, the paint layers are applied cold, hence this artistic technique doesn’t involve a firing step.
Our multidisciplinary project investigates the art historic backgrounds, the painting techniques and materials of modern reverse paintings on glass. More than 1000 paintings from ~100 artists were discovered in the framework of our project. A selection of 60 paintings could be analyzed using non-invasive, in-situ methods such as Raman and VIS spectroscopy, Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) and X-ray fluorescence (XRF). In this paper we want to point out the key role of Raman spectroscopy for our research. It offers the unique opportunity to measure paint layers from both sides. (front = through the glass; reverse = directly on the paint layer).
In the near future, phosphorus (P) recycling will gain importance in terms of decreasing primary resources. Sewage sludge (SSL) is an adequate secondary P-resource for P-fertilizer production but it is also a sink for heavy metals and organic pollutants. The present study is an investigation on thermochemical P-recycling of SSL. Various temperatures and amendments were tested regarding their performance to remove heavy metals and polycyclic aromatic hydrocarbons (PAH) and simultaneous increase of the plant-availability of P. The investigations were carried out on two types of SSL originating from wastewater treatment plants with chemical P-precipitation and enhanced biological P-removal, respectively. The results show that thermochemical treatment with chlorine donors is suitable to remove the majority of heavy metals and that a combination of a gaseous chlorine donor (HCl) and sodium additives leads to both high heavy metal removal and high plant availability of P. Furthermore, plant experiments Show that almost all investigated thermochemical treatments can significantly reduce the bioavailability and plant uptake of heavy metals. Furthermore, PAHs are secondarily formed during low-temperature treatments (400–500 ° ), but can be significantly reduced by using sodium carbonate as an additive.
Direct and indirect effects (DIERec) of the recovery of secondary resources are in the range of 500 million tons per year in Germany; energy savings are 1.4 million TJ. These savings are between 10 and 20% of the total. The effects of materials recovery exceed those of energy recovery by far except for secondary plastic material, where DIERec from energy recovery is higher by factor of 2.7. Untapped potential for the recovery of secondary resources exists in the fine fraction of bottom ash from municipal solid waste incineration, mainly Cu and precious metals, and in urban mining.
Potential use of incineration bottom ash in construction – Evaluation of environmental impact
(2018)
Around 5 million tonnes of MSWI bottom ash (BA) are generated per year in Germany. The incineration itself serves for metals as a concentrating and cleaning process. However, due to the almost exclusive wet extraction out of the furnace chamber the various metals are integrated in a heterogeneous and instable matrix. The metal recovery is therefore still a challenge relating the recovery rate and the purity, respectively. With state of the art treatment trains in Germany around 7.7% of ferrous metals and 1.3% of non-ferrous metals can be recovered out of MSWI BA. Large quantities of the mineral fraction are reused for sub-base material in road construction. A three month ageing period has been established as the common practice of further treatment of bottom ash before reuse applications. In the course of this aging the pH value of bottom ash decreases and contaminants are immobilized by processes like carbonation, hydration and oxidation. In particular leaching of heavy metals may be reduced to environmentally acceptable levels. However, the aging results in fixing of other valuable resources such as metals. Two laboratory scale lysimeters (30 cm in diameter) are being operated for more than three years aiming at the investigation of the long-term leaching behavior of a 0.25/45 mm mineral material obtained by treatment of MSWI bottom ash directly after incineration by a wet processing technology. Artificial rainwater is used as leachant (pH ≈ 6, ingredients NO32-, Cl-, SO42-, Na+, K+, Ca2+, Mg2+). The lysimeters are irrigated related to an average annual precipitation rate of 600 mm/a leading to a liquid to solid ratio (L/S) of about 0.7 per year of operation. Lysimeter tests are more adequate to simulate field scenarios and long-term leaching behavior in contrast to laboratory column tests particularly due to the unsaturated conditions and realistic contact time with the leachant.
In comparison to the leaching of bottom ash (aged for 3 month and non-treated) in column tests the chloride and sulfate leaching in the lysimeters was reduced as a consequence of the previous wet processing. The sulfate release kept almost constant limited by CaSO4 solubility up to an L/S of about 0.7 l/kg. The chloride concentrations dropped quickly, starting from 7300 mg/l, and are now at an almost constant level of 50 mg/l which is significantly above the chloride concentration in the leachant. After an initial decrease of the pH from about 10.4 to 8 at L/S of 0.2 l/kg, the pH increased again and leveled out around 9.8 up to L/S 2.2 l/kg. At an L/S of about 2.5 l/kg now, Cr, Cu are still released. The Cu and Cr concentrations in the leachates were about 760 µg/l and 90 µg/l respectively at the beginning. For both metals the concentration decreased to about 35 µg/l now. The Mo concentrations dropped steadily from 1300 to 250 µg/l, whereas V and Sb concentrations increased in the course of the tests. Fe and Mn are not detectable anymore. More results of this experimental study will be presented and discussed with a special focus on elements forming oxyanions.
Whereas the behavior of geosynthetics in landfill engineering is well studied and documented since decades, little is known on application in applications such as coastal protection or ballast layers for wind energy plants.
However, due to the rapid expansion of offshore wind energy, rising water levels and more extreme weather conditions as a result of climate change more and more hydraulic engineering projects will be realized in the future.
Construction with geosynthetics has various advantages, but it has to be ensured that there is no negative environmental impact from the application of geosynthetics in hydraulic engineering.
It is expected that any effect will be visible only on the long-term. Therefore, accelerated testing is needed to derive requirements for geosynthetics in hydraulic engineering.
Die Präsentation erläutert die Hintergründe der nationalen Anforderungen für die Verwendung von Kunststoffdichtungbahnen in Deponieabdichtungen. Die Beständigkeit wird diskutiert. Anforderungen an das Qualitatsmanagement während der Produktion der Produkte und der Bauphase werden aufgezeigt und die Auswirkungen auf die langzeitige Funktionserfüllung werden beschrieben.
Microbiologically influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms, either chemically (formation of hydrogen sulfide) or electrically (direct electron uptake). Methanogenetic Archaea are also known to be involved in iron corrosion, forming a multi-species biofilm on corroding metallic structures. However, mechanistic details and kinetics of the overall process in methanogen-induced MIC are poorly understood.
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, it is accepted that most of the "endpoints" or more precisely measurement variables are applicable also for nanomaterials. 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.
The poster will present the status quo on recent TGs and GDs development for nanomaterials at OECD level with relevance for physical-chemical characterisation. Emphasis will be given to the proposed OECD TG on particle size and size distribution for manufactured nanomaterials. The development of such a TG is of special importance as particle size and size distribution is considered as major information for nanomaterial identification and characterization. A reliable and reproducible characterisation of particle size and size distribution is also needed for chemicals risk assessment of nanomaterials, for instance to interpret and compare test results and - in future – to forecast interaction and effects of nanomaterials. The presented poster will illustrate the way from the idea for a new TG and new GD to an accepted OECD TG/GD.