Sanitär- und Kommunaltechnik; Umwelttechnik
Filtern
Erscheinungsjahr
Dokumenttyp
- Vortrag (506)
- Posterpräsentation (313)
- Beitrag zu einem Tagungsband (118)
- Zeitschriftenartikel (62)
- Buchkapitel (14)
- Sonstiges (11)
- Dissertation (7)
- Forschungsdatensatz (6)
- Beitrag zu einem Sammelband (3)
- Zeitschriftenheft (Herausgeberschaft für das komplette Heft) (3)
- Tagungsband (Herausgeberschaft für den kompletten Band) (2)
- Sammelband (Herausgeberschaft für den kompletten Band) (1)
- Corrigendum (1)
- Handbuch (1)
- Video (1)
- Preprint (1)
- Forschungsbericht (1)
Sprache
- Englisch (1051) (entfernen)
Referierte Publikation
- nein (1051) (entfernen)
Schlagworte
- Microplastics (46)
- Biocides (39)
- Corrosion (37)
- Antimicrobial resistance (30)
- Fluorescence (29)
- Mobile Robot Olfaction (27)
- Immunoassay (25)
- Biofilm (23)
- Soil (23)
- Environment (18)
Organisationseinheit der BAM
- 4 Material und Umwelt (353)
- 1 Analytische Chemie; Referenzmaterialien (154)
- 4.1 Biologische Materialschädigung und Referenzorganismen (121)
- 6 Materialchemie (94)
- 8 Zerstörungsfreie Prüfung (80)
- 7 Bauwerkssicherheit (79)
- 1.8 Umweltanalytik (69)
- 8.1 Sensorik, mess- und prüftechnische Verfahren (67)
- 4.3 Schadstofftransfer und Umwelttechnologien (65)
- 4.0 Abteilungsleitung und andere (61)
Only a few myxobacteria are known to date that are classified as marine, owing to their salt dependency. In this study, the salt tolerance mechanism of these bacteria was investigated. To this end, a growth medium was designed in which the mutated Escherichia coli strain BKA13 served as sole food source for the predatory, heterotrophic myxobacteria. This enabled measurement of the osmolytes without any background and revealed that the closely related strains Enhygromyxa salina SWB007 and Plesiocystis pacifica SIR-1 developed different strategies to handle salt stress. Ple. pacifica SIR-1, which was grown between 1 and 4% NaCl, relies solely on the accumulation of amino acids, while Enh. salina SWB007, which was grown between 0.5 and 3% NaCl, employs, besides betaine, hydroxyectoine as the major compatible solute. In accordance with this analysis, only in the latter strain was a locus identified that codes for genes corresponding to the biosynthesis of betaine, ectoine and hydroxyectoine.
Lanthanide-doped up-converting nanoparticles (UCNPs) are promising reporters for medical diagnostics and bioimaging, which are excited in the near infrared (NIR) by multiphoton absorption processes, and show multiple narrow emission bands in the visible (vis) and NIR, long luminescence lifetimes in the μs range, and excellent photostability. Current limitations present their relative low absorption cross sections and low fluorescence efficiencies, with the latter being affected by particle size, surface chemistry, and microenvironment, particularly water.
Here, we present results from systematic studies of the excitation power density dependent upconversion luminescence spectra, intensities/intensity ratios of the individual emission bands, slope factors, and quantum yields of UCNPs of varying size, dopant concentration, and surface chemistry in different microenvironments as well as the up- and downconversion luminescence decay kinetics of the different emission bands. Moreover, first studies of the energy transfer from UCNPs to surface-bound organic dyes acting as fluorescence acceptors are shown. Based upon these measurements, fluorescence deactivation channels are identified and spectroscopic parameters for the screening of material performance are derived.
Photodegradation of the „novel“ brominated flame retardant tris-(2,4,6-tribromophenoxy)-s-triazine
(2016)
Brominated flame retardants (BFRs) comprise a class of structurally diverse compounds that are functionally related and used in materials to reduce the flammability of polymers. Due to their global distribution, potential persistence, bioaccumulation and toxicity most of the BFRs of the first Generation are banned or restricted, and replaced by new ones. However, based on similar properties these new compounds may also pose a serious risk by causing adverse effects to human health and the environment.
These alternative BFRs were grouped into two classes: „novel” and „emerging” BFRs. Emerging BFRs are defined as compounds that have been identified in any environmental compartments whereas novel BFRs are only detected in materials and/or goods above 0.1 wt.-%.
The environmental fate of these alternative BFRs is partially unknown. Over the past years a multitude of studies on the photodegradation of BFRs in environmental matrices have been conducted to assess the photochemical behavior and fate in the environment. The photolytic debromination reaction is particularly induced among BFRs by UV exposure.
The novel brominated triazine-based flame retardant tris-(2,4,6-tribromophenoxy)-s-triazine (TTBPTAZ) (Table 1) is a BFR that is mainly used in acrylonitrile butadiene styrene and high impact polystyrene.
Ballesteros-Gómez et al. detected TTBP-TAZ in 8 of 13 plastic parts of consumer products and in 9 of 17 indoor dust samples but the photochemical behavior and fate is not known until now.
The results of the present study, focused on photodegradation processes were performed for the first time for TTBP-TAZ to identify the photolysis intermediates and products to assess the environmental fate.
The repair of earthen structures is not an easy task. Earth as a construction material has comparatively weak mechanical properties. It is also susceptible towards liquid water, were it can lose cohesion very quickly if certain moisture contents are exceeded. Repair concepts of structures built with such materials are therefore challenging. Historical earthen structures often exhibit damages in form of extensive cracking, which may have been caused by static or dynamic loads. Frequently these cracks are insufficiently or inappropriately repaired because of lack of knowledge and / or technology. In particular, the behaviour of crack repair by grouting poses a challenge in earthen materials and demands specific requirements for the grouting mortar, such as low water content, good water retention, low shrinkage. Grouting materials require additional specifications such as compatible strengths and Young’s modulus as well as good adhesion to the earthen substrates. In addition, grouts have to be sufficiently flowable to fill small cracks and voids without segregation or bleeding. Therefore, the rheological behaviour has to be well understood and controlled to gain the desired effects.
The repair of cracks in earthen buildings is traditionally done by stuffing manually mortar into the gap. Naturally, this method is only usable for cracks with large widths. Another disadvantage is that cracks going through thicker walls cannot be completely reached by the tools used for stuffing the mortar into the crack. Lime based grouts for earthen materials were usually used for re-attachment of plasters but less for structural reasons. Due to the nature of earthen materials grouts based on formulated or hydraulic lime (according to the definition in EN 459-1) have to meet considerable demands on a variety of properties, which are related to compatibility, durability and in particular to the ability of being injected. The goal of this study was to create a grout, which can be used to re-establish structural continuity in cracked earthen masonry or other massive earth walls (rammed earth and cob) with the focus on grouting cracks. The grout material was based on hydrated lime (calcium hydroxide) with additions of pozzolana and lime stone filler.
Contaminated land, landfills and sediments pose a serious environmental threat by polluting groundwater in the surrounding area. In 14 European countries contamination caused by uranium represents a particularly serious danger where drinking water resources might be affected. Other heavy metals and organic pollutants can also have a strongly deleterious effect on groundwater. Available technologies (e.g. pump- and-treat) fall short of solving the problem because their performance is not yet adequate for effective remediation. The aim of the project is to elaborate the scientific basis for laboratory and pilot-scale testing of and the practical application of a considerably more efficient and cost-effective in-situ reactive barrier technology targeting the above contaminants. The primary model test site will be an area in Southern Hungary contaminated by uranium mining- thus including a region which is due to become part of the European Union.
The approach taken to meet the project objectives was the characterisation of different reactive materials and relevant attenuation processes in the reactive matrix of the permeable barrier with special respect to their long-term behaviour. The experimental work included laboratory experiments at different scales, going from bench-scale tests up to pilot-scale, and field-scale experiments. Experimental conditions were predetermined by the characteristics of the model site, such as geologic and hydrogeological settings, soil composition, and type, extent and spreading of the contamination. Technological methods to enhance the long-term efficacy and cost-effectiveness of permeable reactive barrier systems were developed and tested under realistic conditions.
The use of renewable energy technologies, such as photovoltaics (PV) should be sustainable and environmentally compatible and therefore protect the environment from risks and damaging impacts. Regarding the growing number of installed photovoltaic systems, the end-of-life management of the pv-modules will become increasingly important. Thin film panels contain hazardous substances that may harm the environment if they are not recycled or disposed properly after reaching the end of their service life. Heavy metals, for example, can be toxic as well as carcinogenic or teratogenic. Processing methods for the recycling of PV thin film modules have to take these facts into account. Currently the available recycling techniques usually utilise chemicals such as acids for a wet-chemical treatment of end-of-life modules. The aim of RESOLVED was to identify and test alternative methods for a wet-mechanical treatment in order to reduce the consumption of chemicals in the recycling of thin film modules. Furthermore, the recovered Cadmium-Telluride (CdTe) and Copper-Indium-Diselenide/Disulfide (CIS) should be helping to save scare resources especially for limited elements such as tellurium and indium. The project RESOLVED investigated the recovery of semiconductors material as secondary raw material and the decontamination of the residues of the PV thin film modules. These goals were achieved by testing and optimising existing technologies for the recycling process as well as for the enrichment of the semiconductor materials. The target is to re-use the enriched recovered material in the production of new PV modules. Special efforts were made to look into life cycle analysis, process sustainability, economical aspects, and resource availability.
In-plane shear behaviour of earthen materials panels strengthened with polyester fabric strips
(2016)
An experimental investigation was carried out to study the in-plane shear behaviour of earthen material Panels strengthened with polyester fabric strips. Strengthened panels were developed to exploit the strength potential of earthen materials and to solve its lack of tensile strength, significantly improving not only strength but also ductility. Three earthen materials were considered: cob, earth block masonry (EBM) and rammed earth (RE). As first approach the strengthening configuration, based on different adhesive materials, was tested only for cob panels. As part of the study the results of a big testing campaign of unstrengthened Panels were considered. Seven strengthened panels were tested in diagonal compression/shear.A unique reinforcement orientation was used. The results of these tests are presented in this paper, and include the load-displacement behaviours, crack patterns, failure modes. The results showed that the reinforcement was the most effective in EBM panels, with increase in strength and ductility observed. In RE and cob panels the reinforcement did not likely contribute significantly to the shear resistance, due to a lack of embedment length of the strips. Instead, in EBM it was likely that the vertical reinforcement acted in tension to restrain shear induced dilation and to restrain sliding.
The paper presents a comparison between two different numerical modelling approaches aimed to simulate the in-plain behaviour of rammed earth walls, namely under axial, diagonal and cyclic shearcompression loading. In the first part of the study the mechanical characterisation of wallets tested under uniaxial compression and diagonal compression and walls tested under in-plane cyclic shear-compression loading is presented. The results were used to implement and validate the finite element simulations. The numerical modelling of the rammed earth samples tested is then discussed in the second part. A non-linear constitutive law based on the total strain rotating crack model (TSRCM) was employed as implemented in the DIANA® software [1]. The aim of the numerical analyses presented here is to simulate the behaviour of rammed earth under different inplane loading conditions. For the wallets, tests under static loading both macro- and micro-modelling approaches were considered for the simulation of the experimental tests. For the walls subjected to cyclic loading only the micro-modelling approach was applied for the simulation of the experimental tests. The respective FEM model was calibrated with the experimental results. The rammed earth layers were represented by continuum elements, the contact surfaces between layers by interface elements. This approach allowed assessing the influence of the apparent weakness of the interfaces between layers on the shear behaviour of rammed earth. The goal of the numerical simulation of the cyclic tests was to establish the adequacy of common analytical methods (e. g. used for masonry) applied to the analysis of rammed earth. Rammed earth exhibits brittle characteristics similar to masonry materials and is used in geometrical typologies, such as walls, common in masonry construction.
The repair of earthen structures is not an easy task. Earth as a construction material has comparatively weak mechanical properties. It is also susceptible towards liquid water, were it can lose cohesion very quickly if certain moisture contents are exceeded. Repair concepts of structures built with such materials are therefore challenging. Historical earthen structures often exhibit damages in form of extensive cracking, which may have been caused by static or dynamic loads. Frequently these cracks are insufficiently or inappropriately repaired because of lack of knowledge and / or technology. In particular, the behaviour of crack repair by grouting poses a challenge in earthen materials and demands specific requirements for the grouting mortar, such as low water content, good water retention, low shrinkage. Grouting materials require additional specifications such as compatible strengths and Young’s modulus as well as good adhesion to the earthen substrates. In addition, grouts have to be sufficiently flowable to fill small cracks and voids without segregation or bleeding. Therefore, the rheological behaviour has to be well understood and controlled to gain the desired effects.The repair of cracks in earthen buildings is traditionally done by stuffing manually mortar into the gap. Naturally, this method is only usable for cracks with large widths. Another disadvantage is that cracks going through thicker walls cannot be completely reached by the tools used for stuffing the mortar into the crack. Lime based grouts for earthen materials were usually used for re-attachment of plasters but less for structural reasons.Due to the nature of earthen materials grouts based on formulated or hydraulic lime (according to the definition in EN 459-1) have to meet considerable demands on a variety of properties, which are related to compatibility, durability and in particular to the ability of being injected. The goal of this study was to create a grout, which can be used to re-establish structural continuity in cracked earthen masonry or other massive earth walls (rammed earth and cob) with the focus on grouting cracks. The grout material was based on hydrated lime (calcium hydroxide) with additions of pozzolana and lime stone filler.
