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Several restoration projects of stained-glass windows have been performed in Lower Silesia (Poland) since 2010. The aim of the projects was to protect stained-glass windows against environmental impact of industial pollutants and acid rain by installing a protective glazing. The usefulness of protective glazing has been proved by climate measurements and determination of environmental impact before and after installation.
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.
Injection of poly(methyl methacrylate) cements, one standard Treatment for osteoporotic vertebral body fractures, may lead to critical loads and subsequent fractures in adjacent vertebral bodies. Biodegradable calcium phosphate cements (CPC) with bioinductive growth factors may be an alternative, since they have a Young’s modulus comparable to that of cancellous bone. Non-destructive tests with μCT and quantitative Image evaluation are used to assess new bone growth and material resorption following intravertebral injection of CPC. Immediate deep-freezing of excised bone prevents shrinkage or tissue disintegration and the samples have to be kept frozen for all following steps, including transport, μCT measurements, and subsequent biomechanical tests. Here we will report on a set-up to preserve the frozen state of the material and allow stable long-term serial μCT measurements. In addition, the image processing technique for the evaluation of bone growth and selected results on subsequently carried out compressive strength tests will be presented.
Die europäischen BVT-Merkblätter beschreiben die besten verfügbaren Techniken zum emissionsarmen Betrieb von industriellen Produktionsprozessen, von technischen Verfahren zur Gewinnung und Verarbeitung von Rohstoffen, von Anlagen zur Erzeugung von Strom und Wärme und zur Behandlung und Verwertung von Abfällen und anderen technischen Prozessen. Die Abfallwirtschaft ist bei den Arbeiten zur Revision der BVT-Merkblätter gleich mit zwei Aktivitäten beteiligt, da sich aktuell sowohl das BVT-Merkblatt Abfallbehandlung als auch das BVT-Merkblatt Abfallverbrennung in der Revision befinden. Das Umweltbundesamt hat die Aufgabe, die Überarbeitung der BVT-Merkblätter national zu koordinieren und an den Arbeiten in Sevilla im EIPPC Büro und bei der Europäischen Kommission fachlich mitzuwirken. Der Beitrag beschreibt die aktuellen Aktivitäten zur Revision des BVT-Merkblattes Abfallverbrennung und Stand des Überarbeitungsprozesses auf europäischer Ebene mit dem inhaltlichen Schwerpunkt bei den zu erwartenden Anforderungen an die Entsorgung von Aschen und Schlacken aus der Abfallverbrennung mit einem Schwerpunkt bei den Siedlungsabfallverbrennungsanlagen.
The standard is intended to offer participants in waste management planning such as authorities, decision makers and planners, including the critical public, the possibility to learn about evaluation methods as planning instruments and place them in the context of planning decisions.
The standard should help those who use it to formulate transparent decisions for the application of particular waste treatment and recovery methods in the scope of integrated waste management, thus reaching a documented decision under consideration of the system boundaries and life cycle inventories of the respective methods.
This paper presents an innovative way to combine an external ultra-high performance concrete (UHPC) supporting layer with an insulation layer of autoclaved aerated concrete (AAC) or cellular lightweight concrete (CLC) to create light-weight façade elements, which are improved in functionality and in energy efficiency. The durability of the façade elements is improved by developing UHPC with self-cleaning properties. One approach is based on the photocatalytic activation of the external UHPC shell by incorporation of TiO2 particles. The second approach consists of the modification of the UHPC surface by micro structuring in combination with the application of water-repellent agents to create durable super hydrophobicity. The current results obtained from laboratory testing are promising and demonstrate the feasibility of the approaches.
Single wire Gas Metal Arc Welding (SGMAW) and high power Tandem GMAW (TGMAW) are evaluated with respect to energy efficiency. The key performance indicator Electrical Deposition Efficiency is applied to reflect the energy efficiency of GMAW in different material transfer modes. Additionally, the wall-plug efficiency of the equipment is determined in order to identify the overall energy consumption. The results show that energy efficiency as well as economic process performance can be significantly increased by application of tandem processes. A comparative Life Cycle Assessment of a 30 mm thick weld is conducted to investigate the influences of the energy efficiency on the environmental impacts. Environmental burdens in the categories Global Warming Potential, Acidification Potential, Eutrophication Potential and Photochemical Ozone Creation Potential can be reduced up to 11% using an energy efficient TGMAW process
In diesem Beitrag soll in Kürze darüber informiert werden, welche Themen und Fragestellun-gen den Fachbeirat der BAM, seine Arbeitsgruppen und die BAM beschäftigt haben. Bereits in den letzten Jahren wurde an dieser Stelle über die Anforderungen an Kunststoff Drän-elemente berichtet. Vor dem Hintergrund unserer Beiträge zu diesem Thema, kam eine in-tensive Fachdiskussion im Fachbeirat der BAM und in weiteren Fachgremien in Gang. So wurden die Bemessungsgrundsätze der DGGT (Deutsche Gesellschaft für Geotechnik), die GDA (Geotechnik der Deponien und Altlasten) E (Empfehlung) 2-20 (Entwässerungsschich-ten in Oberflächenabdichtungssystemen), in einigen Punkten angepasst. Eine Musterverle-geanleitung für Kunststoff Dränelemente wurde erarbeitet. Der aktuelle Bearbeitungsstand soll hier vorgestellt werden. In diesem Zusammenhang wurde ein Untersuchungsprogramm zum Einfluss von Überlappstößen auf das Wasserableitvermögen von Kunst-stoff Dränelementen angestoßen. Die Ergebnisse sollen hier in Kürze vorgestellt und die Bedeutung für die Abminderungsfaktoren und damit für die Bemessung erläutert werden. Zu welchem Zeitpunkt muss ein Kunststoff Dränelement überbaut werden und welche weiteren Regelungen müssen hier beachtet werden? Was steckt eigentlich hinter diesen strengen Regelungen? Diese Fragen sollen im Folgenden diskutiert werden.
Die Deponieverordnung (DepV) fordert eine Akkreditierung der fremdprüfenden Stellen nach verschiedenen Normen. Die fachlichen Anforderungen an den „Fremdprüfer-Kunststoff“ legt die Richtlinie Fremdprüfer der BAM fest. Um diese Anforderungen im Akkreditierungsprozess ausreichend berücksichtigen zu können, wurde nun eine sogenannte DAkkS Regel erarbeitet, die die Anforderungen der Richtlinie spiegelt. Über den aktuellen Bearbeitungsstand soll berichtet werden.
Auch über die aktuelle Arbeit in Zusammenhang mit den Kunststoffdichtungsbahnen (KDB) soll berichtet werden. Der Prüfhinweis B14 (Bestimmung der Maßhaltigkeit von geosyntheti-schen Dichtungsbahnen aus Polyethylen hoher Dichte (PEHD)) wurde überarbeitet. Voran-gegangen war eine intensive Entwicklung der Prüfeinrichtung sowie ausgiebige Ringversuche im AK GWS (Arbeitskreis Grundwasserschutz). In diesem Zusammenhang wurden neue Anforderungen an die Produkte gestellt. Die Hintergründe dazu sollen kurz vorgestellt werden. Die DVS (Deutscher Verband für Schweißen und verwandte Verfahren) Richtlinie 2225-4 regelt das Schweißen der KDB auf der Deponiebaustelle. Werden KDB im strukturierten Bereich miteinander verschweißt, werden die Strukturen in der Regel vorher abgetragen. Die DVS Richtlinie 2225-4 sieht unter bestimmten Voraussetzungen von einem Abtragen der Strukturen ab. Vor diesem Hintergrund wurde ein Untersuchungsprogramm initiiert, das die Auswirkungen aufzeigen soll. Der Bearbeitungsstand wird vorgestellt.
An approach to achieve “zero leakage” is discussed with respect to the experience in Germany, where strict regulations for landfill lining and capping systems have been developed and issued because of large environmental problems related to landfills that accumulated in the 1970’s and 1980’s. Using a thick, high quality HDPE geomembrane (GMB), which is installed free of residual waves and wrinkles in intimate contact with a compacted clay liner (CCL) or geosynthetic clay liner (GCL) of very low permeability, by a qualified, experienced, well equipped and properly third-party controlled installer and which are protected by heavy protection layers designed with respect to long-term performance of the GMB, may result in a liner or capping system of practically no leakage. This is demonstrated by analyzing results of measurements obtained from permanently installed leak detection systems in combination with HDPE GMBs. The survey is based on 32 German landfills with 1,276,500 m² of installed HDPE GMB.