In-plane shear behaviour of earthen materials panels strengthened with polyester fabric strips
(2016)
An experimental investigation was carried out to study the in-plane shear behaviour of earthen material panels strengthened with polyester fabric strips. Strengthened panels were developed to exploit the strength potential of earthen materials and to solve its lack of tensile strength, significantly improving not only strength but also ductility. Three earthen materials were considered: cob, earth block masonry (EBM) and rammed earth (RE). As first approach the strengthening configuration, based on different adhesive materials, was tested only for cob panels. As part of the study the results of a big testing campaign of unstrengthened Panels were considered. Seven strengthened panels were tested in diagonal compression/shear.A unique reinforcement orientation was used. The results of these tests are presented in this paper, and include the load-displacement behaviours, crack patterns, failure modes. The results showed that the reinforcement was the most effective in EBM panels, with increase in strength and ductility observed. In RE and cob panels the reinforcement did not likely contribute significantly to the shear resistance, due to a lack of embedment length of the strips. Instead, in EBM it was likely that the vertical reinforcement acted in tension to restrain shear induced dilation and to restrain sliding.
Biocide leaching was investigated for acrylate and vinyl acetate based coatings containing biocides either as liquid formulations or microcapsules. Laboratory and field tests indicate similar relations of results on carbendazim, diuron, terbutryn and OIT from different coatings in laboratory and field experiments. Emissions were higher in EN 16105 laboratory tests than from vertically installed test specimens exposed to weathering, and slower for microencapsulated biocides. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. Emission curves related to runoff water were similar in repeated field experiments. Relative humidity, temperature and global radiation were identified as meteorological factors that affect leaching by complex interaction besides the amount of driving rain.
Many wooden artworks are contaminated by DDT (dichlorodiphenyltrichloroethane) as a result of a surface treatment by means of Hylotox-59©. The liquid preservative was used until the end of the 80s. DDT crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen.
The removal of DDT was evaluated employing femtosecond and nanosecond laser radiation and cold atmospheric plasma technique using different working gases (air, nitrogen, and argon).
Before laser application, a chlorine measurement is done by X-ray fluorescence (XRF) analysis as reference. After laser processing, the XRF analysis is used again at the same surface position to determine depletion rates. Additionally, a documentation and characterization of the sample surface is done before and after laser and plasma treatment using optical microscopy. For plasma processing with various systems a chlorine measurement is done by gas chromatographic-mass spectrometry (GCMS) analysis.
For laser treatment a depletion of the chlorine concentration of 55-70% and 75% was achieved for 1064-nm nanosecond pulses and 800-nm femtosecond pulses, respectively. For the application of 30-fs laser pulses, no crystalline DDT residues remain on the sample surfaces. This holds also for the plasma processing with nitrogen as working gas.
The increasing pollution of terrestrial and aquatic ecosystems with plastic debris, which leads to the accumulation of microscopic plastic particles of still unknown fate, is an upcoming problem of our time. In order to monitor the degree of contamination and to understand the underlying processes of degradation and internalization of plastic debris, analytical methods are urgently needed, which help to identify and quantify microplastics. Currently, expensive collected and purified materials enriched on filters are investigated by (micro) infrared spectroscopy (FTIR). Few studies using micro-Raman spectroscopy have been published as well. In contrast to FTIR, Raman spectroscopy can handle wet samples, but it suffers from interference of fluorescent materials. Both micro-FTIR- and micro-Raman, always include time consuming scanning and mapping procedures followed by the manual inspection and measurement of selected particles.
The vibrations of soil and foundations are demonstrated for different types of loading. Train-induced ground vibrations are studied in a measurement campaign where a test train has run with regularly varied speeds. The measured train-induced soil vibration at 2 to 100 m distance from the track is compared with the wave propagation due to hammer excitation and with the theoretical wave field. The strong influence of the soil and the train speed on the amplitudes and frequencies of the vibration has been analysed for passages of the locomotive and the carriages. - The generation of ground vibration by strong explosions has been studied on a large testing area with sandy soil. The propagating waves were measured in a regular grid of measuring points in 10 to 1000 m. Therefore, the dominance of certain waves at certain distances and the changes of compressional waves and Rayleigh waves could clearly be observed. The results are compared with impulse hammer measurements in the range of 5 to 50 m. - A drop test facility has been built on the testing area of the Federal Institute of Materials Research and Testing (BAM). Heavy masses (containers) of up to 200 t can be dropped from 10 m height on a big reinforced concrete foundation. The foundation was instrumented by accelerometers, strain gauges and pressure cells to give information about the loading condition and by geophones to measure the vibration of the surrounding soil and building. Both excitation processes, the release of the mass and the impact, produce high vibration amplitudes. On a smaller drop foundation, the influence of the drop height and the target stiffness has been studied more systematically.
Reliable analysis of chemical indicators in water, sediment and soil samples for the purpose of environmental pollution assessment poses one of the greatest analytical challenges, having in mind the complexity of sample matrix and low concentrations of pollutants. Organics (pesticides, PAHs, PCBs, etc.) and heavy metals (Hg, Cd, Ni, Pb and As) represent target parameters. Laboratories performing sampling and tests in this field regulated by respective EU directives, need strong support in terms of providing them with appropriate matrix CRMs enabling the process of quality control. NMIs and DIs with proven metrological capabilities for the production and certification of such materials are necessary for the provision of quality data. This project is aiming to develop capacity to produce CRMs for environmental analysis by transferring the theoretical and practical know-how between the partners and combining their skills to focus on environmental CRM production in accordance with ISO Guide 34. Production process includes good manufacturing practices for processing materials, method development and validation for homogeneity, stability and characterisation tests, characterisation of selected analytes together with additional information about matrix constituents, the calculation of individual uncertainties (between units inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of the matrix reference materials. Inter laboratory comparison registered as EURAMET project is set as the ultimate project outcome, confirming the partners’ capabilities in applying newly acquired skills.
Reliable analysis of chemical indicators in water, sediment and soil samples for the purpose of environmental pollution assessment poses one of the greatest analytical challenges, having in mind the complexity of sample matrix and low concentrations of pollutants. Organics (pesticides, PAHs, PCBs, etc.) and heavy metals (Hg, Cd, Ni, Pb and As) represent target parameters. Laboratories performing sampling and tests in this field regulated by respective EU directives [1], need strong support in terms of providing them with appropriate matrix CRMs enabling the process of quality control. NMIs and DIs with proven metrological capabilities for the production and certification of such materials are necessary for the provision of quality data. This project is aiming to develop capacity to produce CRMs for environmental analysis by transferring the theoretical and practical know-how between the partners and combining their skills to focus on environmental CRM production in accordance with ISO Guide 34 [2]. Production process includes good manufacturing practices for processing materials, method development and validation for homogeneity, stability and characterisation tests, characterisation of selected analytes together with additional information about matrix constituents, the calculation of individual uncertainties (between units inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of the matrix reference materials. Inter laboratory comparison registered as EURAMET project is set as the ultimate project outcome, confirming the partners’ capabilities in applying newly acquired skills.
Essential processes in the establishment and maintenance of rock biofilms include photosynthesis, production of extracellular polymeric substances, substrate penetration and atmospheric nutrient enrichment. Functional diversity is supported by a complex subaerial biofilm (SAB) community of heterotrophic and phototrophic microorganisms. Stress tolerant and melanised Ascomycetes dominate heterotrophic SABs while diverse algae and cyanobacteria comprise the phototrophic consortia. Laboratory simulation of SABs permits use of molecular-genetic methods coupled with geochemical and microscopic analyses to study weathering. Our in vitro model includes two free-living and symbiosis-competent, genetically tractable microorganisms: the cyanobacterium Nostoc punctiforme and the microcolonial rock-inhabiting fungus Knufia petricola. This genetically amenable cyanobacterium/fungus model biofilm allows development of quantitative methods tailored to the natural diversity of SABs. Precise, reproducible studies using this model biofilm have shown that both the melanised fungus, as well as the combined bacterial/fungal system, enhances the weathering of minerals. Geochemical signatures of these in vitro rock biofilms can now be obtained and compared with bacterial/fungal mutants of varied EPS composition and substrate penetration patterns. And finally, precise study of the model cyanobacterium/fungus biofilm will Permit prediction of the effects of conservational treatments.
The characterization of the optical properties of photoluminescent systems, that scatter, like dispersions of nanoparticles with sizes exceeding about 25 nm or solid nanophosphors is of increasing importance for many applications in the life and material sciences. Examples present nanoscale optical reporters and dye-doped microparticles for bioimaging, fluorescence assays or DNA sequencing as well as nanocrystalline emitters like semiconductor quantum dots and rods or lanthanide-based nanophosphors embedded into solid matrices for solid state lighting, display technologies, or barcoding/security applications. The assessment and comparison of material performance as well as the development of rational design strategies for improved systems require spectroscopic tools, which enable the determination of the signal-relevant optical properties like photoluminescence quantum yields and brightness values.
This encouraged us to built up an integrating sphere setup enabling absolute measurements of photoluminescence spectra and quantum yields of transparent and scattering photoluminescent dispersions and solid samples in different measurement geometries, i.e., direct and indirect illumination and the combination of both geometries and perform first measurements with selected emitters. Here, the design of this setup is presented and first recommendations concerning suitable measurement geometries are given.
A reversed phase high performance liquid chromatography coupled to an inductively coupled plasma mass spectrometer (HPLC-ICP-MS) approach in combination with isotope dilution analysis (IDA) for the separation and parallel quantification of nanostructured and ionic silver (Ag) is presented. The main focus of this work was the determination of the ionic Ag concentration. For a sufficient stabilization of the ions without dissolving the nanoparticles (NPs), the eluent had to be initially optimized. The determined Ag ion concentration was in a good agreement with results obtained using ultrafiltration. Further, the mechanism of the NP separation in the HPLC column was investigated. Typical size exclusion effects were found by comparing results from columns with different pore sizes. Since the recovery rates decreased with increasing Ag NP size and large Ag NPs did not elute from the column, additional interactions of the particles with the stationary phase were assumed. Our results reveal that the presented method is not only applicable to Ag NPs, but also to gold and polystyrene NPs. Finally, IDA-HPLC-ICP-MS experiments in single particle mode were performed to determine the particle cut-off size. The comparison with conventional spICP-MS experiments resulted in a similar diameter and particle size distribution.
The interface between materials and the environment is populated by microorganisms which organize on surfaces to form specially adapted and resistant microbial associations, so-called biofilms. Surface-bound biofilm growth is associated with substantial secretion of metabolic products that can significantly influence material corrosion. Here, a group of material-inhabiting fungi are presented, which colonize and weather air-exposed materials such as building façades, roofs and solar systems. A selected model fungus is used to carry out genetic and molecular biology experiments, which are microbiologically cutting-edge and allow for the development of novel time-saving techniques for material testing. The degree of material damage under the influence of this model fungus shows a measure of the aggressiveness of the biofilm under defined environmental conditions - and thus explores fundamental components of the interaction between material and biofilm.
The European Water Framework Directive (WFD) 2000/60/EC specifies a list of 33 priority water pollutants. For these substances, Environmental Quality Standards (EQS), equivalent to the maximum allowable concentrations, had been defined at very low levels.
EQS values refer to the whole water body, i.e. include contaminants which are associated to suspended solids or colloids present in the natural water. For several priority pollutants primary analytical methods capable of measuring the target analytes at EQS level in natural water are still missing. The project has developed and validated such methods for three selected compounds, namely Tributyltin (TBT), Polybrominated Diphenylether (PBDE) and Polycyclic Aromatic Hydrocarbons (PAH).
The occurrence of persistent organic pollutants like polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) in the environment is still a matter of concern, even years after their use was abolished. Hence, threshold values are regulated by law which reference a number of national and international standards for determination of said contaminants. In this context, soil is an especially difficult matrix, because several defining parameters can vary in a wide range. Organic matter content in particular has a crucial influence on extractability of contaminants because it largely governs formation of non-extractable or bound residues.
For this study, four soils of different total organic carbon (TOC) content were generated from uncontaminated reference soil (RefeSol 01-A) and compost which were spiked to contaminant levels representative of the Bundes-Bodenschutz-Verordnung (BBodSchV). These test materials were extracted using accelerated solvent extraction (ASE), Soxhlet extraction, and liquid-liquid extraction. For the latter method, samples were initially extracted for 15 minutes employing acetone. The follow-up extraction step was carried out using cyclohexane and the extraction time varied between 15 minutes and 16 hours. After clean-up, extracts were analysed via gas chromatography-mass spectrometry (GC MS) and with a gas chromatograph equipped with an electron capture detector (GC ECD).
Statistical analysis of the experimental values showed that recovery was not dependent on matrix TOC content. Also, no clear preference for a single method could be detected. Concerning liquid-liquid-extraction, it is merely observed that prolonged extraction time results in slightly higher recoveries, while moderate extraction times appear to yield the most robust results. Although Soxhlet and ASE show high recoveries, they also lead to larger standard deviations and are not suitable for determination of thermolabile pesticides.
In addition to recovery by different extraction methods, the agreement of values obtained by ECD and MS was evaluated. For ECD, standard deviations are generally higher but overall the values obtained by MS and ECD are comparable.
Trans-Zearalenone(ZEN)is a non-steroidal estrogenic mycotoxin which frequently contaminates cereal grains worldwide. Ingestion of food and feed containing ZEN causes numerous mycotoxicoses in animals and possibly humans with pronounced estrogenic effects. Due to the trans-configurated double bond, ZEN isomerizes to the cis-configuration upon the influence of light. This work investigates the instrumental analysis, metabolism and toxicity of ZEN and cis- ZEN. The first part focused on the determination of ZEN in edible oils. Due to a maximum level of 400 µg/kg ZEN in the European Union (EU), reliable analytical methods are needed. A comprehensive method comparison proved dynamic covalent hydrazine chemistry (DCHC) to be the most suitable approach. Thus, an automated solid phase extraction (SPE) coupled online to high performance liquid chromatography (HPLC) was developed with the novelty of a covalent SPE step comprising the DCHC principle. The automated online system allows an accurate, selective and reliable quantification of ZEN in edible oils in compliance with EU performance criteria while significantly reducing workload and thereby personnel costs. In contrast to ZEN, reference standards and analytical methods are missing for cis- ZEN which causes a lack of data on the occurrence, fate and risks of cis-ZEN. Therefore, a native and an isotopically labeled cis-ZEN standard were synthesized and implemented in an existing stable isotope dilution analysis HPLC tandem mass spectrometry (HPLC-MS/MS) method. Using this method, a large extent of cis-ZEN formation was observed for ZEN contaminated maize germ oils when exposed to daylight which confirms that cis-ZEN can be a relevant food contaminant and should be considered in the analysis of food and feed. Furthermore, this work investigated the in vitro phase I metabolism of ZEN and cis-ZEN in rat and human liver microsomes by using HPLC-MS and -MS/MS analyses. The metabolic pathways of cis-ZEN were found to be essentially similar to ZEN including reduction and oxidation reactions generating α- and β-cis- zearalenol as well as 13- and 15-OH-cis-ZEN. A previously unidentified oxidative metabolic pathway for both isomers of ZEN results in the formation of cis-ZEN-11,12-oxide and ZEN-11,12-oxide in human liver microsomes. The estrogenicity of cis-ZEN and its reductive metabolites was assessed using the E-Screen assay. cis-ZEN proved to be slightly more estrogenic than ZEN. Biotransformation of cis-ZEN to β-cis-ZEL corresponds to a detoxification, whereas metabolism to α-cis-ZEL resembles a metabolic activation as its estrogenicity considerably exceeds that of cis-ZEN. The catecholic metabolites can be expected to show a decreased estrogenicity as demonstrated for 15-OH- ZEN. Independent of the estrogenic effects, the catecholic and epoxidic metabolites identified in this work can be expected to act genotoxic and carcinogenic. The epoxides in particular could fundamentally change the widely accepted view of ZEN causing adverse effects exclusively through endocrine disrupting actions.
While organic pollutants have been extensively studied in urban and agricultural areas, data from forested regions are relatively rare.
Within the framework of a forest soil inventory in Germany polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were analyzed in 1500 soil samples taken from 3 soil horizons at 447 sites. An analytical protocol was developed and validated for the simultaneous extraction and measurement of all analytes in humic rich soil at trace level range. It included pressurized liquid extraction (PLE) and a two step cleanup procedure consisting of gel permeation chromatography (GPC) followed by solid phase extraction (SPE). Quantification was carried out using gas chromatography combined with mass spectrometry (GC-MS). In line with the monitoring campaign a comprehensive quality assurance concept was implemented to guarantee constant analytical measurement conditions for two years. The protocol is applicable for field laboratories with a high level of automation and for analyzing high sample amounts.
At most sampling sites pollutant concentrations gradually decrease with depth. Only few spots showed highest concentrations in the upper mineral soil. In the O-horizon the sum concentrations of 16 PAHs range from 104 to 14.000 µg/kg, of 6 PCBs from <1 to 106 µg/kg and the sum of DDT and metabolites range from <1 to ca. 4.000 µg/kg.
The observed concentration of PAH, PCB and OCP reflect an ubiquitous background contamination at most sites. Relatively high concentrations of PAH and PCB are related to industrial areas and peak concentrations only of PAH are associated with open cast mining of brown coal areas. The spatial distribution of the contents of DDT and metabolites in German forest soils can clearly be attributed to historic application. A contribution of ubiquitous background pollution derived from long-range atmospheric transport is likely for some compounds in the studied area, e.g., DDT in the western part of Germany. The results generally reflect the distribution of POPs in densely populated and industrialized countries located in temperate regions].
The determination of organochlorine pesticides (OCP) and polychlorinated biphenyls is challenging because they are strongly physical and chemical bound to soil organic matter. There are various valid standards for the determination of these analytes in soil that differ especially in the extraction method and extraction time. In order to make profound assessments concerning the extraction efficiency seven extraction procedures namely pressurized liquid extraction (PLE), soxhlet and shaking with different extraction times 0.5 h, 1 h, 3 h, 6 h and 16 h were compared. For the study four soils of different total organic carbon (TOC) content were generated from uncontaminated reference soil and compost which were spiked to contaminant levels representative of the Bundes-Bodenschutz-Verordnung. Clean-up and measurement conditions using gas chromatography with mass spectrometry (GC-MS) were kept constant. Statistically analysis of the experimental values showed that recovery rates were not dependent on matrix TOC content. In consideration of measurement uncertainties of 10% - 20% for the determination of OCP and PCB in soil no differences in the efficiency between the tested extraction procedures could be observed.
CHEF provides knowledge about flood protection of cultural heritage objects and directly supports the European Floods Directive by giving recommendations on how to assess the vulnerability of monuments. A comprehensive analysis of protective measures BEFORE, DURING and AFTER a flood has been carried out within the project, including technical and administrational measures. An overview of these measures is given, followed by recommendations on how to establish the most effective protective strategies.
The aim of this work is to develop measurement procedures to provide full traceability and robust uncertainty statements for dissolved elemental mercury (Hg(0)), inorganic mercury (Hg(II)) and methyl-mercury (MeHg) in freshwater and sea water, and inorganic mercury (Hg(II)) and methyl-mercury (MeHg) in biota. Accurate measurements with low uncertainties e.g. <50 % at the EQS level are required to assess concentration levels and trends in these important environmental reservoirs for mercury.
In particular this work aims to:
Develop and validate primary measurement procedures for Hg speciation (Hg(II), MeHg and Hg(0)) in fresh and sea waters at sub-ng levels in the presence of suspended particular matter and/or colloidal fractions,
Apply the developed IDMS procedures in water in order to evaluate possible artefacts associated with sample collection and preparation, preserving speciation and/or correcting for possible post-sampling interconversions,
Develop and validate primary measurement procedures for the accurate quantification of Hg(II) and MeHg in biota, using samples from the Federal Environmental Specimen Bank,
Apply the developed IDMS procedures in biota in order to evaluate the effect of different treatments for fish sample preparation.
Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS.
The polycyclic musks 6-Acetyl-1,1,2,4,4,7-hexamethyltetraline (AHTN) and 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-ɣ-2-benzopyran (HHCB) are widely used fragrances in cosmetics, products of daily care and cleaning products for households and industry. They are in the focus of interest due to their estrogenic potential. Both compounds can be found at low μg/L concentrations in surface water where they are introduced mainly by sewage treatment plants supplied by municipal wastewater. In order to disinfect wastewater in sewage treatment plants or water in swimming pools, chlorine can be added to water as gas or hypochlorite solution. This disinfectant has a high oxidation potential resulting in the formation of disinfection by-products, the estrogenicity and toxicity of which might differ from their precursor. In this work the behaviour of AHTN and HHCB upon treatment with sodium hypochlorite solution was investigated and chlorinated possible disinfection by-products could be identified as well as a carboxylic acids and lactones derived from AHTN and HHCB. The identified species were characterized by GC-MS, LC-MSn and 1H-NMR. The elucidated structures of potential disinfection by-products are verified by X-ray crystallography. Finally the estrogenicity between the parent analytes and generated transformation products were compared. For that task, MCF-7 assay has been chosen for being most relevant to humans. Moreover metabolism studies were carried out using AHTN, HHCB and their disinfection by-products.
Fluorophore labeled proteins and antibodies, referred to also as targeted optical probes, present a promising strategy for a variety of applications from fundamental cell-based biological studies to in vivo diagnostics and image guided surgeries in humans. In this respect, design strategies for the preparation of such conjugates from different dyes including analyte-responsive fluorophores are presented as well as their analytical and spectroscopic characterization employing Absorption spectroscopy and steady state and time-resolved fluorometry. Special emphasis is dedicated to the influence of dye hydrophilicity and labeling density on the optical properties and binding behavior of these dye-bioconjugates including their performance in in vitro and in vivo bioimaging studies.
An Annex XV restriction dossier for cadmium in artists’ paints was submitted by an EU member state to the European Chemicals Agency ECHA. By cleaning used brushes under the tap cadmium can enter the food chain via waste water treatment and subsequent agricultural application of the sewage sludge. It was estimated that 110 kg Cd per year is spread on agricultural land via this exposure route. Other sources of Cd amount to almost 120 tons per year.
The mobility of Cd from pigments was studied in a field-like scenario by leaching experiments using soil samples amended with sewage sludge and spiked with Cd pigments in percolation columns. The redox conditions were confirmed to be the decisive factor for the release of Cd. The release of Cd from artists’ paints was in most cases 1% or lower in the experiments performed.
Cd from artists’ paints in sewage sludge applied in agriculture will be mobilized for intake by crops or to leaching either by oxidation of sulfide to sulfate or by dissolution at lower pH values. The quantity of Cd from artists’ paints calculated in the restriction dossier is however negligible compared to other sources of Cd to agricultural soil. Therefore ECHA did not consider the proposed restriction to be the most appropriate EU wide measure to address the negligible level of risk. In the presentation sources of Cd on agricultural land will be discussed together with possible policy instruments to mitigate such emissions.
It is thought that the primary function of soldier castes in insect societies is to protect colonies against macroscale predators and parasites. By comparison, little attention has been paid to the role of soldiers against pathogenic microorganisms. This is a significant gap in knowledge because in non-hymenopteran societies, such as the eusocial termites, the first-evolved, and arguably most important sterile caste, is the soldier.
Here, we investigate whether soldiers of the wood-eating termite, Mastotermes darwiniensis, play a significant role in social immunity. Firstly, we show that uninfected soldiers improve the survival of worker nestmates exposed to a lethal dose of a fungal pathogen, despite the fact that soldiers (unlike workers) cannot allogroom. Hazard ratios of pathogen-exposed workers decreased from 6.616 in infected groups to 4.376 and 2.786 in infected groups containing uninfected workers and soldiers, respectively. To explore the basis of soldier protection, we applied soldier-derived oral secretions to infected worker cuticle, resulting in significantly improved worker survival. Soldiers that contacted infected workers were also more active and produced secretions with significantly greater mass variance than soldiers exposed to uninfected workers.
Significantly, we show that secretions produced by soldiers inhibit the growth of a broad range of microorganisms, including gram-negative and gram-positive bacteria, in addition to fungi. Our findings demonstrate that soldiers can contribute powerful antimicrobial factors to external immune defenses, effectively complementing behaviour-based protective activities provided by workers.