An approach to achieve “zero leakage” is discussed with respect to the experience in Germany, where strict regulations for landfill lining and capping systems have been developed and issued because of large environmental problems related to landfills that accumulated in the 1970’s and 1980’s. Using a thick, high quality HDPE geomembrane (GMB), which is installed free of residual waves and wrinkles in intimate contact with a compacted clay liner (CCL) or geosynthetic clay liner (GCL) of very low permeability, by a qualified, experienced, well equipped and properly third-party controlled installer and which are protected by heavy protection layers designed with respect to long-term performance of the GMB, may result in a liner or capping system of practically no leakage. This is demonstrated by analyzing results of measurements obtained from permanently installed leak detection systems in combination with HDPE GMBs. The survey is based on 32 German landfills with 1,276,500 m² of installed HDPE GMB.
In diesem Beitrag soll in Kürze darüber informiert werden, welche Themen und Fragestellun-gen den Fachbeirat der BAM, seine Arbeitsgruppen und die BAM beschäftigt haben. Bereits in den letzten Jahren wurde an dieser Stelle über die Anforderungen an Kunststoff Drän-elemente berichtet. Vor dem Hintergrund unserer Beiträge zu diesem Thema, kam eine in-tensive Fachdiskussion im Fachbeirat der BAM und in weiteren Fachgremien in Gang. So wurden die Bemessungsgrundsätze der DGGT (Deutsche Gesellschaft für Geotechnik), die GDA (Geotechnik der Deponien und Altlasten) E (Empfehlung) 2-20 (Entwässerungsschich-ten in Oberflächenabdichtungssystemen), in einigen Punkten angepasst. Eine Musterverle-geanleitung für Kunststoff Dränelemente wurde erarbeitet. Der aktuelle Bearbeitungsstand soll hier vorgestellt werden. In diesem Zusammenhang wurde ein Untersuchungsprogramm zum Einfluss von Überlappstößen auf das Wasserableitvermögen von Kunst-stoff Dränelementen angestoßen. Die Ergebnisse sollen hier in Kürze vorgestellt und die Bedeutung für die Abminderungsfaktoren und damit für die Bemessung erläutert werden. Zu welchem Zeitpunkt muss ein Kunststoff Dränelement überbaut werden und welche weiteren Regelungen müssen hier beachtet werden? Was steckt eigentlich hinter diesen strengen Regelungen? Diese Fragen sollen im Folgenden diskutiert werden.
Die Deponieverordnung (DepV) fordert eine Akkreditierung der fremdprüfenden Stellen nach verschiedenen Normen. Die fachlichen Anforderungen an den „Fremdprüfer-Kunststoff“ legt die Richtlinie Fremdprüfer der BAM fest. Um diese Anforderungen im Akkreditierungsprozess ausreichend berücksichtigen zu können, wurde nun eine sogenannte DAkkS Regel erarbeitet, die die Anforderungen der Richtlinie spiegelt. Über den aktuellen Bearbeitungsstand soll berichtet werden.
Auch über die aktuelle Arbeit in Zusammenhang mit den Kunststoffdichtungsbahnen (KDB) soll berichtet werden. Der Prüfhinweis B14 (Bestimmung der Maßhaltigkeit von geosyntheti-schen Dichtungsbahnen aus Polyethylen hoher Dichte (PEHD)) wurde überarbeitet. Voran-gegangen war eine intensive Entwicklung der Prüfeinrichtung sowie ausgiebige Ringversuche im AK GWS (Arbeitskreis Grundwasserschutz). In diesem Zusammenhang wurden neue Anforderungen an die Produkte gestellt. Die Hintergründe dazu sollen kurz vorgestellt werden. Die DVS (Deutscher Verband für Schweißen und verwandte Verfahren) Richtlinie 2225-4 regelt das Schweißen der KDB auf der Deponiebaustelle. Werden KDB im strukturierten Bereich miteinander verschweißt, werden die Strukturen in der Regel vorher abgetragen. Die DVS Richtlinie 2225-4 sieht unter bestimmten Voraussetzungen von einem Abtragen der Strukturen ab. Vor diesem Hintergrund wurde ein Untersuchungsprogramm initiiert, das die Auswirkungen aufzeigen soll. Der Bearbeitungsstand wird vorgestellt.
In this study, bulked adhesives were examined regarding changes in properties for their use in the restoration of stained-glass windows. Two epoxy adhesives commonly used in the restoration of flat glass, Araldite® 2020 and Hxtal NYL-1™, were investigated. The adhesives were mixed with various silica-based micro- and nano-particles as fillers. Different tests were carried out on the adhesives with and without fillers in order to characterise their chemical and mechanical properties. The tests included colorimetry, dynamic-mechanical methods of analysis and tests on bending strength. No property changes could be ascertained in the bulked adhesives that would be negative for the restoration of delicate flat glass.
Aerosol emissions from brake pads are evolving into the focus of industrie and regulation. Many institutes are extending their dynamometer test stands with aerosol measurement equipement. While this is in general a good developement, the details of aerosol measurement and the special problems in the case of brake pad emissions need some special attention. The instrumentation can not be used out of the box and the important parameters will be highlighted in this presentation.
Polybromierte Flammschutzmittel (PBFSM) werden seit den 1960er Jahren zur Herabsetzung der Entflammbarkeit von Polymeren verwendet. Diese stehen auf Grund ihrer potentiell persistenten, bioakkumulierenden sowie toxischen Eigenschaften bis heute im Fokus der Wissenschaft und Gesetzgebung. In den letzten Jahren kam es verstärkt zum Einsatz neuer („emerging“) sowie neuartiger („novel“) PBFSM. Diese Verbindungen wurden bereits in der Umwelt bzw. oberhalb von 0,1 Gew.-% in Bedarfsgegenständen nachgewiesen. Zwei Vertreter, über deren Vorkommen, physikochemischen Eigenschaften und Umwelt-verhalten nur wenig bekannt ist, wurden daher ausgewählt, um das Abbau- und Transformationsverhalten näher zu untersuchen. Um eine Einschätzung über das Umweltverhalten bzw. die Metabolisierung dieser Verbindungen vornehmen zu können, werden sowohl Untersuchungen der cyto-chromabhängigen Biotransformation (Phase I/II) anhand mikrosomaler Ansätze als auch die Simulation oxidativer/reduktiver Abbauprozesse durch die Kopplung aus elektrochemischer Zelle (EC) und massenspektrometrischer Detektion (MS) herangezogen. Ziel der präsentierten Arbeit ist es, ein erstes Verständnis des Umweltverhaltens dieser neuartigen Kontaminanten zu entwickeln, um so eine Bewertung über die toxikologische Relevanz dieser Verbindungen bzw. deren Umwelt-/Bio-Transformationsprodukte geben zu können.
Phosphor ist ein für alle Lebewesen essentielles Element und in seinen Funktionen nicht zu ersetzen. Der Bedarf wird aus der Nahrung gedeckt, daher wird Phosphor letztendlich durch Ackerbau den Böden entzogen. Der Nährstoff muss ersetzt werden, um dauerhafte Landwirtschaft zu ermöglichen. Das geschieht zum einen durch den Einsatz von Wirtschaftsdüngern, aber zu einem großen Teil auch durch Mineraldünger. Das hierfür benötigte Rohphosphat wird bergmännisch aus fossilen Lagerstätten gewonnen. Die entsprechende Reichweite wird auf über 300 Jahre geschätzt. Daher besteht zwar keine unmittelbare Gefahr, dass dieser lebenswichtige Nährstoff zu Neige geht, es bestehen jedoch erhebliche Versorgungsrisiken. Zum einen ist Europa nahezu vollständig von Importen abhängig und damit auch Schwankungen der Weltmarktpreise ausgesetzt. Darüber hinaus liegen Förderung und Reserven von Rohphosphaten entweder in Ländern mit hohem Eigenbedarf (USA, China) oder in politisch instabilen Regionen (Marokko, West Sahara). Außerdem sind viele Rohphosphate mit Schwermetallen wie Uran, Thorium und Cadmium belastet. Das Umweltbundesamt schätzt, dass jährlich mehr als 160 t Uran durch Mineraldünger auf deutsche Ackerflächen ausgebracht werden. Rückgewinnung von Phosphor könnte helfen, diese Probleme zu reduzieren. Ein bedeutendes Potential dafür stellt der Abwasserstrom dar. Die Menge an Phosphor darin wird deutschlandweit auf etwa 70.000 t jährlich geschätzt. Das entspricht etwa der Hälfte der Menge an Phosphor, die derzeit für Mineraldünger benötigt wird. Der Vortrag würde sich mit möglichen Prozessen der Rückgewinnung, deren Wirtschaftlichkeit und Herausforderungen der Analytik befassen:
- in den letzten Jahren wurden zahlreiche Verfahren zur Rückgewinnung von Phosphor aus verschiedensten Phasen der Abwasserreinigung entwickelt (wässrige Phase, Klärschlamm, Klärschlammasche). Ausgewählte Verfahren würden vorgestellt und bewertet.