In addition to individual immunity, social insects have evolved collective defence strategies against pathogens, which consist of behavioural, physiological and organisational adaptations. The importance of social immunity in preventing disease transmission in insect societies is well known. However, we still lack a clear understanding of how collective defence mechanisms are regulated and how they interact with the other regulatory systems of the organism such us the individual immune system. Here we assess how individual immune factors shape the collective immune response to pathogens by inhibiting a key Termite immune effector: gram-negative binding protein (tGNBP-2). tGNBP-2 triggers downstream innate immunity, in addition to cleaving fungal and bacterial pathogens directly in the external environment. We established mini-colonies of Reticulitermes flavipes inside planar arenas where we were able to observe and record hygienic behaviours (i.e. allogrooming and cannibalism) in near-natural nest conditions. Colonies were either treated with the tGNBP-2 inhibitor or a control solution, after which 5 focal workers were introduced into each colony. Focal workers were pre-exposed to either: 1) the fungal pathogen Metharizium anisopliae 2) the t-GNBP-2 inhibitor + M. anisopliae 3) a control solution. Colonies were recorded and the hygienic behaviours performed by nestmates towards focal termites were analysed. We examined the impact of tGNBP-2 inhibition on individual innate immune regulation, in addition to exploring the wider impact of immune suppression on collective social behavioural responses.
Due to the increasing presence of microplastic particles (MP) in the Environment and the unknown risks arising from them, there is an urgent need for analytical methods that allow for an efficient identification and quantification of microplastics (MP), i.e. particles < 5 mm, in environmental samples. So far, mostly timeconsuming (micro) infrared or micro-Raman spectroscopic methods are applied. Here an faster alternative Approach is presented based on a Raman processspectrometer with fiber-optical probes in combination with multivariate data analysis.
A 400 m² soil test field with gas injection system was built up, which enables an experimental validation of linear gas sensors for specific applications and gases in an application-relevant scale. Several injection and soil watering experiments with carbon dioxide (CO2) at different days with varying boundary conditions were performed indicating the potential of the method for, e.g., rapid leakage detection with respect to Carbon Capture and Storage (CCS) issues.
Prospects and Restrictions of the Metal Magnetic Memory Technique
Biocide leaching was investigated for acrylate and vinyl acetate based coatings containing biocides either as liquid formulations or microcapsules. Laboratory and field tests indicate similar relations of results on carbendazim, diuron, terbutryn and OIT from different coatings in laboratory and field experiments. Emissions were higher in EN 16105 laboratory tests than from vertically installed test specimens exposed to weathering, and slower for microencapsulated biocides. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. Emission curves related to runoff water were similar in repeated field experiments. Relative humidity, temperature and global radiation were identified as meteorological factors that affect leaching by complex interaction besides the amount of driving rain.
Biocide leaching was investigated for acrylate and polymer based coatings containing biocides either as liquid formulations or microcapsules. Laboratory and field tests indicate similar relations of results on carbendazim, diuron, terbutryn and OIT from different coatings in laboratory and field experiments. Emissions were higher in EN 16105 laboratory tests than from vertically installed test specimens exposed to weathering, and slower for microencapsulated biocides. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. Emission curves related to runoff water were similar in repeated field experiments. Relative humidity, temperature and global radiation were identified as meteorological factors that affect leaching by complex interaction besides the amount of driving rain.
There is significant contamination of our water resources and an accelerating accumulation of hazardous species in the aquatic biosphere. Whether for instance mercury as a contaminant constantly released from a multitude of industrial processes or chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB) or Soman (GD) as highly toxic remnants of World War II, released from dumped containers upon their progressive corrosion, are concerned such hazards can cause serious problems to human health even at low concentration and monitoring them becomes increasingly essential. Conclusively, it is necessary to develop sensors for such hazards that combine high sensitivity, good selectivity, fast responses and can dispense with complex instrumentation.
Here, we present SBA-15-type mesoporous silica materials containing boron–dipyrromethene (BODIPY) probes in their pore systems that allow for the sensitive and selective detection of the two target analytes CWAs and Hg2+ in natural waters via a change in the optical properties. In case of Hg2+, the BODIPY dye is directly adsorbed on the (inner and outer) surface of the highly porous material and coordinates the metal ion, leading to an enhancement of fluorescence with a limit of detection (LOD) of 15 ppt. Using the same silica material but incorporating a covalently attached BODIPY dye, the CWAs GA, GD and GB can be detected via fluorescence quenching induced by an intraannular cyclization. The obtained LOD in natural waters is in the pM range and hence below the Maximum Permissible Concentrations for CWAs in drinking water. Aspects of system design as well as application in water and food analysis (fish extracts) will be presented.
There is significant contamination of our water resources and an accelerating accumulation of hazardous species in the aquatic biosphere. Whether for instance mercury as a contaminant constantly released from a multitude of industrial processes or chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB) or Soman (GD) as highly toxic remnants of World War II, released from dumped containers upon their progressive corrosion, are concerned such hazards can cause serious problems to human health even at low concentration and monitoring them becomes increasingly essential. Conclusively, it is necessary to develop sensors for such hazards that combine high sensitivity, good selectivity, fast responses and can dispense with complex instrumentation.
Here, we present SBA-15-type mesoporous silica materials containing boron–dipyrromethene (BODIPY) probes in their pore systems that allow for the sensitive and selective detection of the two target analytes CWAs and Hg2+ in natural waters via a change in the optical properties. In case of Hg2+, the BODIPY dye is directly adsorbed on the (inner and outer) surface of the highly porous material and coordinates the metal ion, leading to an enhancement of fluorescence with a limit of detection (LOD) of 15 ppt. Using the same silica material but incorporating a covalently attached BODIPY dye, the CWAs GA, GD and GB can be detected via fluorescence quenching induced by an intraannular cyclization. The obtained LOD in natural waters is in the pM range and hence below the Maximum Permissible Concentrations for CWAs in drinking water. Aspects of system design as well as application in water and food analysis (fish extracts) will be presented.
Concrete is one of the most widely used construction materials and, accordingly, the concrete industry is an important stakeholder in the field of sustainable construction. Therefore various approaches have been implemented to increase the sustainability of concrete. Besides reducing CO2-emissions during cement production, increasing the energy efficiency of buildings and extending their life span, the end-of-life performance of concrete is also an essential aspect of sustainability. Reusing concrete as a secondary building material meets the requirements of sustainability in several ways: the extended time availability of primary raw materials and, thereby, the protection of natural resources as well as conserving landfill site. Furthermore, the production of recycled concrete aggregates (RCA) is a good example for closed-loop recycling.
However, regarding the use of RCA as a substitute for natural aggregates in concrete, attention must be paid to all issues of sustainability: this means that environmental, economic and social aspects have to be considered. Since RCA generally have inferior building material properties, such as higher porosity and lower density, the implementation of closed-loop recycling of concrete only makes sense if the technical quality assurance is secured. This paper focusses on the implementation of techniques for the deconstruction/demolition of buildings and the subsequent treatment of concrete rubble in order to improve the building material properties of RCA with regard to the requirements of sustainability and also technical rules and standards.
Concrete is one of the most widely used construction materials and, accordingly, the concrete industry is an important stakeholder in the field of sustainable construction. Therefore various approaches have been implemented to increase the sustainability of concrete. Besides reducing CO2-emissions during cement production, increasing the energy efficiency of buildings and extending their life span, the end-of-life performance of concrete is also an essential aspect of sustainability. Reusing concrete as a secondary building material meets the requirements of sustainability in several ways: the extended time availability of primary raw materials and, thereby, the protection of natural resources as well as conserving landfill site. Furthermore, the production of recycled concrete aggregates (RCA) is a good example for closed-loop recycling.
However, regarding the use of RCA as a substitute for natural aggregates in concrete, attention must be paid to all issues of sustainability: this means that environmental, economic and social aspects have to be considered. Since RCA generally have inferior building material properties, such as higher porosity and lower density, the implementation of closed-loop recycling of concrete only makes sense if the technical quality assurance is secured. This paper focusses on the implementation of techniques for the deconstruction/demolition of buildings and the subsequent treatment of concrete rubble in order to improve the building material properties of RCA with regard to the requirements of sustainability and also technical rules and standards.
Due to the large quantities of construction and demolition waste (CDW) in Europe, its reuse or recycling is of particular importance. Although several countries already recycle high amounts of CDW, the use as secondary raw materials is often limited by inferior building material properties. Specific characteristics, like high porosity and low density are caused by hardened cement paste in crushed concrete and the content of mortar and plaster in brick debris. Impurities like wood or gypsum and also harmful substances like organic pollutants may be a major problem for a reuse and should be minimized. Therefore unwanted materials and impairing substances have to be separated from the secondary building material stream. This can be done during the demolition process by using techniques for selective dismantling or during the subsequent treatment of the resulting rubble. Since almost all processing steps are associated with environmental impacts, the benefits of saving natural resources by applying secondary building materials should be weighed carefully. An environmental performance evaluation was undertaken to assess different techniques for reducing gypsum in recycled concrete aggregates, aiming at a minimization of elutable sulfates. These results were compared to the environmental impacts of the extraction of natural aggregates for concrete.
2,4-Dichlorophenoxyacetic acid (2,4-D) is one important and well-known herbicide that is widely used in agriculture because of its advantages to regulate plant growth. However, the use of large quantities of the treated plants as animal feed leads to residues in meat, milk and eggs. Furthermore, the herbicide can drain away and contaminate ground and drinking water. The ingestion of 2,4-D-contaminated food and water causes damage to the inner organs of humans and animals, e.g., the kidneys and the liver.
Analytical assays based on molecularly imprinted polymers (MIPs) have emerged as a valuable tool in the field of environmental analysis due to the low production costs, stability, format adaptability and the possibility to imprint and thus their ability to recognize a wide variety of target analytes.5 With regard to optical sensing technologies, however, MIPs have only been used in considerably few applications, especially in fluorescence sensors. This limitation is basically due to the fact that the incorporation of a fluorescently responding moiety into a polymer matrix is challenging. One way to overcome this limitation is to use tailor-made fluorescent indicator monomers for direct transfer of the binding event into an optical signal and coat the MIP via reversible addition-fragmentation chain transfer (RAFT) polymerization as a thin layer onto the surface of silica nanoparticles as primary sensing element.
Here, we present the response behavior of the fluorescent MIP sensor particles in terms of sensitivity for 2,4-D detection (the so-called imprinting factor), discrimination ability against structurally similar compounds and performance in a phase-transfer assay (PTA) on chip, i.e., the implementation of the assay into a microfluidic chip environment, offering a novel simple and rapid way for the detection of herbicides.
The pollution of the environment with microplastics MP (particles < 5mm) is a problem of increasing concern.1 A consistent methodology that facilitates detection of MP is still missing. Here we present the data recorded by applying different MP identification methods to a soil fortified with known amounts of MP.
Fungal extracellular materials reinforce a constant interaction between their cell wall and the environment. A dynamic mixture of chitin, glucans, mannans, glycoproteins, glycolipids and pigments supports the success of all fungal life styles – from symbiotic to the free-living and pathogenic. Fungi are perfectly adapted to grow on surfaces and in porous environments, where they form medically and geochemically relevant biofilms. Fungal EPS are critical in adhesion to other fungi, other cells or substratum as well as in the following interaction with the host immune system or material they attack, degrade and deteriorate respectively. Characterisation of extracellular compounds and understanding of its function is necessary to limit damage caused by fungal activity. All necessary methodology from chemical characterization to complete genetic analyses has been developed for medically important fungi. Now it is time to apply this knowledge to the numerous, largely aerobic and very active organisms that occupy a wide range of atmosphere-exposed habitats in the upper lithosphere. One can expect that analogies between medically- and environmentally-relevant model fungal species will help us to address the dynamics of the fungal cell EPS matrix in much more efficient and widely applicable ways.
Some results of our measurements of the Intercity experimental are presented together with simulated results and their interpretation. Three frequeny ranges could be measured and calculated: low frequencies which decrease very rapidly with distance (the quasi-static part), high frequencies (mainly due to the sleeper passage), and a mid-frequency which has the weakest attenuation with distance and is therefore dominant at the far field. Mono-frequent excitations get a wide frequency band due to the Doppler effect of the moving high-speed train.
Biofilms living on gold (Au) grains play a key role in the biogeochemical cycle of Au by promoting the dispersion of Au via the formation of Au nanoparticles as well as the formation of secondary biomorphic Au. Gold grains from Queensland, Australia, are covered by a polymorphic, organic-inorganic layer that is up to 40 μm thick. It consists of a bacterial biofilm containing Au nanoparticles associated with extracellular polymeric substances as well as bacterioform Au. Focused ion beam (FIB) sectioning through the biofilm revealed that aggregates of nanoparticulate Au line open spaces beneath the active biofilm layer. These aggregates (bacterioform Au type 1) resulted from the reprecipitation of dissolved Au, and their internal growth structures provide direct evidence for coarsening of the Au grains. At the contact between the polymorphic layer and the primary Au, bacterioform Au type 2 is present. It consists of solid rounded forms into which crystal boundaries of underlying primary Au extend, and is the result of dealloying and Ag dissolution from the primary Au. This study demonstrates that (1) microbially driven dissolution, precipitation, and aggregation lead to the formation of bacterioform Au and contribute to the growth of Au grains under supergene conditions, and (2) the microbially driven mobilization of coarse Au into nanoparticles plays a key role in mediating the mobility of Au in surface environments, because the release of nanoparticulate Au upon biofilm disintegration greatly enhances environmental mobility compared to Au complexes only.
The role of c-di-GMP in biofilm formation of the filamentous cyanobacterium Nostoc punctiforme
(2016)
The signaling molecule c-di-GMP is a ubiquitous second messenger in bacterial species including cyanobacteria. C-di-GMP stimulates the biosynthesis of extracellular polymeric substances (EPS) in biofilms and regulates the transition between a motile and a sessile life style in many bacteria. In our study we focus on c-di-GMP function and EPS production associated with biofilm Formation in Nostoc punctiforme, which is known to produce EPS in biofilms and liquid culture.
Among the borates in the Middle European Zechstein Salt Succession boracite Mg3[B7O13Cl] is the most common mineral in quantity and local distribution. An exceptional enrichment is observed in Stassfurt Serie Z2) in the Stassfurth seam K2H. Boracite is to be found in two varieties: individual crystals in cubic, tetrahedral or dodecahedral habit on the one hand and fibrous crystals so-called “stassfurtite” on the other hand. The formation conditions such widely spread borates in the salt succession are ambiguous in two respects. First of all the synthetic formation of boracites is to be made by hydrothermal or melt conditions. Both processes can be suspended for the salt succession. Furthermore the cubic modification is stable above 265°C for the Mg-boracite. The cubic, tetrahedral or dodecahedral habit could be used as a geothermometer, but such conditions can be exclude by the paragenetic minerals, esp. carnallite (MgKCl3 x 6H2O). The chemical composition of orthorhombic, pseudo-cubic boracite depends on the location. Pure Mg-boracite in hexahedral habit and in fibrous habit, so-called “stassfurtite”, occurs in the North Harz region, whereas the Fe-, Mn-, Mg-boracite appears in the South Harz region. Until now the source of boron, the time of formation of crystals, but also the reasons for the differences in habit of the single hexahedral crystals are still unclear. The formation during a diagenetic/metamorphic process is evident. However, the preferred formation in Stassfurt seam could be an indication for the boron enrichment in an early diagenetic process. Furthermore permit the determination of the thermal stability and the volatile content of crystals conclusions to the chemical composition of the fluid. The observed variation suggests that the condition of crystal growth as well as the chemical composition of fluid repeatedly changed over the time. Randomly occuring xenomorpheous anhydrite and magnesite inclusions within single boracite crystals have been interpreted as an indication to factors of chemical milieu during the formation of crystals. The reversible phase transition temperature of the boracite is a linearly function of the iron and manganese content and varies from 265°C for Mg-boracite to 330°C for Fe(Mn)-boracite. The thermal decomposition of boracite is determined by two processes. The decomposition started with a boron-chlorine release (BOCl?), having a maximum rate at 1050°C. Additionally to this release one observes a simultaneous emission of H2O, HCl, HF, CO2 , N2 , SO2 , H2 , and hydro carbons. The results give evidence for the aged approach of a secondary formation of boracite within the complete Stassfurt seam, possibly in connection with the formation of salt diapirs in the Jura and Cretaceous period. The wider environmental distribution of borates is an indication of chemical transport processes within the salt succession. This should be a more important issue in the discussion about the utilisation of salt diapirs for the storage of nuclear waste.
Microbiological biofilms on rocks are ubiquitous in nature and their influence on soil formation through rock weathering has been shown (Gorbushina 2007). However, most previous studies on rock weathering are limited to understanding the physical and chemical aspects overlooking the impact of biota. Due to the enormous amounts of variables that come with a biological process, the quantification of its influence is only possible by using well-controlled and simplified laboratory models. Thereby gaining more insight on the impact of rock inhabiting biofilms on mineral weathering. This presentation will show the impact of biotic weathering in terms of olivine dissolution rates
Natural forsterite was incubated in batch reactor flasks with and without a model consortium consisting of the phototrophic cyanobacterium Nostoc punctiforme and the rock-inhabiting ascomycete Knufia petricola, and submerged in a growth solution (pH 6). The flasks were incubated for 30 days under 25°C, 90 µmol photons/m2s and were shaken at 150 rpm. qPCR was performed to quantify the cell number of both organisms, BET to gather the specific surface of the used olivine and ICP-OES to follow up the change of concentration of the leached out metals.
Our results show that our model consortium, especially K. petricola does increase the dissolution rate of olivine. The pH increased from the initial 6 to around 7.2 for all setups. Initially Mg was preferentially released over Si (Mg/Si of 3.5), until after two days the ratio starts equilibrating around stoichiometric dissolution. During this timeframe the dissolution rate drops by nearly two orders of magnitude, just as observed by Daval et al., (2011). The difference in dissolution rates between the different setups is initially non-existent, but increases over time. After 30 days the setup with K. petricola gives a dissolution rate of 1.08 10-13 moles/cm2s, compared to 9.23 10-14 moles/cm2s for the abiotic setup.
We expect this study to cause awareness on the impact of microbiology on mineral weathering. Additionally it is a starting point for other, more complicated experiments using for instance flow through or drip flow reactors or other minerals.
Microcolonial fungi (MCF) are the most stress-resistant eukaryotes known to date. Black fungi are an interesting object to study mechanisms of stress resistance and to perform applied research to prevent material colonization and biodeterioration. Pigments, like melanin and carotenoids, have been proven to contribute to the unique robustness of MFCs. We study how these pigments ameliorate oxidative stress responses - one of the most significant environmental challenges encountered by MCF - using the model rock fungus Knufia petricola (Chaetothyriales) strain A95.
Genetic manipulation of protective pigments in a rock-inhabiting model fungus Knufia petricola A95
(2016)
Black ascomycetous microcolonial fungi are persistent inhabitants of rock surfaces, but are especially conspicuous in hostile environments like cold and hot deserts. The unique robustness of MFCs is supported by protective pigments, like melanin and carotenoids. We study the role of these pigments in the stress resistance of the model rock fungus Knufia petricola (Chaetothyriales) strain A95.
Microcolonial fungi (MCF) are able to survive extreme environmental conditions. This study is focusing on responses to oxidative stress - using the rock fungus Knufia petricola strain A95. Comparative gene expression analyses of a wild type and a PKS mutant are used to identify genes which are especially regulated under oxidative stress conditions to help elucidate mechanisms of cell wall maturation and oxidative stress defence strategies.
The industrial sector of incinerator bottom ash (IBA) treatment from municipal solid waste (MSW) is currently changing. Since established techniques are not yet suitable for fine grain sizes, pollutants are enriched and the effort for the treatment increases exponentially it is nowadays generally landfilled. Innovative treatment trains for the recovery of minerals and metals from the fine fraction will be presented and discussed. In fresh IBA this fraction < 2 mm amounts to around 25 % and contains different precious elemental and chemically bonded metals, especially copper. All copper species have higher densities compared to the bulk minerals. Investigations for the enrichment of copper carried out with a centrifugal classifier will be introduced.
Emerging infectious diseases (EIDs) have contributed significantly to the current biodiversity crisis, leading to widespread epidemics and population loss. Owing to genetic variation in pathogen virulence, a complete understanding of species decline requires the accurate identification and characterization of EIDs. We explore this issue in the Western honeybee, where increasing mortality of populations in the Northern Hemisphere has caused major concern. Specifically, we investigate the importance of genetic identity of the main suspect in mortality, deformed wing virus (DWV), in driving honeybee loss. Using laboratory experiments and a systematic field survey, we demonstrate that an emerging DWV genotype (DWV-B) is more virulent than the established DWV genotype (DWV-A) and is widespread in the landscape. Furthermore, we show in a simple model that colonies infected with DWV-B collapse sooner than colonies infected with DWV-A. We also identify potential for rapid DWV evolution by revealing extensive genome-wide recombination in vivo. The emergence of DWV-B in naive honeybee populations, including via recombination with DWV-A, could be of significant ecological and economic importance. Our findings emphasize that knowledge of pathogen genetic identity and diversity is critical to understanding drivers of species decline.
Emerging infectious diseases (EIDs) have contributed significantly to the current biodiversity crisis, leading to widespread epidemics and population loss. Owing to genetic variation in pathogen virulence, a complete understanding of species decline requires the accurate identification and characterization of EIDs. We explore this issue in the Western honeybee, where increasing mortality of populations in the Northern Hemisphere has caused major concern. Specifically, we investigate the importance of genetic identity of the main suspect in mortality, deformed wing virus (DWV), in driving honeybee loss. Using laboratory experiments and a systematic field survey, we demonstrate that an emerging DWV genotype (DWV-B) is more virulent than the established DWV genotype (DWV-A) and is widespread in the landscape. Furthermore, we show in a simple model that colonies infected with DWV-B collapse sooner than colonies infected with DWV-A. We also identify potential for rapid DWV evolution by revealing extensive genome-wide recombination in vivo. The emergence of DWV-B in naive honeybee populations, including via recombination with DWV-A, could be of significant ecological and economic importance. Our findings emphasize that knowledge of pathogen genetic identity and diversity is critical to understanding drivers of species decline.
Diverse animal species consume toxins, minerals or secondary compounds as an adaptive response to pathogen infection – a process termed self-medication. Recent studies have also shown that macronutrients can play an important role in an individual’s infection response. For instance African army worm caterpillars select a diet rich in protein and low in carbohydrate upon baculovirus infection. Here we investigate whether dietary choice of macronutrients also plays a role in immunity in the omnivorous cockroach: Blatta orientalis. After challenging individual cockroaches with a common entomopathogenic soil bacterium, Pseudomonas entomophila, we conducted food-choice experiments using two artificial diets differing in their relative protein to carbohydrate ratio. We show for the first time that cockroaches are able to self-select a protein-enriched diet as a response to bacterial infection. This is driven by a sharp decline in carbohydrate intake rather than an increase in protein intake. Additionally, infected cockroaches reduced their overall nutrient intake, which is consistent with an illness-induced anorexia-like response. The feeding pattern of bacteria-challenged individuals returned to normality approx 4 days after challenge. We also investigate whether cockroach survival and hemolymph immunity are enhanced in individuals when restricted to a protein-rich vs. carbohydrate-rich diet. Overall, our findings demonstrate that macronutrient preferences follow a general pattern independent of pathogen type. Furthermore, we show that interactions between nutrition and immunity are highly conserved in evolution, highlighted by the fact that caterpillars and cockroaches diverged some 386 million years ago.
The first analysis of environmental samples shows, that the use of TED-GC-MS is suitable to analyse microplastic in environmental samples. Compared to the micro-spectroscopic methods this method is faster and gives good hints to the occurrence of high loadings of MP in environmental samples. In consequence, the method allows the monitoring of the situation and the investigation of MP distribution pathways in environment, to assess the relevance of various inputs.
Genetic manipulation of protective pigments in a rock-inhabiting model fungus Knufia petricola A95
(2016)
Sub-aerial biofilms typically form on bare rock. They consist of 99% cell material and extracellular polymeric substances (EPS) metabolising at low water availability. Rock-inhabiting melanised fungi represent an important part of the microbial community in these environments, playing important roles in the colonisation of mineral surfaces, rock weathering and soil formation in the ecological/geochemical context. Different cellular stress responses make rock-inhabiting ascomycetes fit for survival under extremely changing irradiation, as well as water, energy sources and nutrient availability. Melanised, rock-inhabiting fungi possess multiple protective pigments, form facultative symbiotic associations with photobionts and weather minerals. Melanised fungi build a protective layer around the cell that is critical in adhesion to other living partners, for the colonisation of the substrate and in the subsequent damage of the colonised surface. We chose Knufia petricola (Chaetothyriales) as a model species to analyse colonisation of surfaces. The basic physiology of K. petricola strain A95 is studied, its full genome sequence has been prepared for annotation and methods for deleting specific genes have been established. Unique features of K. petricola including the protective pigments (melanin and carotenoids) and EPS/cell wall properties are now being dissected genetically. As K. petricola strain A95 is in the basic clade of Chaetothyriales, it is an ancestor of both important human pathogens including Exophiala and lichens from the Verrucariaceae family. For this reason studies with A95 can help clarify the basis of fungal pathogenicity – as well as explain interactions with microscopic phototrophic partners like unicellular green algae and cyanobacteria. With Knufia petricola we will establish a canon of experimental approaches to characterise and quantify fungi that actively contact inanimate solid materials. The set of methods developed for Knufia will be adapted to heavily melanised and EPS-producing ascomycetes and can be broadly applied to medically important as well as material-colonising fungi.
The presence of plastic debris and especially small plastic particles in marine ecosystems has been recognized in the 1970`s. Since then various other environmental systems all over the world, like rivers, lakes and biota have been found to be polluted by plastics. Lately, agriculturally used land, waste-water treatment and biogas facilities come into focus as possibly relevant distribution vectors. To monitor the situation and investigate distribution pathways, the need for fast and reliable analytical procedures is high.