- für einen Einsatz der so gewonnenen Recyclingphosphate als Düngemittel muss die Schadstofffreiheit und Pflanzenverfügbarkeit der Nährstoffe sichergestellt werden. Dazu ist zu prüfen, ob die zurzeit gängigen Verfahren der Probenvorbereitung und Analytik auch auf Recyclingphosphate anwendbar sind. Das gilt neben der Bioverfügbarkeit von Phosphor besonders für Schadstoffe, da die Recyclingdünger aus Abfallmaterialien gewonnen werden, die stark belastet sein können. Das gilt besonders für die speziesspezifische Analytik von Chrom (Chrom (VI) vs. Chrom (III)) in verschiedenen Matrices.
Analytische Verfahren zur On-Line-Bestimmung von Elemementkonzentrationen in Pulvern und Aschen
(2016)
Die Aufbereitung kommunaler Abwässer leistet einen wichtigen Beitrag zum Schutz der Umwelt und der Reinhaltung der Gewässer. Im Zuge der Abwasserreinigung entstehen deutschlandweit jährlich ca. 2,4 Millionen Tonnen Klärschlamm. Diese Massen stellen für die Anlagenbetreiber oft eine Herausforderung bei der Entsorgung dar. Es sind jedoch neben zahllosen Schadstoffen auch anorganische Wert- und Nährstoffe enthalten deren Nutzung zunehmend attraktiv wird. Ein essenzieller und in Lagerstätten begrenzt vorhandener Nährstoff ist Phosphor. Dieser ist in Klärschlämmen enthalten und erreicht in Klärschlammaschen Konzentrationen von bis zu 10 %. Eine Verwertung als Düngemittel in der Landwirtschaft ist jedoch nur für schadstoffarme Materiale mit guter Pflanzenverfügbarkeit der Nährstoffe zulässig. Für die Aufbereitung von Klärschlämmen und Schadstoffentfrachtung von Klärschlammaschen existieren verschiedene technologische Ansätze. Für jeden Prozess ist eine analytische Überwachung der Nährstoffwerte sowie der Schadstoffgrenzwerte erforderlich. Im Vortrag werden die Ergebnisse eines Projektes zur on-line Analytik thermisch aufbereiteter Klärschlammaschen vorgestellt. Es werden die Methoden der Röntgenfluoreszenz (RFA) und der Laserplasmaspektroskopie (LIBS) parallel angewendet und verglichen.
In the last years, secondary low-energy electrons (LEE) emerged as important, if not predominant, reductive pathway in ionizing damage of biomolecules. These electrons are created in copious amount as result of inelastic scattering of high energy radiation at water. Until now, all experiments the quantification of the effects of LEEs on the biomolecular damage was either performed in vacuum with LEE sources or with DNA on surfaces in humid atmosphere.
We present a new experimental setup to irradiate biomolecules with electrons under physiological conditions. In combination with monte carlo simulations this setup makes it possible to determine microdosimetric quantities for biomolecules in liquid environment under electron irradiation.
This opens up new possibilities in radiation research to access the LEE damage under well defined physiological condition, for more complex systems, such as DNA-Protein complexes and even living cells.
Radiation damage to DNA is one of the main causes for cancer and likewise a major tool in its treatment. One of the dogma of the classical radiochemistry and physics involves the opinion that radicals such as OH° produced by ionizing radiation are the most lethal agents. This scenario is increasingly disputed as secondary low-energy electrons are emerging [1] as important, if not predominant, reductive pathway in ionizing damage of biomolecules. These electrons are generated in copious amount in aqueous environment as secondary scattering products. But until now all research concerning the quantification of the effects of low energy electrons on the biomolecular damage was either performed in vacuum with low energy electron sources or with DNA plasmids on metallic surfaces in humid environment. In this work we present detailed experimental and simulation microdosimetry data on electron damage to plasmid DNA in liquid environment: Well-defined electron energy and dosage irradiation was achieve by using an EM and the irradiation through a nanomembrane. The results are analyzed in terms of single- and double-strand break probabilities in the dependence of dose, energy, number of primary and secondary electrons. The results are important not only from the basic scientific point of view but also for the development of effective radiosensitizers, either as protecting or enhancing (radiotherapy) cofactors.
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 metabolisation in the environment and technical installations. Transformation products (TP) and metabolites may exhibit properties other than those of the mother substance. They can be more harmful 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.1 However, only little data is available concerning their TP and metabolites. During 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. Both pesticides are considered persistent in soil and very stable towards aqueous photolysis.2 In this case however, the role of natural organic matter has not yet been examined. Since both pesticides also show moderate mobility in soils they may end up in ground water from which drinking water is produced. During this process, waters are treated with chlorine agents, ozone, and energy-rich UV radiation. Owing to the vigorous conditions the formation of a variety of technical TP can be expected. Additionally, for all environmental compartments the degradation of the fungicides by bacteria is a factor which needs to be taken into account. For this survey, iron-oxidising bacteria of the leptothrix variety were chosen as model organisms. Their potential for the metabolisation of the analytes 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 characterised by NMR. Toxicity assessment of these TP is essential to define threshold values in the environment. The model reaction system considering the interaction with organic matter will be presented and possible TP will be shown.
In recent years 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 organic compounds. However incomplete degradation reactions during this process can result in transformation products due to the oxidative conditions. The transformation products may have a higher toxicity than the precursor substances and are often only partly removed during the waste water treatment. Since a lot of these compounds are still unknown, the 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. Among various semiconductors, 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 with light of an energy higher than the band gap of the semiconductor, 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. To study photocatalytic reactions, a model system has been developed to simulate environmental relevant conditions for photocatalytic reactions of organic substances on 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 occurrence, behavior and fate in the environment. Metformin is the drug of choice for treating type 2 diabetes. The drug therapy for diabetes mellitus has increased significantly in recent years. 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 an analogon of the neurotransmitter γ-aminobutyric acid (GABA) which is used as antiepileptic drug and for the treatment of neuropathic pain. Gabapentin 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.
Flame retardants are increasingly used in consumer products as e.g. electronics and furniture as well as in construction. Along with the increased usage, concerns about negative effects of flame retardants on human health and the environment have been raised. Concerning construction products one application for flame retardants is the furnishing of steel structures with reactive flameproof coatings. These coatings consist of a complex mixture of different chemicals, additives and solvents. For the evaluation of the risk possibly posed by their application to the environment, this whole mixture should be tested.
Two different leaching tests were applied according to DIN/TS 16637-2 (sample permantly submerged in water) and DIN EN 16105 (immersion and drying cycles), respectively, which can be used for plate-like products. Eluates were divided into subsamples for the measurement of different parameters: pH-value, conductivity, total organic carbon (TOC), cation and anion concentration. For screening of organic compounds, aqueous samples were liquid/liquid extracted using three solvents with different polarity (toluene, hexane and ethylacetate). GC-MS chromatograms were recorded in the SCAN mode and mass spectra of the peaks were compared with spectras stored in the NIST library.
Eluates of leaching test accroding to DIN CEN TS 16637-2 showed low electrical conductivity (20 to 150 µS/cm) and low release of cation and anions often near the LOQ. Diffferences could be observed for plates treated with the reactive coating at both sides and plates coated only at one side, while the other side is only furnished by the corrosive protection layer. Release of TOC and Zn was approx twice or 10 fold higher in the case of plates coated on one side. Furthermore, the comparison of the results for both types of plates showed that a large portion of the released compounds originate rather from the corrosion protection layer than from the reactive coating itself. Leaching tests according to DIN EN 16105 have not been finished yet, but first results show that the conductivity is much lower (1-4 µS/cm) than for the tests according to DIN/TS 16637-2 leading to the assumption that the release of compounds is lower.