Up to now, there is no standard procedure for sampling, concentrating and analyzing plastic particles in environmental samples. Our group recently reported the development of a new analyzing method for microscale plastic particles, thermal extraction desorption gas chromatography mass spectrometry (TED-GC-MS). This method consists of thermal extraction of the sample via thermogravimetric analysis, collection of the evolved gaseous decomposition products on a solid-phase adsorber and analysis of the loaded adsorber using Thermal-Desorption-GC-MS. This technique utilizes the characteristic decomposition products of polymers for identification and even quantification of plastics in environmental samples.
In the present work we investigated samples of fermentation residues taken from a biogas plant. The results of sample preparation, concentration and analysis are presented as well as a comparison with alternative methods.
Recovery of rare earth elements - optimized elemental analysis of fluorescent lamp shredder waste
(2016)
Rare earth elements (REE) are a crucial component of fluorescence lamps. Several procedures have been developed to recovery these technological important elements. Nevertheless, actual REE recycling from fluorescence lamps is scarce so far (recovery rate of less than 1 %), with current recycling approaches concentrating on glass recovery. Since most recycling processes include several, also wet-chemical steps, a complete knowledge of the actual elemental composition of the respective mass flows is necessary for an efficient REE recovery. We tested seven different reagent mixtures for microwave-assisted digestion of fluorescent lamp shredder, including HF, HClO4, and H2O2. We determined the concentrations of 25 of the most relevant rare earth and other trace elements in the respective dilutions. Two independent digestions, one a mixture of perchlorid/nitric/hydrofluoric acid and the other aqua regia, showed the highest concentrations of 23 of these elements, excluding only Sn and Tb. The REE concentrations in the tested lamp shredder sample (stated in g/kg) were 10.2 (Y), 12.1 (La), 7.77 (Ce), 6.91 (Eu), 1.90 (Gd), and 4.11 (Tb).
Populations of genetically identical cells that share the same environment can differ markedly in their phenotypes. This phenomenon has been termed phenotypic heterogeneity. While a few molecular mechanisms that lead to heterogeneity in gene expression have been elucidated, it remains unclear how heterogeneity in gene expression is transmitted to heterogeneity in activity; especially in metabolism. Metabolic activity of single bacterial cells can be quantified by labeling the substrate with stable isotopes and by measuring label uptake with nanometer-scale secondary ion mass spectrometry (NanoSIMS). Here we combined NanoSIMS with single-molecule mRNA fluorescence in situ hybridization (smFISH) to link heterogeneity in gene expression and metabolism in nitrogen fixing bacteria. We find that gene expression and metabolic activity are decoupled in single cells. However, heterogeneity in gene expression is correlated with heterogeneity in metabolic activity on the population level. Gene expression kinetics can provide insights into the molecular mechanisms that lead to heterogeneity in metabolism.
Populations of genetically identical cells that share the same environment can differ markedly in their phenotypes. This phenomenon has been termed phenotypic heterogeneity. While a few molecular mechanisms that lead to heterogeneity in gene expression have been elucidated, it remains unclear how heterogeneity in gene expression is transmitted to heterogeneity in activity; especially in metabolism. Metabolic activity of single bacterial cells can be quantified by labeling the substrate with stable isotopes and by measuring label uptake with nanometer-scale secondary ion mass spectrometry (NanoSIMS). Here we combined NanoSIMS with single-molecule mRNA fluorescence in situ hybridization (smFISH) to link heterogeneity in gene expression and metabolism in nitrogen fixing bacteria. We find that gene expression and metabolic activity are decoupled in single cells. However, heterogeneity in gene expression is correlated with heterogeneity in metabolic activity on the population level. Gene expression kinetics can provide insights into the molecular mechanisms that lead to heterogeneity in metabolism.
Recovery of rare earth elements - optimized elemental analysis of fluorescent lamp shredder waste
(2016)
Rare earth elements (REE) are a crucial component of fluorescence lamps. Several procedures have been developed to recovery these technological important elements. Nevertheless, actual REE recycling from fluorescence lamps is scarce so far (recovery rate of less than 1 %), with current recycling approaches concentrating on glass recovery. Since most recycling processes include several, also wet-chemical steps, a complete knowledge of the actual elemental composition of the respective mass flows is necessary for an efficient REE recovery. We tested seven different reagent mixtures for microwave-assisted digestion of fluorescent lamp shredder, including HF, HClO4, and H2O2. We determined the concentrations of 25 of the most relevant rare earth and other trace elements in the respective dilutions. Two independent digestions, one a mixture of perchlorid/nitric/hydrofluoric acid and the other aqua regia, showed the highest concentrations of 23 of these elements, excluding only Sn and Tb. The REE concentrations in the tested lamp shredder sample (stated in g/kg) were 10.2 (Y), 12.1 (La), 7.77 (Ce), 6.91 (Eu), 1.90 (Gd), and 4.11 (Tb).
Most microorganisms live in environments where nutrients are limited and fluctuate over time. Cells respond to nutrient fluctuations by sensing and adapting their physiological state. Recent studies suggest phenotypic heterogeneity in isogenic populations as an alternative strategy in fluctuating environments, where a subpopulation of cells express a function that allows growth under conditions that might arise in the future. It is unknown how environmental factors such as nutrient limitation shape phenotypic heterogeneity in metabolism and whether this allows cells to respond to nutrient fluctuations. Here, we show that substrate limitation increases phenotypic heterogeneity in metabolism, and this heterogeneity allows cells to cope with substrate fluctuations. We subjected the N2-fixing bacterium Klebsiella oxytoca to different levels of substrate limitation and substrate shifts, and obtained time-resolved single-cell measurements of metabolic activities using nanometre-scale secondary ion mass spectrometry (NanoSIMS). We found that the level of NH4+ limitation shapes phenotypic heterogeneity in N2 fixation. In turn, the N2 fixation rate of single cells during NH4+ limitation correlates positively with their growth rate after a shift to NH4+ depletion, experimentally demonstrating the benefit of heterogeneity. The results indicate that phenotypic heterogeneity is a general solution to two important ecological challenges - nutrient limitation and fluctuations - that many microorganisms face. Currently, we use NanoSIMS to develop a new approach that defines functionally-relevant, phenotypic biodiversity in microbial systems.
Phosphorus is essential for all animate beings and not replaceable in its functions. Recovered phosphorus from secondary sources is expected gain importance in the future due to supply risks and environmental concerns regarding fossil phosphate rock, the single source of phosphorus so far. Existing regulations, standards, and analytical methods are basically configured for well-established organic and mineral fertilizer but not for the emerging recycling products. Consequently, the respective procedures have to be adapted, especially in terms of matrix effects and so far not regulated pollutants like uranium and emerging pollutants of concern.
Industrial production of the cell protectant ectoine: protection mechanisms, processes, and products
(2014)
Bacteria, Archaea and Eukarya can adapt to Saline environments by accumulating compatible solutes in order to maintain an osmotic equilibrium. Compatible solutes are of diverse chemical structure (sugars, polyols, amino acid derivatives) and are beneficial for bacterial cells not only as osmoregulatory solutes, but also as protectants of proteins by mitigating detrimental effects of freezing, drying and high temperatures. The aspartate derivative ectoine is a wide spread compatible solute in Bacteria and possesses additional protective properties compared with other compatible solutes, and stabilizes even whole cells against stresses such as UV radiation or cytotoxins. The protective properties of ectoine for proteins can be explained by its strong (kosmotropic) interaction with water and subsequent exclusion from Protein surface, the decrease of the solubility of the peptide backbone and the strengthening of intramolecular hydrogen bonds (secondary structures). The stabilizing and UV-protective properties of ectoine attracted industry, which saw the potential to market ectoine as a novel active component in health care products and cosmetics. In joint efforts of industry and research large-scale fermentation procedures have been developed with the halophilic bacterium Halomonas elongata used as a producer strain. The two key technologies that allow for the annual production of ectoine on a scale of tons are the bacterial milking procedure and the development and application of ectoine-excreting mutants (“leaky” mutant). The details of these two procedures including the strain development and Fermentation processes will be introduced and current and future applications of ectoine will be discussed.
The formation of biofilms on different materials provokes high costs in industrial processes, as well as in medical applications. Therefore, the interest in development of new materials with improved surfaces to reduce bacterial colonization rises. In order to evaluate the quality and safety of these new materials, it is highly important to ensure world-wide comparable tests that are relying on statistical evidence. The only way to reach this statistical safety is through a high-throughput Screening under standardized test conditions.
We developed a flow through system for cultivation of biofilm-forming bacteria under controlled conditions with a total capacity for testing up to 32 samples in parallel. Quantification of the surface colonization was done by staining the bacterial cells with a fluorescence marker, followed by epifluorescence microscopy. More than 100 images of each sample were automatically taken and the surface coverage was estimated with the free open source software gmic (http://gmic.eu), followed by a precise statistical evaluation. Overview images of all gathered pictures of the whole material coupon were generated to illuminate the colonization characteristics of the selected bacteria on certain materials.
With this method, differences in bacterial colonization on different materials can be quantified in a statistically validated manner. The innovative and solid test procedure will support the design of improved materials for medical and industrial applications such as implants, ship hulls, pipelines, heat exchangers, aquaculture equipments, photovoltaic-panels and fundaments of wind power plants.
A new tool in material science - Targeted disruption of melanin synthesis in rock-inhabiting fungi
(2016)
The ability to survive almost absolute dehydration through air-drying is a remarkable feature of rock-inhabiting microcolonial fungi (MCF), which colonise rock surfaces in hot and cold deserts. Understanding of the underlying mechanisms which allow this group of fungi to conquer natural and man-made environments requires a set of modern biological techniques and approaches that are under development in our laboratory. We will present an overview of the targeted disruption of melanin biosynthesis genes in the rock-inhabiting Knufia petricola and give inside into the lines of research and the network of supporting laboratories that made this progress possible.
A new tool in material science - Targeted disruption of melanin synthesis in rock-inhabiting fungi
(2016)
The ability to survive almost absolute dehydration through air-drying is a remarkable feature of rock-inhabiting microcolonial fungi (MCF), which colonise rock surfaces in hot and cold deserts. Understanding of the underlying mechanisms which allow this group of fungi to conquer natural and man-made environments requires a set of modern biological techniques and approaches that are under development in our laboratory. We will present an overview of the targeted disruption of melanin biosynthesis genes in the rock-inhabiting Knufia petricola and give inside into the lines of research and the network of supporting laboratories that made this progress possible.
Sewage sludge has one of the highest phosphorus (P) potentials of all waste materials. Therefore, P-recycling from sewage sludge could contribute to close the P-cycle. Recently, various processes for P-recovery have been developed, but most of them were not established in industrial scale due to their poor economic feasibility. In the present study, two common methods (low-temperature conversion at 400-500°C and thermochemical treatment at 950-1000°C were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation with FeCl2 and enhanced biological phosphorus removal.
The halophilic bacterium Halomonas elongata takes up the compatible solute ectoine via the osmoregulated TRAP transporter TeaABC. A fourth orf (teaD) is located adjacent to the teaABC locus that encodes a putative universal stress protein (USP). By RT-PCR experiments we proved a cotranscription of teaD along with teaABC. Deletion of teaD resulted in an enhanced uptake for ectoine by the Transporter TeaABC and hence a negative activity regulation of TeaABC by TeaD. Atranscriptional regulation viaDNA binding could be excluded. ATP binding to native TeaD was shown by HPLC, and the Crystal structure of TeaD was solved in complex with ATP to a resolution of 1.9 A ° by molecular replacement. TeaD forms a dimer-dimer complex with one ATP molecule bound to each monomer, which has a Rossmann-like R/β overall fold. Our results reveal an ATP-dependent oligomerization of TeaD, which might have a functional role in the regulatory mechanism of TeaD. USP-encoding orfs, which are located adjacent to genes Encoding for TeaABC homologues, could be identified in several other organisms, and their physiological role in balancing the internal cellular ectoine pool is discussed.
Numerous membrane importers rely on accessory water-soluble proteins to capture their substrates. These substrate-binding Proteins (SBP) have a strong affinity for their ligands; yet, Substrate release onto the low-affinity membrane transporter must occur for uptake to proceed. It is generally accepted that release is facilitated by the association of SBP and transporter, upon which the SBP adopts a conformation similar to the unliganded state, whose affinity is sufficiently reduced. Despite the appeal of this mechanism, however, direct supporting evidence is lacking. Here, we use experimental and theoretical methods to demonstrate that an allosteric mechanism of enhanced substrate release is indeed plausible.