By comparison of the mass spectra with library data, mainly organic solvents as xylene, 1-methoxy-2-propanol acetate and n-btuyl carbamate have been tentatively identified so far in the first test fraction done by DIN CEN TS 16637-2.
Es wurde ein Online-Analysenverfahren zur Bestimmung von Elementgehalten in Klär-schlammaschen und deren Produkten aus einem thermochemischen Verfahren entwickelt. Durch das thermochemische Verfahren können Wertstoffe aus den Aschen wieder für die Kreislaufwirtschaft nutzbar gemacht und Schadstoffe sicher entfernt werden. Das Analysensystem ist eine Methodenkombination von Online-Laser induzierter Plasma Spektroskopie (LIBS) und Online-Röntgenfluoreszenzanalyse (RFA). Robustheit und modulare Bauweise des Verfahrens sind wichtige Anforderungen um auch für andere Anwendungen nutzbar zu sein.
Die Auswaschung von Bioziden wurde für eine Reihe von behandelten Materialien in Labor- und Freilandversuchen untersucht. Beobachtungen aus Freilanduntersuchungen und Ergebnisse aus Regressionsanalysen zum Einfluss von Witterungsfaktoren werden dargestellt. Verschiedene Untersuchungen zu Materialeigenschaften, die Einfluss auf die Auswaschbarkeit von Bioziden haben können, werden für zwei Farben verglichen. Ein Modellansatz zur Beschreibung von Laborversuchsdaten wird kurz erläutert.
Phosphorrecycling sollte nicht isoliert praktiziert werden, sondern im Kontext der spezifischen Abwasserbehandlung und der Betrachtung weiterer Nährstoffe wie Stickstoff und Kalium.
Hohe Rückgewinnungsquoten um jeden Preis sind nicht immer zielführend und u.U. sogar schädlich für die Kreislaufwirtschaft. Es sollte eine Kombination verschiedener Ansätze je nach vorhandener Infrastruktur verfolgt werden. Fällungsverfahren (Struvit) sind geeignet kostengünstig kleine Mengen Phosphor zurückzugewinnen. Für ein umfassendes P-Recycling muss die Rückgewinnung aus der Asche erfolgen.
Electrocoalescence of aqueous droplets in oil emulsions is commonly contemplated for enhancing separation.
High voltage electric fields can induce charges to Drops evoking merging of adjacent droplets. The newly formed larger Drops then sink faster in gravitational common settlers. Therefore, separation performance of an electrostatic coalescer is strictly linked to characteristics of the electric field and properties of the liquid−liquid system. In this work, the coalescence Performance of water droplets sinking in dodecane at a pulsed DC electric field is investigated. An experimental setup allowing the simultaneous injection of similar sized drops, setting of voltage and pulsation frequency, and particle tracking at high frame rate and resolution is designed. The generated data are used to check the validity of modeling approaches for drag, dipole−dipole forces, and film-thinning. Furthermore, CFD simulations are carried out using a volume of fluid method tracking the interfaces between the two phases.
The annual demand of phosphorus (P) for fertilizer use is more than 550,000 t in Germany. Several of the input streams like mineral fertilizer produced from phosphate rock or sewage sludge are problematic due to contamination with heavy metals and organic pollutants and/or supply risks. Phosphorus recovery from the wastewater stream might help to diminish these problems. Several procedures have been developed to recover P from either sewage sludge ash (SSA) or wastewater via precipitation or crystallization as struvite. This study determined the elemental composition and trace metal mass fractions of 252 SSA samples and 17 struvite samples from wastewater treatment plants (WWTP) to see whether there are differences related to the source of the sludge (municipal/industrial) or the stage of the WWTP where the struvite is produced. Results indicated that there is no clear trend of the elemental mass fractions related to the source of the sludge. All struvite samples show very low heavy metal contents, even though the struvite precipitated from the sludge shows slightly elevated heavy metal mass fractions compared to struvite crystallized from sludge liquor. Struvite is a clean and plant available material for fertilizer production from wastewater streams and has some advantages for the wastewater treatment plant. However, since the P recovery rate of struvite processes is low (7–11%) compared to that from SSA processes (90%), recovery from SSA is necessary for a substantial P recovery from the wastewater stream.
A monitoring method is introduced that creates twodimensional (2D) maps of the soil gas distribution. The method combines linear gas sensing technology for in-situ monitoring of gases in soil with the mapping capabilities of Computed Tomography (CT) to reconstruct spatial and temporal resolved gas distribution maps. A weighted iterative algebraic reconstruction method based on Maximum Likelihood with Expectation Maximization (MLEM) in combination with a source-by-source reconstruction approach is introduced that works with a sparse setup of orthogonally-aligned linear gas sensors. The reconstruction method successfully reduces artifact production, especially when multiple gas sources are present, allowing the discrimination between true and non-existing so-called ghost source locations. Experimental validation by controlled field experiments indicates the high potential of the proposed method for rapid gas leak localization and quantification with respect to Pipeline or underground gas storage issues.
Small-arm shooting ranges often receive a significant input of lead (Pb), copper (Cu) and antimony (Sb) from ammunition. The goal of the present study was to investigate the mobility, distribution and speciation of Pb and Sb pollution under field conditions in both untreated and sorbent-amended shooting range soil. Elevated Sb (19–349 μg L⁻¹) and Pb (7–1495 μg Pb L⁻¹) concentrations in the porewater of untreated soil over the four-year test period indicated a long-term Sb and Pb source to the adjacent environment in the absence of remedial measures. Mixing ferric oxyhydroxide powder (CFH-12) (2%) together with limestone (1%) into the soil resulted in an average decrease of Sb and Pb porewater concentrations of 66% and 97%, respectively. A similar reduction was achieved by adding 2% zerovalent iron (Fe°) to the soil. The remediation effect was stable over the four-year experimental period indicating no remobilization. Water- and 1 M NH₄NO₃-extractable levels of Sb and Pb in field soil samples indicated significant immobilization by both treatments (89–90% for Sb and 89–99% for Pb). Results from sequential extraction analysis indicate fixation of Sb and Pb in less accessible fractions like amorphous iron oxides or even more crystalline and residual mineral phases, respectively. This work shows that amendment with Fe-based sorbents can be an effective method to reduce the mobility of metals both in cationic and anionic form in polluted shooting range soil.
To understand the metabolic fate of food relevant mycotoxins in vitro systems were mainly used as the method of choice, so far. Yet, in recent years coupling of electrochemistry mass spectrometry (EC-MS) gained increasing importance as promising technique for fast simulation of metabolic processes and was successfully applied in particular for drug metabolism [1].
The aim of our work was to investigate the potential of EC-MS to predict phase I metabolites of priority mycotoxins and to compare the results with in vitro experiments. Hence, the EU-regulated Fusarium mycotoxins zearalenone (ZEN) and patulin as well as dihydroergocristine (DHEC) as model compound of ergot alkaloids were electrochemically oxidized and analyzed by EC MS for the first time.
Electrochemical conditions were set-up individually for each of the three mycotoxins. By using a coulometric flow through cell with a diamond working electrode oxidation of the chosen mycotoxins was observed after applying potentials between 1.7 and 2.0 V vs. Pd/H2. The electrochemically generated reaction products were analyzed online by mass-spectrometric detection.
All of the three chosen mycotoxins were electrochemically converted to mono- and/or dihydroxylated products confirming the results of ZEN related metabolism studies [2, 3] and in case of DHEC own results from in vitro assays. Due to a lack of metabolism studies concerning the oxidative fate of patulin, interpretation of EC-MS data and performing microsomal studies is of particular relevance.
Beside the identified products from electrochemical oxidation of ZEN, patulin and DHEC there is still a number of yet unknown compounds. Additional structural characterization of detected compounds by NMR and X-ray analysis will be facilitated by their large-scale production using preparative EC cells.
Im Rahmen eines vom BMBF geförderten KMU-Innovativ Forschungsprojekts (KKZ 0316199B) konnte in Kooperation mit der Firma Greibo Chemie GmbH ein bio-katalysierter Prozess zur Hydrolyse und Veresterung von gastronomischen Altfetten etabliert werden. Unter Anwendung des Enzyms Candida antarctica lipase-A (CAL-A) kann dieser Prozess mit einem teilweise wässrigen Medium durchgeführt werden was prozesstechnisch einige Vorteile mit sich bringt. Im Gegensatz zu anderen Acyltransferasen ist die CAL-A nicht nur in der Lage die Alkoholyse zu katalysieren sondern auch Fettsäuren zu verestern. Dies eröffnet eine breitere Anwendung des Prozesses auf weitere Produktgruppen und Abfallströme. Es wurden Optimierungen mit modifizierten Enzymen und verschiedenen Fetten und Alkoholen vorgenommen. Des Weiteren wurden die verfahrenstechnischen Parameter optimiert und ein Scale-up auf den 0,5 Tonnen Maßstab durchgeführt. Die aus dem Prozess resultierenden Fettsäureester eignen sich als Motoren- oder Hydraulikbasisöle sowie als Metallbearbeitungsöle. Im Vergleich zu den Mineralölkosten von ca. 1,0 - 1,5 € pro kg muss bei einer Umstellung eines Hydrauliköls auf Fettsäureester (konventionell hergestellt) allerdings bei einem Preis von 3 – 5 € pro kg mit Mehrkosten bei gleichbleibendem Verbrauch gerechnet werden. Für die erfolgreiche Markteinführung müssten vermutlich die durchaus vorhandenen ökologischen Vorteile der Altfett-basierten Produkte beworben werden.
Im Rahmen eines vom BMBF geförderten KMU-Innovativ Forschungsprojekts (KKZ 0316199B) konnte in Kooperation mit der Firma Greibo Chemie GmbH ein bio-katalysierter Prozess zur Hydrolyse und Veresterung von gastronomischen Altfetten etabliert werden. Unter Anwendung des Enzyms Candida antarctica lipase-A (CAL-A) kann dieser Prozess mit einem teilweise wässrigen Medium durchgeführt werden was prozesstechnisch einige Vorteile mit sich bringt. Im Gegensatz zu anderen Acyltransferasen ist die CAL-A nicht nur in der Lage die Alkoholyse zu katalysieren sondern auch Fettsäuren zu verestern. Dies eröffnet eine breitere Anwendung des Prozesses auf weitere Produktgruppen und Abfallströme. Es wurden Optimierungen mit modifizierten Enzymen und verschiedenen Fetten und Alkoholen vorgenommen. Des Weiteren wurden die verfahrenstechnischen Parameter optimiert und ein Scale-up auf den 0,5 Tonnen Maßstab durchgeführt. Die aus dem Prozess resultierenden Fettsäureester eignen sich als Motoren- oder Hydraulikbasisöle sowie als Metallbearbeitungsöle. Im Vergleich zu den Mineralölkosten von ca. 1,0 - 1,5 € pro kg muss bei einer Umstellung eines Hydrauliköls auf Fettsäureester (konventionell hergestellt) allerdings bei einem Preis von 3 – 5 € pro kg mit Mehrkosten bei gleichbleibendem Verbrauch gerechnet werden. Für die erfolgreiche Markteinführung müssten vermutlich die durchaus vorhandenen ökologischen Vorteile der Altfett-basierten Produkte beworben werden.
In the recent years, highly crosslinked plasma polymers have started to unveil their potential in numerous biomedical applications in thin-films form. However, conventional diagnostic methods often fail due to their diverse molecular dynamics conformations. Here, glassy dynamics and the melting transition of thin PEO-like plasma assisted deposited (ppPEO) films (thickness 100 nm) were In situ studied by a combination of specific heat spectroscopy, utilizing pJ/K sensitive AC-calorimeter chip, and composition analytical techniques. Different crosslinking densities were obtained by different plasma powers during the deposition of the films. Glassy dynamics was observed for all values of the plasma power. It was found that the glassy dynamics slows down with increasing the plasma power. Moreover, the underlying relaxation time spectra broaden indicating that the molecular motions become more heterogeneous with increasing plasma power. In a second set of experiment, the melting behavior of the ppPEO films was studied. The melting temperature of ppPEO was found to be decreasing with increasing plasma power. This was explained by a decrease of the order in the crystals due to formation of chemical defects during the plasma process.
The organophosphate nerve agents Tabun (GA), Sarin (GB) and Soman (GD) are among the most toxic chemical warfare agents (CWA) known, and exert their biological effects by irreversibly inhibiting acetylcholinesterase enzymes of the human nerve system. The use of these agents in the past century has killed millions of civilians around the world during World Wars I and II, and after that, approximately 40.000 tons of chemical ammunition were dumped into the Baltic Sea, containing ca. 13.000 tons of chemical warfare agents. Since their production, almost all the nations of the world have been strictly avoiding the development and use of CWA, participating in active destruction of CWA stockpiles, especially since the Chemical Weapon Convention (CWC) of 1993. However, CWA have been used in offensive ways against civilian population by terrorists, as for instance in the fatal Tokyo subway terror incident of 1995 or, most recently, against antigovernment demonstrators in Syria in 2013. Due to their higher toxicity and continuous use, it is therefore very important to develop simple and fast detection methods relying on new nerve agent sensing modalities for use in control and inspection.
A practically useful fluorescent probe must possess a rapid response and high sensitivity, and shall be implementable into easy-to-use devices for real time detection by untrained personnel. Taking into account this fact, in this work we have synthesized several mesoporous silica materials containing boron–dipyrromethene (BODIPY) moieties for the detection of nerve agents GA, GB and GD in the gas phase. Development of our system indicated that the most potent materials are able to respond to the presence of nerve agent simulants diethyl cyanophosphonate, diethyl chlorophosphate and diisopropyl fluorophosphate, which have to be used in a laboratory setting, yet also for the real nerve agents Sarin, Soman and Tabun, producing a strong quenching of the fluorescence. Furthermore, a portable device for the detection of GA, GB and GD in the gas phase has been prepared for in situ sensing and rapid screening applications, consisting of strips that are able to indicate the targets down to below 1 mgm-3 which is below the LD50 values.
Zur Basisabdichtung von Mülldeponien werden zunehmend polymere Abdichtungen mit Foliendecken zwischen 1 und 3 mm eingesetzt, die vielfach als absolut dicht gegenüber Sickerwässer und deren Inhaltsstoffen gelten. Durch Permeationsvorgänge ist jedoch mit Restdurchlässigkeiten zu rechnen, die auch bei technisch einwandfreien, intakten Folien auftreten. Es werden Meßmethoden vorgestellt, derartige Restdurchlässigkeitsraten an handelsüblichen Dichtungsbahnen für Deponiebasisabdichtungen zu messen. Als Permeenten dienen neben Sickerwasser aus einer Hausmülldeponie, konzentrierte, reine organische Lösungsmittel, deren Gemische untereinander und stark verdünnte Lösungen organischer Lösungsmittel in Wasser. Meßergebnisse werden angegeben und diskutiert.
Mit der Plasmaspektrometrie (ICP) wurden in Abwässern aus dem Berliner Abwassersystem simultan 11 Elemente (Al, B, Ba, Cr, Cu, Fe, Mn, Ni, P, Ti, Zn) bestimmt. Der erforderliche Arbeitsaufwand ist erheblich geringer als nach Deutschen Einheitsverfahren zur Abwasseruntersuchung. Bestimmungsgrenzen werden mitgeteilt, auf systematische Fehlermöglichkeiten wird eingegangen. Durch Eindampfen der Proben lassen sich die Nachweisgrenzen in den meisten Fällen um den Faktor 10 weiter senken. Die Hydridtechnik zur Verbesserung der Nachweisempfindlichkeit bei den Elementen Sn, As, Sb, Se erwies sich in der Abwassermatrix als problematisch.
Influence of the of dealumination and porosity on the acid sites of natural zeolite clinoptilolite
(2016)
Heavy feedstock from crude and bio oil is a widely available and renewable resource for production of fuel and starting materials for other organic valuables by cracking or hydrocracking. Catalytic processing of heavy feedstock can meet the increased demand of energy up to a great extent. It requires the application of acidic catalysts like zeolites. However, the used synthetic catalysts are difficult to recover and reuse and are mostly spent.
The use of natural zeolite as spent catalysts may open new perspectives in the chemical use of heavy feed feedstock by chemical conversion. Natural zeolites are not expensive, widely available and environment friendly. Clinoptilolite is the most abundant natural zeolite. Clinoptilolite has a crystalline structure with a defined micropore system of medium size showing unique ion exchange and sorption properties. However, it is catalytically active only in the H-form. Also certain porosity is required for improvement of the accessibility of active sites.