First, we report the atomic-resolution structure of APO TeaA, the SBP of the Na!-coupled ectoine TRAP transporter TeaBC from Halomonas elongata DSM2581T, and compare it with the substrate-bound structure previously reported. Conformational freeenergy landscape calculations based upon molecular Dynamics simulations are then used to dissect the mechanism that couples ectoine binding to structural change in TeaA. These insights allow us to design a triple mutation that biases TeaA toward apo-like conformations without directly perturbing the binding cleft, thus mimicking the influence of the membrane transporter. Calorimetric measurements demonstrate that the ectoine affinity of the conformationally biased triple mutant is 100-fold weaker than that of the wild type. By contrast, a control mutant predicted to be conformationally unbiased displays wild-type affinity. This work thus demonstrates that substrate release from SBPs onto their Membrane transporters can be facilitated by the latter through a mechanism of allosteric modulation of the former.
Compared to the designated European upper reference level of 300 Bq/m³ for indoor radon concentrations, the contribution of building materials appears to be low. Taking into account the recommended limit of 100 Bq/m³ by WHO as well as the increased dose conversion factor, the contribution of building products is quite relevant, especially at low air change rates. Therefore in Germany a maximum contribution of building materials to the indoor radon concentration of 20 Bq/m³ is discussed.
Because measurements of low concentrations are associated with high uncertainties, radon exhalation rates are often determined in chambers without air exchange and indoor conditions are extrapolated.
This study investigated the suitability of direct low level radon measurement under simulated indoor conditions with commercially available instruments, based on the preliminary EU standard for the determination of the emission of volatile organic compounds (VOC) from building materials in test chambers.
Measurements are possible with a relative uncertainty ranging from 7 to 18%. Four major problems were identified:
1. Detector sensitivity: Two of four instruments were identified to determine low radon concentrations in a sufficiently short measuring time.
2. Thoron discrimination: Thoron was discriminated by aging the sampled air in a hose before the detector.
3. Sampling setup: An external chamber measurement was feasible as long as all main system parts were under slight overpressure.
4. Blank value: For VOC-emission testing ambient air, conditioned by filtration and sorption, is used to generate an air exchange. Regarding radon, this treatment is non-effective. If all instrument background levels have been characterized, the blank value must be measured with a second detector in parallel.
Compared to the designated European upper reference level of 300 Bq m-3 for indoor radon concentrations, the contribution of building materials appears to be low. Taking into account the recommended limit of 100 Bq m-3 by WHO as well as the increased dose conversion factor, the contribution of building products is quite relevant, especially at low air change rates. Therefore in Germany a maximum contribution of building materials to the indoor radon concentration of 20 Bq m-3 is discussed.
Because measurements of low concentrations are associated with high uncertainties, radon exhalation rates are often determined in chambers without air exchange and indoor conditions are extrapolated.
This study investigated the suitability of direct low level radon measurement under simulated indoor conditions with commercially available instruments, based on the preliminary EU standard for the determination of the emission of volatile organic compounds (VOC) from building materials in test chambers.
Measurements are possible with a relative uncertainty ranging from 7 to 18 %. Four major problems were identified:
1. Detector sensitivity: Two of four instruments were identified to determine low radon concentrations in a sufficiently short measuring time.
2. Thoron discrimination: Thoron was discriminated by aging the sampled air in a hose before the detector.
3. Sampling setup: An external chamber measurement was feasible as long as all main system parts were under slight overpressure.
4. Blank value: For VOC-emission testing ambient air, conditioned by filtration and sorption, is used to generate an air exchange. Regarding radon, this treatment is non-effective. If all instrument background levels have been characterized, the blank value must be measured with a second detector in parallel.
Sewage sludge ashes (SSA) contain up to 13% P and are thus promising raw materials for fertilizer production. However, SSAs also contain heavy metals and the main P-bearing mineral phases whitlockite and aluminium phosphate are poorly bioavailable. We developed and patented a process that produces fertilizers from SSA addressing the above mentioned challenges. SSA is thermo-chemically treated at ~950°C under reducing conditions (reductive: dry sewage sludge) in a rotary kiln together with an alkali compound such as sodium or potassium sulfate, hydroxide or carbonate. Some undesired trace elements such as As, Hg, Pb and Cd are evaporated and separated via off gas treatment system. The poorly soluble phosphates are transformed into calcium alkali phosphates (CaNaPO4 or CaKPO4) that are not water soluble but completely soluble in neutral ammonium citrate solution (NAC). Pot experiments showed that the fertilizer performance of the treated SSA containing calcium alkali phosphates as the single P-bearing mineral phase was comparable to the performance of triple superphosphate. The PNAC-solubility of fertilizer products correlated very well with the resulting contents of calcium alkali phosphates and the P-uptake of plants in pot experiments. The effect of the ratio alkali/P on the PNAC-solubility was investigated by crucible experiments and trial series with a medium scale rotary kiln using different SSAs and alkali phosphates. The effects of operational parameters such as the temperature and the retention time were investigated as well as concurring side reactions of the alkali compounds e.g. with SiO2 present in SSA. The alkali/P ratio must be roughly adjusted at 2 to achieve 100% PNAC-solubility for a common type of SSA. A demonstration trial with an output of 2 t recycling fertilizer was carried out in an industrial rotary kiln (product output 30 kg/h). The PNAC-solubility of the product varied between 60% and 80% during the 4 days campaign showing that the transformation of the mineral P-phases to calcium alkali phosphates was not complete. This was observed although the amount of Na2SO4 additive was dosed according to the results of the pre-investigations. Structure analysis by XRD showed that besides the target compound CaNaSO4 also some Ca3(PO4)2 remained in the SSA as well as some unreacted Na2SO4 additive. Obviously, the conditions in the industrial rotary kiln were not optimal for the process showing that some process aspects have to be reconsidered for the scale-up.
Pot experiments are often performed to analyze the plant-availability of phosphorus (P) in P-fertilizers. However, these experiments do not determine the P compounds present in the soil which are responsible for the yield increase. In order to better understand the results of pot experiments we analyzed the soils by P K-edge X-ray absorption near-edge structure (XANES) spectroscopy to determine the P species and unravel transformation processes. We carried out pot experiments with maize testing different waste water derived recycling P-fertilizers on an acidic and a neutral soil. Soils samples before sowing and after harvest were collected and prepared for analysis. A combination of macro- and µ-XANES spectroscopy was used to determine the chemical state of the overall soil P and to identify P compounds in P-rich spots localized by micro-X-ray fluorescence (µ-XRF). P K-edge macro-XANES spectroscopy detected organic P and/or P sorbed onto organic matter or other substrates in the unfertilized and fertilized soils. In addition, µ-XRF mapping in combination with P K-edge µ-XANES spectroscopy evidenced that some P phases present in recycling P-fertilizers (magnesium phosphate and calcium sodium phosphate) react with co-fertilized ammonium nitrate and form highly plant-available ammonium phosphates in the soil. In opposite, apatites were not affected by the presence of ammonium. Thus, for a boost of the plant-availability of P in recycling P-fertilizers these fertilizers should be directly co-fertilized with nitrogen (N) sources that contain a high amount of ammonium instead of nitrate. Possibly, a specific preparation of NP-fertilizers by granulation of recycling P-fertilizers with ammonium compounds and a nitrification inhibitor could enhance the plant-availability of the produced fertilizer whereby they become more competitive to commercially available NP-fertilizers based on phosphate rock.
Sub-aerial biofilms (SAB) are ubiquitous, self-sufficient microbial ecosystems found on mineral surfaces at all altitudes and latitudes. SABs, which are the principal causes of weathering on exposed terrestrial surfaces, are characterized by patchy growth dominated by associations of algae, cyanobacteria, fungi and heterotrophic bacteria. A recently developed in vitro system to study colonization of rocks exposed to air included two key SAB participants - the rock-inhabiting ascomycete Knufia petricola (CBS 123872) and the phototrophic cyanobacterium Nostoc punctiforme ATCC29133. Both partners are genetically tractable and we used them here to study weathering of granite, K-feldspar and plagioclase. Small fragments of the various rocks or minerals (1–6 mm) were packed into flow-through columns and incubated with 0.1% glucose and 10 μM thiamine-hydrochloride (90 μL min−1) to compare weathering with and without biofilms. Dissolution of the minerals was followed by: (i) analysing the degradation products in the effluent from the columns via Inductively Coupled Plasma Spectroscopy and (ii) by studying polished sections of the incubated mineral fragments/grains using scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analyses. K. petricola/N. punctiforme stimulated release of Ca, Na, Mg and Mn. Analyses of the polished sections confirmed depletion of Ca, Na and K near the surface of the fragments. The abrupt decrease in Ca concentration observed in peripheral areas of plagioclase fragments favored a dissolution-reprecipitation mechanism. Percolation columns in combination with a model biofilm can thus be used to study weathering in closed systems. Columns can easily be filled with different minerals and biofilms, the effluent as well as grains can be collected after long-term exposure under axenic conditions and easily analyzed.
The worldwide produced plastic amount was about 314 m tones in 2013. A content of about 5-12 m tones of plastic products is estimated to attain to the environment. There, they are exposed to environmental aging conditions like UV light, abrasion, water, oxidation etc. and degrade to small particles. If the particles reach a dimension < 5 mm they are called microplastic. Today microplastic is almost ubiquitary and was found in the aquatic as well as in the terrestrial environment. The main representatives are polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyethylene terephthalat (PET).
Analyzing microplastics in environmental samples turned out to be very challenging, due to the fact that there are only a few synthetic particles beside a huge number of natural. Furthermore, the different polymers particles vary in their shape, their density and their chemical characteristics. Until now, there is no standard procedure for sampling, concentration and analyzing. We developed a thermal decomposition method for analyzing micro plastics in environmental samples. The method is a combination of a thermal extraction on solid-phase adsorption agents with a subsequent analysis of the decomposition products by thermal desorption gas chromatography mass spectrometry. In contrast to more established methods, such as IR or Ramen spectroscopy, our method enables measurements within few hours and gives an integration result of polymer specific decomposition products. Therefore, it is possible to identify and to quantify polymers in environmental matrices.
The use of the method is demonstrated for various polymers (PE, PP, PS, PET) in spiked and first time also in real environmental samples.
Small grain sizes of municipal solid waste incineration (MSWI) bottom ash (BA) contain elemental and chemically bonded metals in appreciable amounts, especially copper. As different copper species have in general a higher density compared to the prevalent minerals, processes for density separation seemed to be favorable for the recovery of copper. Investigations with a centrifugal classifier were therefore carried out with BA from MWSI which have been used for a few years as the covering material for a landfill. The results show an appreciable enrichment of the precious copper. The concentrates contained up to 60 mg/kg copper in the dry weight (DW) (in general about 30 – 40 mg/kg DW) with enrichment factors of around 20 and a copper recovery of up to 50 % (in general around 20 %). A test series in order to evaluate the potential benefit for sequential processing illustrate the low efficiency for a further processing of the tailings.
The widespread use of antibiotics in livestock farming leads to trace residues in food products and wastewater, potentially entailing antimicrobial resistance in food-borne pathogens. The determination of antibiotics in aqueous environments and foodstuff is thus of major concern.
Analytical assays based on molecularly imprinted polymers (MIPs) have emerged as a valuable tool in this field due to the low production costs, stability, format adaptability and the possibility to imprint and thus their ability to recognize a wide variety of target analytes. With regard to optical sensing technologies, however, MIPs have only been used in considerably few applications, especially in fluorescence sensors. This limitation is basically due to the fact that the incorporation of a fluorescently responding moiety into a polymer matrix is challenging. One way to overcome this limitation is to use tailor-made fluorescent indicator monomers for direct transfer of the binding event into an optical signal. If such a monomer is integrated into a thin MIP-shell on microspheres such core/shell particles can be readily used in advanced multiplexing sensory fiber-optic microarrays.
Here, we propose such a fiber-optic microarray based on fluorescent MIP microspheres for antibiotics. The binding behavior and the selectivity of a microarray using these MIP were examined and compared with a non-imprinted polymer (NIP) control, employing the target molecules and other structurally closely related antibiotics.
Reactive geomembranes and geotextiles are an innovative approach to control the migration of contaminants in geotechnical applications. Within a joint research project in cooperation with a medium-sized enterprise, the preparation and characterization of “reactive” geomembranes and geotextiles modified by the addition of zero-valent metal nanoparticles was performed. Zero-valent iron (ZVI) nanoparticles were added to polyethylene or to the fillings of geo-containers or geosynthetic clay liners. These geosynthetic products consist of mixtures of sand with clay or bentonite, typically embedded in geotextile nonwovens or geomats. The permeability of these geo-containers can be adjusted by the ratio of clay or bentonite to sand. ZVI nanoparticles were also added as reactive material to geomembranes made of polyethylene with additives like the antioxidant Irganox 1010 or glycerin. These additives prohibit oxidation of the nanoparticle and act as hydrogen donor in the dechlorination of chlorinated hydrocarbons. Contaminates such as chlorinated hydrocarbons and toxic heavy metal compounds are either decomposed or converted to less toxic species (e.g. Cr-(VI) reduction to Cr-(III)). The paper reports the first experimental results from manufacturing of the reactive geomembrane model materials and characterization of the products with microscopic techniques. First breakthrough measurements of the ZVI modified geomembrane compared to a reference sample are presented.