This paper deals with the tuning of acid properties and of the mesoporosity of the clinoptilolite by variation of the Si/Al framework ratio, extra-framework aluminum and modification of the porosity by specific acid and water vapor treatment. The preparation of hierarchical pore structures containing interconnected micro-meso-macropores is an important factor influencing the catalytic performance.
The obtained materials have been characterized by XRD, TEM, FTIR, Raman, TG/DSC. The chemical composition has been determined by ICP-AES. The porosity have been investigated by nitrogen adsorption desorption measurements. The acidity has been measured by Ammonia-TPD. The extent of dealumination, stability of the clinoptilolite against acid treatment and the change in the nature of acid sites and their local structure has been studied by solid state 29Si and 27Al MAS NMR spectroscopy in detail. The catalytic activity has been investigated in the acetalization of benzaldehyde with 1,3-butanediol. The impact of the porosity, change of the Si/Al ratio as well as present Al species on catalytic properties will be discussed.
Tapping mode AFM (TM-AFM) is a standard technique to image biomolecules and cells avoiding damage to susceptible samples.
For preparing AFM samples we fixed (untreated and radiated) plasmids chemically on ultra-smooth mica silanized with APTES.
The recorded AFM images were examined concerning the contour length, the conformation and the writhing number of the plasmids.
We found that the measured contour length is in accordance with the number of base pairs. Apart from that, we indicate different structures of plasmids from our AFM images, which were assigned to our plasmid data from agarose gel-electrophoresis.
One-part-geopolymers, produced by addition of water to a mixture of solid silica and sodium alumi-nate, are a less exhaustively studied approach to form geopolymeric binders. Depending on the silica source, the reaction products show significant amounts of zeolite Na-A besides amorphous compounds. Previously, 29Si MAS NMR has been used to analyze the chemical structure of such one-part geopolymers, having crystalline structures and amorphous phases (Q2, Q3, Q4).
In this work, pure zeolites and three different one-part-geopolymers cured for 1 day were investigated by 29Si-27Al TRAPDOR NMR. It was used to identify aluminum phases in overlapping silicon sites. Zeolites Na-X (Si/Al=1.4) and Na-Y (Si/Al=2.7) served as model systems to measure the TRAPDOR effect of the structural units Q4(mAl). Both materials show several Q4(mAl) signals, which are all separated by their chemical shifts. The more aluminum surrounds the silicon tetrahedron the higher are the normalized TRAPDOR difference signals (S0/∆S). The intensity ratios between Q4(mAl) to Q4({m-1}Al) of these signals is fixed but vary slightly between both zeolites. These results are transferred to the complex geopolymer structure.
Many microorganisms possess circular molecules of plasmid DNA. Their conformation may vary from more compact to relaxed forms. Structural changes have important consequences for the physiological role of plasmids and will influence plasmid transcription, replication and their susceptibility to environmental stresses. Radiation is a common form of stress and can cause structural damage to DNA such as single (SSB) and double strand breaks (DSB). Recently, it has been indicated that secondary low-energy electrons play an important role in biological damage under vacuum condition. Therefore, our studies focus on irradiating the plasmid pUC19 with low-energy electrons for the first time under physiological conditions.
A droplet-based microfluidic sensor was developed for the detection of Hg2+ traces in water. The approach uses gated mesoporous nanoparticles loaded with a fluorescent BODIPY dye. The squaraine-based gating mechanism is highly selective for Hg2+ and the indicator release mechanism ensures sensitive detection. The microfluidic system is modular and was assembled from simple PTFE/PFA tubes, while detection was realized with standard optomechanic, optic, and electronic parts. The sensor shows a stable response without memory effects and allows the detection of Hg2+ in water down to 20 ppt.
Background: 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.
Results: 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.
Conclusions: Application of sewage sludge containing Cd from artist paints does not increase the amount of Cd leached from this soils. Furthermore the quantity of Cd from artists’ paints calculated in the restriction dossier is 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.
Microorganisms accumulate molar concentrations of compatible solutes like ectoine to prevent proteins from denaturation. Direct structural or spectroscopic information on the mechanism and about the hydration shell around ectoine are scarce. We combined surface plasmon resonance (SPR), confocal Raman spectroscopy, molecular dynamics simulations, and density functional theory (DFT) calculations to study the local hydration shell around ectoine and its influence on the binding of a gene-S-protein (G5P) to a single-stranded DNA (dT(25)). Due to the very high hygroscopicity of ectoine, it was possible to analyze the highly stable hydration shell by confocal Raman spectroscopy. Corresponding molecular dynamics simulation results revealed a significant change of the water dielectric constant in the presence of a high molar ectoine concentration as compared to pure water. The SPR data showed that the amount of protein bound to DNA decreases in the presence of ectoine, and hence, the protein-DNA dissociation constant increases in a concentration-dependent manner. Concomitantly, the Raman spectra in terms of the amide I region revealed large changes in the protein secondary structure. Our results indicate that ectoine strongly affects the molecular recognition between the protein and the oligonudeotide, which has important consequences for osmotic regulation mechanisms.
To study the mechanical interface behavior of single-walled carbon nanotubes (CNTs) embedded in a noble metal, we performed CNT-metal pull-out tests with in situ scanning electron microscope experiments. Molecular dynamics (MD) simulations were conducted to predict force-displacement data during pull-out, providing critical forces for failure of the system. In MD simulations, we focused on the influence of carboxylic surface functional groups (SFGs) covalently linked to the CNT. Experimentally obtained maximum forces between 10 and 102 nN in palladium and gold matrices and simulated achievable pulling forces agree very well. The dominant failure mode in the experiment is CNT rupture, although several pull-out failures were also observed. We explain the huge scatter of experimental values with varying embedding length and SFG surface density. From simulation, we found that SFGs act as small anchors in the metal matrix and significantly enhance the maximum forces. This interface reinforcement can lead to tensile stresses sufficiently high to initiate CNT rupture. To qualify the existence of carboxylic SFGs on our CNT material, we performed analytical investigation by means of fluorescence labeling of surface species and discuss the results. With this contribution, we focus on a synergy between computational and experimental approaches involving MD simulations, nano scale testing, and analytics (1) to predict to a good degree of accuracy maximum pull-out forces of single-walled CNTs embedded in a noble metal matrix and (2) to provide valuable input to understand the underlying mechanisms of failure with focus on SFGs. This is of fundamental interest for the design of future mechanical sensors incorporating piezoresistive single-walled CNTs as the sensing element.
Zur Bestimmung von Arzneimittelrückständen in Oberflächengewässern wird häufig die LC-MS/MS als Methode der Wahl eingesetzt. Obwohl sich dieses Nachweisverfahren durch eine hohe Empfindlichkeit und Selektivität auszeichnet, gibt es vor allem bei geringen Substanzkonzentrationen häufig störende Einflüsse durch Matrixeffekte. Diese Matrixeffekte können unterschiedliche Ursachen haben.
Einige Matrixeffekte werden am Beispiel des Wirkstoffs Carbamazepin erläutert. Carbamazepin wird durch Kläranlagen nur partiell aus dem Abwasser entfernt und ist im Spurenbereich auch noch im Trinkwasser nachzuweisen. Wenn für die LC-MS/MS wasserbasierte Anteile in der mobilen Phase genutzt werden, befinden sich trotz Verwendung einer Labor-Reinstwasseranlage in der mobilen Phase noch kleinste Konzentrationen von Carbamazepin, welche einen Blindwert im unteren ppt-Bereich verursachen.
Weitere Matrixeffekte treten durch die unterschiedliche Qualität der Oberflächenwasserproben auf. Koelutionen von weiteren Inhaltstoffen zeitgleich mit dem Zielanalyten führen zu einer Diskriminierung des Meßsignals. Verbindungen, die den gleichen Massenübergang bei nahezu identischer Retentionszeit zeigen, erfordern eine reproduzierbare chromatographische Vortrennung oder die Wahl einer alternativen HPLC-Säule.
N4-acetyl-SMX is the most important cross-reacting compound for the SMX-ELISA with concentrations of 1064 - 2488 ng/L in influent wastewater and 40 - 160 ng/L in effluent wastewater.
The ELISAgrams for estrone show less interfering signals than for SMX.
ELISAgrams of SMX and estrone display in effluent wastewater more interfering signals than in influent wastewater.
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.
Multiple anthropogenic stressors cause worldwide amphibian declines. Among several poorly investigated causes is global pollution of aquatic ecosystems with endocrine disrupting compounds (EDCs). These substances interfere with the endocrine system and can affect the sexual development of vertebrates including amphibians. We test the susceptibility to an environmentally relevant contraceptive, the artificial estrogen 17α-ethinylestradiol (EE2), simultaneously in three deeply divergent systematic anuran families, a model-species, Xenopus laevis (Pipidae), and two non-models, Hyla arborea (Hylidae) and Bufo viridis (Bufonidae). Our new approach combines synchronized tadpole exposure to three EE2-concentrations (50, 500, 5,000 ng/L) in a flow-through-system and pioneers genetic and histological sexing of metamorphs in non-model anurans for EDC-studies. This novel methodology reveals striking quantitative differences in genetic-male-to-phenotypic-female sex reversal in non-model vs. model species. Our findings qualify molecular sexing in EDC-analyses as requirement to identify sex reversals and state-of-the-art approaches as mandatory to detect speciesspecific vulnerabilities to EDCs in amphibians.
Pyrotechnic smoke generators fall under the Directive 2013/29/EU in Europe and could potentially belong to all categories except consumer fireworks. These types are especially present in the field of “Other Pyrotechnic Articles” of the categories P1 and P2, e.g. as simulation devices for paintball or airsoft gaming. The specific users of these products are aware of the corresponding smoke liberation during use and usually wear protective equipment to minimize exposure to potentially harmful aerosols. However, such products are often misused against the labelling requirements in locations where these articles are not supposed to be used, like football stadiums and demonstrations. In contrast to the intended use, uninvolved third parties are likely exposed to these reaction products without proper protective equipment. This study aims at identifying the transient particle size range of the aerosols emitted during the functioning of such common smoke generators for simulation purposes. In total four different types of articles were investigated, with five colors per type (white, blue, green, red, orange). Results show that the majority of the particles were emitted in a range between 40 nm and 350 nm, with some variation depending on the smoke color. Particles with diameters of less than 100 nm are generally of specific concern, as they can penetrate the alveolar system of the human lungs and therefore present a specific hazard.
Rising temperatures worldwide pose an increasing challenge for safe and healthy living conditions. Particularly inner cities have been affected by these environmental changes because of the materials used to build houses, streets and infrastructure. The most common building material is concrete. It shows a specific heat capacity, while the heat conductivity for Standard concrete is low. Thus, the use of concrete generates a high capacity of heat storage. In addition, extensive soil sealing also contributes to the temperature rise of inner city areas compared to
their surroundings. To mitigate this so-called urban heat island effect, a self-cooling concrete paver was developed. This paver is able to store water. The evaporation of the water at elevated temperatures provides a cooling effect. This paper focuses on determination of this new paver’s capability to cool the surface and the surrounding. The new paver’s cooling Qualities were analysed in a series of laboratory tests. To prove the results outside of laboratory conditions, two fields (12 m × 8 m) with self-cooling and reference pavers were installed in Spain.
This paper presents and discusses the results of the tests. Correlation between reduced surface temperature of the self-cooling concrete pavers and the air temperature is examined.
Afin de garantir la qualité des eaux en Europe, la Commission Européenne a demandé aux États Membres, de leur fournir des résultats de mesure comparables et traçables pour l’analyse des polluants critiques. Devant ces enjeux considérables pour la protection de l’environnement, l’apport de la métrologie est nécessaire pour améliorer la fiabilité des analyses et permettre la comparabilité des résultats. C’est pourquoi, le projet de recherche européen Euramet/EMRP/ENV08 « Traçabilité des mesures pour la surveillance des polluants critiques de la DCE, Directive Cadre européenne sur l’Eau (2000/60/CE) », financé par l’EMRP, avait pour objectif de fournir des éléments pour la mise en place d’une base métrologique. Des méthodes de référence primaires permettant d’analyser des substances dangereuses prioritaires y sont développées pour répondre aux exigences de la DCE en termes de niveaux de performance (limites de quantification et incertitudes). Les hydrocarbures aromatiques polycycliques (HAP), substances dangereuses prioritaires « orphelines » de méthodes DCE compatibles, font partie des polluants ciblés par le projet. Le développement et la validation de la méthode d’analyse des HAP dans l’eau totale ont été réalisés. La méthode qui satisfait au mieux les exigences de la DCE en termes de concentrations et d’incertitudes accessibles est l’extraction en phase solide (SPE) sur un support disque suivie d’une analyse par dilution isotopique associée à la chromatographie en phase gazeuse couplée à la spectroscopie de masse (DI-CG/SM).
The European Water Framework Directive 2000/60/EC requires monitoring of organic priority pollutants in so-called whole water samples, i.e. in aqueous nonfiltered samples that contain natural colloidal and suspended particulate matter. Colloids and suspended particles in the liquid phase constitute a challenge for sample homogeneity and stability. Within the joint research project ENV08 ‘‘Traceable measurements for monitoring critical pollutants under the European Water Framework Directive 2000/60/EC’’, whole water test materials were developed by spiking defined amounts of aqueous slurries of ultrafinely milled contaminated soil or sediment and aqueous solutions of humic acid into a natural mineral water matrix. This paper presents the results of an European-wide interlaboratory comparison (ILC) using this type of test materials. Target analytes were tributyltin, polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in the ng/L concentration range. Results of the ILC indicate that the produced materials are sufficiently homogeneous and stable to serve as samples for, e.g. proficiency testing or method validation. To our knowledge, this is the first time that ready-to-use water materials with a defined amount of suspended particulate and colloidal matter have been applied as test samples in an interlaboratory exercise. These samples meet the requirements of the European Water Framework Directive. Previous proficiency testing schemes mainly employed filtered water samples fortified with a spike of the target analyte in a water-miscible organic solvent.
We have prepared and evaluated three whole water test materials containing eight polycyclic aromatic hydrocarbons (PAHs), six polybrominated diphenyl ethers (PBDEs) and tributyltin (TBT) with respect to homogeneity and short-term stability. The test materials were used as samples in two inter-laboratory comparisons. The materials were composed of natural mineral water and model suspended particulate matter (SPM) containing the target compounds at ng L-1 levels. The expanded uncertainty of the estimated mass concentrations in the final test materials was obtained by combining contributions from the homogeneity, the stability and the model SPM characterization.
The whole water materials were sufficiently homogeneous and stable at 4 °C for their intended use. In total, 12 out of 15 investigated target parameters could be assessed to be present with a relative combined expanded uncertainty below 25 %. The outcome of the two interlaboratory comparisons confirmed the good quality of the test materials and the level of uncertainties associated with the estimated mass concentrations. These findings are an important contribution towards the development of whole water matrix reference materials certified for PAH, PBDE and TBT in support of the Water Framework Directive of the European Union.
Phosphorus-fertilizers from secondary resources such as sewage sludge ash (SSA) will become more important in the future as they could substitute conventional fertilizers based on the nonrenewable resource phosphate rock. Thermochemical approaches were developed which remove heavy metals from SSA prior to its fertilizer application on farmlands. We analyzed the chemical state of mercury and selenium in SSA before and after thermochemical treatment under different conditions for P-fertilizer production by X-ray absorption near edge structure (XANES) spectroscopy. In some incineration plants the mercury loaded carbon adsorber from off-gas cleaning was collected together with the SSA for waste disposal. SSAs from those plants contained mercury mainly bound to carbon/organic material. The other SSAs contained inorganic mercury compounds which are most probably stabilized in the SSA matrix and were thus not evaporated during incineration. During thermochemical treatment, carbon-bound mercury was removed quantitatively. In contrast, a certain immobile fraction of inorganic mercury compounds remained in thermochemically treated SSA, which were not clearly identified. HgSe might be one of the inorganic compounds, which is supported by results of Se K-edge XANES spectroscopy. Furthermore, the chemical state of selenium in the SSAs was very sensitive to the conditions of the thermochemical treatment.
In 2011, the German Association of Engineers (VDI) started working on a set of guidelines towards increased resource efficiency. These guidelines represent a framework that defines resource efficiency and outlines considerations for the producing industry. A special guideline for SMEs is included as well as guidelines on methodologies for evaluating resource use indicators, such as the cumulative raw material demand of products and production systems. Resource efficiency, defined here as the ratio of specific quantifiable use to natural resource consumption, can be evaluated by defining a function which expresses the specific use and quantifies the resource requirements through a set of indicators (use of raw materials, energy, water, land and ecosystem services including sinks). The results from this also depend on the system boundary parameters and the allocation rules for by-products and waste treatment options. Optimising resource use is possible at all stages of a product’s or production system’s life cycle chain (raw material extraction, production and manufacturing, use and consumption, and the end-of-life stage). VDI guidelines are widely accepted across Germany’s industrial sector and therefore represent an important means of mainstreaming resource efficiency in this target area. As well as providing a methodological framework, the guidelines describe strategies and measures towards increasing resource efficiency, and they enable industrial producers and service providers to identify potential areas of improvement. The full article presents an overview of the methodology and contents of these guidelines and discusses their impact in achieving absolute reductions in the industrial use of natural resources.