Advanced oxidation processes have become an important part of research due to their capacity to degrade many environmental pollutants during water treatment. Especially the heterogeneous photocatalysis is a promising method because it often results in a full mineralization of many hazardous compounds. Incomplete degradation reactions can result in transformation products due to oxidative conditions. The transformation products may have a higher toxicity than the precursor substances and are often only partly removed during water treatment. Since a lot of these compounds are still unknown, transformation products are not detected by target analysis used in sewage treatment plants and are often released into the aquatic ecosystems. Therefore, extensive and effective non-target analytical methods are necessary for the monitoring and identification of the transformation products which can be generated during waste water treatment.
Titanium dioxide (TiO2) is the most frequently used photocatalyst because of its inexpensiveness, non-toxicity, chemical stability and its high photocatalytic activity. If TiO2 is irradiated electron-hole pairs are generated on the surface of the TiO2, resulting in the formation of active oxidized species such as hydroxyl radicals which can react with environmental pollutants.
A model system has been developed to simulate photocatalytic reactions in a laboratory scale. The commonly used pharmaceuticals metformin and gabapentin were selected as model substances because of their high input in waste water and the little information about their fate during water treatment. Metformin is the drug of choice for treating type 2 diabetes. More than half of the total amount of pharmaceuticals in the environment are the antidiabetic agent metformin and its major transformation product guanylurea. Gabapentin is used as antiepileptic drug and for the treatment of neuropathic pain. It is found in waste water influent in the high ng/L range.
First results of the optimization of the photocatalyst and its application are shown.
The recent experience of Italian seismic events provided wide observational information about typical behaviour, damage patterns and intrinsic vulnerability of monumental buildings. Evidence indicates that historical constructions are by far the most vulnerable from the seismic point of view. As a consequence, they demand for the definition of urgent strategies for the protection of cultural heritage from seismic hazard. The main goal of an in-depth knowledge of the structure should help to avoid inadequate, unsuitable or dangerous rehabilitation operations, as well as to select non-invasive and reversible techniques for the best exploitation of material and technology features. The definition of reliable models and methods for seismic risk assessment of historical constructions is today a very important topic. Typical problems of masonry structures concern aspects like inherent structural lacks, material degradation, geotechnical problems, buckling behaviour of slender elements and dynamic loading vulnerability. Modelling the mechanical behaviour of masonry may play an important role, due to both inherent material complexity and great scatter in mechanical properties. Effective procedures for the identification of the structural parameters from static and dynamic testing are thus required. In particular, dynamic measurements may be very useful for the identification of mechanical properties and soil restraints and, consequently, for the calibration of advanced numerical finite element models. The paper addresses two case studies of structural monitoring and seismic assessment of medieval masonry towers in Italy: the bell tower of Aversa and the bell tower of Capua. These monuments, placed in the Campania region, were monitored by means of full-scale environmental vibration testing. Measured responses are then used for modal identification with a typical finite element model updating technique based on vibration test results. Parameters optimization is carried out on the basis of a criterion which minimises a weighted error on modal properties. A satisfactory improvement in the determination of modal parameters is thus obtained, resulting in a close agreement between the modal properties observed in dynamic tests and those calculated from numerical model. Seismic assessment is finally performed based on nonlinear static analysis of the tower under multimodal distributions of lateral loads. Results from nonlinear analysis indicate the potential collapse mechanisms and evidence dangerous structural weakness which may play a role in the seismic vulnerability of the towers.
In the beginning of the 1980s earth building has undergone a renaissance, which nowadays leads to an increasing use of load-bearing earth constructions and in particular, earth block masonry. At present there are no common structural standards according to the semi-probabilistic calculation concept, which is the state-of-the-art in European standards. A solid database is needed for the determination of the materials partial safety factor. Therefore, compressive strength tests were carried out with two types of earth blocks and two types of prefabricated earth mortar. The evaluation showed that the variation of the compressive strength was remarkably less than expected, which seems to indicate high quality standards of the components earth block and mortar with regard to industrial production. On the basis of these results and together with the reliability method, a partial safety factor for earth block masonry subjected to compression was determined. The main aim of the research was the development of a first valid database for material parameters of earth block masonry with particular regard to statistical characteristics. The results showed that a common calculation method for earth block masonry based on partial safety factors following the valid masonry construction standard is feasible.
The surface chemistry / functionalization of nanomaterials and microparticles largely controls the stability of these materials as well as their solubility and subsequent biofunctionalization and their interactions with biological systems. Moreover, in the case of some nanomaterials like semiconductor quantum dots or lanthanide-based upconversion nanocrystals, the ligand shell strongly affects their optical properties, e.g., via passivation of surface states and traps that favor luminescence quenching or the protection of surface atoms from quenching water molecules. This renders analytical methods for the quantification of surface groups like functionalities very important. Targets of broad interest are here amino, carboxyl, alkine and maleimide groups used for common bioconjugation reactions and typical ligands like thiols and polyethylene glycol (PEG) molecules of varying length, used for the tuning of material hydrophilicity and biocompatibility, minimization of unspecific interactions, prevention of biofouling, and enhancement of blood circulation times as well as surface-bound biomolecules like streptavidin or other biomolecules relevant e.g., for diagnostic assays. Here, we focus on simple optical methods relying on standard laboratory instrumentation, validated by method comparison and/or mass balances and present examples for their use for the characterization of different types of nanomaterials and microparticles.
Luminescence-based detection methods, ranging from fluorescence spectroscopy for photophysical and mechanistic studies over sensing applications, chromatographic separation techniques and the microarray technology with fluorescence detection to fluorescence microscopy, flow cytometry, single molecule spectroscopy, and molecular imaging to integrating sphere spectroscopy, are among the most widely used methods in the life and material sciences. This is due to e.g., their unique sensitivity enabling the detection of single molecules, potential for multiplexing, ease of combination with spatial resolution, and suitability for remote sensing. Many of these advantages are closely linked to the choice of suitable molecular and nanoscale fluorescent reporters, typically required for signal generation. This includes organic dyes without and with sensor function, fluorophore-encoded polymeric and silica nanoparticles as well as nanocrystalline systems like semiconductor quantum dots and upconversion phosphors, emitting in the visible (vis), near-infrared (NIR), and IR (infrared). Current challenges present the environment sensitivity of most fluorophores, rendering fluorescence spectra, measured intensities/fluorescence quantum yields, and fluorescence decay kinetics matrix-dependent, and instrument-specific distortions of measured fluorescence signals that need to be considered for quantification and comparability of data, particularly fluorescence spectra.
Here, current applications of luminescence-based methods and different types of reporters will be presented. In this context, suitable spectroscopic tools for the characteri-zation of the optical properties of fluorescent reporters and fluorophore-encoded microparticles, analytical tools for the determination of the surface chemistry of different types of particles, and different multiplexing strategies will be discussed.
We have studied the influence of gamma rays on physical properties of different commercially available silica optical fibers stepwise irradiated up to a total dose of 100 kGy. The detection of radiation-induced changes in silica glass offers the possibility of using selected optical fibers as distributed radiation sensors. The measurements performed by us were based on optical backscatter reflectometry and Brillouin distributed sensing. The measurement methods enable an analysis of radiation-induced modification of the group refractive index and density of the optical fibers. The most distinct physical effect observed by us concerns the increase of the optical attenuation with rising total radiation doses. Quantitative measurement results indicate a crucial impact of fiber dopants on radiation-induced physical and sensory characteristics of silica optical fibers affected by differences in fiber fabrication techniques. Based on the obtained results, the suitability of distributed Brillouin sensing for dosimetry applications seems to be improved by modifying the refractive index profile of the fiber core.
This study presents diagnostic techniques to assess the structural vulnerability of earthen buildings. Medieval structures at Ambel (near Zaragoza, Spain), once a preceptory or monastic house belonging to the Military Orders, provide a useful case study. After more than a thousand years of construction, failure and repair from the 10th century to the present day, Ambel preceptory today is characterised by marked inhomogeneities: construction materials and structural typologies are juxtaposed, with structural discontinuities at the interfaces between construction phases. This paper argues that, while static analysis is an essential prerequisite before a suitable maintenance program can be defined, no evaluation of the structural behaviour of any historic building can ignore an understanding of the building’s history.
Fungal secondary metabolites such as phomopsin A (PHO-A) produced by the fungus Diaporthe toxica are referred to as “emerging” mycotoxins. Recently, we developed a biosynthetic approach to gain access to 15N-isotopically labelled PHO-A as internal standard (IS) for PHO-A matrix independent quantification of PHO-A in various commodities. Aim of the present work was to elucidate the applicability of the new IS for accurate quantification and to investigate the phomopsin formation on various legume seeds as well as plant material. In summary, the applicability of the SIDA-HPLC-MS/MS method could be proven and the potential of D. toxica to produce high amounts of phomopsins under unfavorable conditions on lupins and other legume seeds could be shown. Moreover, a novel toxic methylated PHO-A derivative was unveiled in natural samples infested with D. toxica.
The goal of the present study is to assess the feasibility to develop a first reliable database of materials parameters for Earth Block Masonry (EBM). The database is crucial when defining the materials safety factors. In the first part an experimental campaign of compressive tests were carried out on two types of earth block and two types of earth mortar. The results showed that the mean variation of the compressive strength was remarkably less than expected. This low variation is related to a production with high quality standards of the materials employed. In the second part a partial safety factor for EBM under uniaxial compression was determined through the reliability method. The results proved the reliability of a common calculation method for EBM based on partial safety factors following the current standards.
UHPC-AAC/CLC composite panels with self-cleaning properties. Materials and production technology
(2016)
The aim of this study is to show the development of a façade composite panel combining either an autoclaved aerated concrete or a cellular lightweight concrete insulation layer with a box-type external ultra-high performance concrete (UHPC) supporting layer. The paper presents the materials characteristics of the different components and the production technology of the panel. The efficiency of surface modifications of the materials forming the external shell of the panel is reported. The activation of self-cleaning properties is described. The test results showed that the most efficient way to use the water-repellent agent is its application on the substrate before the concrete cast.
Concerning the production technology, the preliminary studies showed more advantages of a two-step manufacturing procedure of the UHPC boxes than a one-step procedure.
In order to provide nutrition for a growing world population pesticides are a necessary tool. Crop protection agents may be considered safe, if handled correctly. Nevertheless, they are subject to transformation processes and metabolization in the environment and technical installations. Transformation products (TP) and metabolites may be more harmful than the mother substance and thereby pose a threat to environmental and human health.
With 19 % market share in 2014, triazole pesticides are the class of organic fungicides which are most commonly used in Germany. However, only little data is available concerning their TP and metabolites. In this study the fate of the triazole fungicides propiconazole and difenoconazole in soil and water using model reaction systems mimicking their pathway in the environment and the industrial water treatment is investigated.
During application the substances may directly contaminate soil as well as surface waters. In these compartments, transformation by global irradiation needs to be considered. Due to their moderate mobility both pesticides may also end up in ground water from which drinking water is produced. Owing to the vigorous conditions during drinking water production the formation of a variety of technical TP can be expected. Additionally, for all compartments the degradation by bacteria is a factor which needs to be taken into account. For this survey, the potential for metabolization by model organisms is investigated.
In this work degradation and transformation of the fungicides is monitored using quantitative target analysis. Major components in the reaction mixtures are identified by non-target analysis. GC-EI-MS-spectra, HR-MS-measurements, or the comparison with native standards are utilised for structural elucidation. For identification, products will be isolated and characterized by NMR. Toxicity assessment of these TP is essential to define threshold values in the environment.
The model reaction systems will be presented and possible TP will be shown.
Here, we present an overview of the research activities of division Biophotonics concerning the design and (bio)analytical application of molecular and nanoscale functional chromophores for e.g., biomarker analysis including methods for the reliable determination of their application relevant properties. This includes the absolute determination of their brightness and photoluminescemce quantum yield, determining the signal size from the material side, as well as the development of fluorescence standards for such measurements and instrument calibration strategies, thereby providing important prerequisites for the comparison of material performance, the mechanistic understanding of nonradiative decay channels, and the rational design of new optical reporters. Moreover, for particle-based systems, ranging from nm-sized semiconductor quantum dots to m-sized polymeric and silica beads, simple optical methods and assays for the assessment of their surface chemistry are presented, which enable the quantification of the number of total and derivatizable surface functionalities, ligands per particle and particle-bound biomolecules. In addition, validation concepts for such methods are introduced utilizing method comparisons, multimodal and cleavable probes.