In the last several decades, the rural exodus has led to an increasing number of inhabitants in the urban areas. The increased building and infrastructural construction caused the transformation of the landscape and to an increased land sealing in these areas. Consequently, the increased land sealing influences the air temperatures in the cities, since houses, streets and squares heat up continuously. As a result, the city and metropolitan areas became significantly warmer than their surroundings - the effect is known as Urban Heat Island (UHI). These changes have a negative impact for the quality of life. To deal with the negative effects of UHI, a high level of technical and financial effort is necessary. The costs caused by the UHI effects are in the range of several billion US dollars worldwide per year. The recent studies on UHI showed that the established methods like parks and green spaces or bright coatings for roof areas will soon not be able to effectively cope with the UHI effect in urban areas. Therefore there is a need for additional methods to mitigate UHI effect in the cities. The streets, sidewalks and squares represent approximately 30% to 40% of the inner cities areas. If these areas are designed functionally, they can have a significant impact on the UHI. This contribution focuses on development of a concrete paving stone with self-cooling properties. For the cooling effect the evaporative cooling is used. The paving stone is able to store large quantities of water and deliver during appropriate environmental conditions. This paper deals with the results of the long-term experiments on the test-fields under different climatic conditions. To interpret the test-field-results, laboratory tests were carried out as well. The paper presents and discuss the obtained results, and points out the difficulties occurred.
- Spurenelementanalytik aus Fluoreszenzlampen optimiert
- Königswasseraufschluss Methode der Wahl für REE
- Perchlorsäure-/Flusssäureaufschluss in Kombination mit Königswasseraufschluss für die meisten Elemente geeignet
- Teilweise starke Abhängigkeit der Aufschlusseffizienz vom Element bzw. der vorliegenden Elementspezies
- Nicht aufgelöste Glasmatrix stört die Analytik nicht
A biological impact on weathering was recognized already at the beginning of the twentieth century, when biochemical influence of the lichen growth on rocks was convincingly demonstrated. Later it was shown that the
progress of solid rock weathering initiated by biological colonization was affected by the initial porosity system and sensitivity of mineral association. In the meantime
a considerable amount of diverse scientific data confirm the importance of biological rock colonizers (lichens and free-living rock biofilms) in mineral material dynamics as they occur at the atmosphere-exposed rock surfaces on local as well as global scale. Subaerial rock biofilms—microbial ecosystem including free-living heterotrophic and phototrophic settlers of bare rock surfaces—are characteristic for the first stage of primary succession of terrestrial ecosystems on mineral substrates.
These cultivable and free-living communities are dominated by fungi and set the stage for the later development of a lichen cover, but in comparison to lichens also represent a new tool for laboratory experimentation and thus open a new stage of work in geomicrobiology. The Minerals sensitivity to microbially induced biological weathering can be demonstrated by studies of natural samples as well as by the laboratory mesocosm experiments.
In 2011, the German Association of Engineers (VDI) started working on a set of guidelines dealing with the improvement of resource efficiency. These guidelines represent a framework that defines resource efficiency and outlines proposals for the producing industry. A special guideline for small and medium-sized enterprises (SMEs) is included as well as guidelines on methodologies for evaluating resource use indicators, such as the cumulative raw material demand of products and production systems. The work on resource use indicators is still in progress. The evaluation of raw materials expenditure will include water, soil and land use. The model will include the availability of raw materials (criticality). Improving resource efficiency at the end-of-life stage is illustrated in this paper by the example of materials recovery from waste, here from residues out of municipal solid waste incineration (MSWI). With mechanical treatment valuable materials like ferrous and non-ferrous metals and secondary construction material can be extracted from MSWI bottom ash. The potential contribution on the resource efficiency is discussed.
Bottom ash from municipal solid waste incineration (MSWI) consists of elemental metals in considerable amounts. The exergy of bottom ash was calculated to be some 100 kJ/mol, mainly as a result of the presence of elemental Fe and Al. From this it can be shown that the recovery of elemental metals Cu, Al and Fe is beneficial. The fine fraction <4 mm additionally contains chemically bound metals (oxides, carbonates, silicates). Separation prospects with techniques as in ore processing (flotation, density separation, bioleaching, hydrothermal solution) are discussed. Although the concentration of Cu compounds in bottom ash is in the range of today’s exploited ores the economic viability of the recovery of metal compounds is uncertain. For sufficient enrichment different concerted treatment steps are required.
Mit der Parole „all liners leak“ fordern namhafte Protagonisten der US-amerikanischen Geo-kunststoffszene, dass man auch bei der Verwendung von Kunststoffdichtungsbahnen (KDB) die Deponieabdichtungen als Doppeldichtung mit Kontrolldränage ausführen muss. Dem wird von deutschen Fachleuten der „zero leakage approach“ entgegengesetzt. Danach kann unter bestimmten Voraussetzungen eine Kombinationsdichtung aus mineralischer Dichtung und KDB so gebaut werden, dass dieser „liner“ tatsächlich dicht ist und die KDB als eine echte „Konvektionssperre“ wirkt. Im deutschen Deponiebau ist man mit dieser Herangehensweise vertraut. Dennoch sollen hier nochmals die wesentlichen Elemente des „zero leakage approach“ herausgestellt werden. Auf eines dieser Elemente, die Zulassung von KDB, wird näher eingegangen. Anhand von Messungen mit Dichtungskontroll¬systemen wird dann gezeigt, dass dieser „approach“ auch funktioniert.
Gas sensors in linear form based on the measuring principle of gas selective permeability through a membrane were developed and introduced for the detection and quantification of gas concentrations. A current field study focuses on measuring CO2 concentrations for a spatially distributed monitoring of subsurface CO2 gas storage sites in near real time. A 400 m² test site and a corresponding laboratory system were built up to characterize, validate, and optimize the sensor. A calibration routine was developed, which can be applied subsequently to underground installation. First measurement results indicate the potential of the method.
Monitoring the ingestion of microplastics is challenging and suitable detection techniques are insufficiently used. Thus, misidentifying natural for synthetic microfibres cannot be avoided. As part of a framework to monitor the ingestion of microplastics in eelpout, this short report addresses the accurate identification of microfibres. We show that, following visual inspections, putatively synthetic microfibres are indeed of natural origin, as ascertained by spectrometric analyses. Consequently, we call for an inclusion of spectroscopic techniques in standardized microplastic monitoring schemes.
The reliable characterization of subsurface contamination of spatially extended contaminated sites is a challenging task, especially with an unknown history of land use. Conventional technologies often fail due to temporal and financial constraints and thus hinder the redevelopment of abandoned areas in particular. Here we compare two site screening techniques that can be applied quickly at relatively low cost, namely Direct Push (DP)-based groundwater sampling and tree core sampling. The effectiveness of both methods is compared for a rural megasite contaminated with chlorinated hydrocarbons. Unexpected pollution hot spots could be identified using both of these methods, while tree coring even enabled the delineation of the contaminant plume flowing into an adjacent wetland inaccessible for DP units. Both methods showed a good agreement in revealing the spatial pattern of the contamination. The correlation between groundwater concentrations and equivalent concentrations in wood was linear and highly significant for trichloroethene. Correlation was less obvious for its metabolite cis-dichloroethene, but still significant. As outcome of our study we recommend tree coring and for initial screening in combination with a DP sampling to retrieve quantitative data on groundwater pollutants in order to assess the contamination situation of a non- or only partly investigated site. The subsequent placement of monitoring wells for long-term monitoring of contamination levels is recommended. A combination of methods would achieve more relevant information at comparable or possibly even lower efforts in comparison to a conventional site investigation.
This report supports the implementation of European regulations on biocidal products for the product types 7, 9 and 10. Emission of active substances from material preservatives into environmental compartments can occur due precipitation. Risk characterisations have to be based on estimations of environmental concentrations of target substances leached from material preservatives. Harmonised test procedures are required to predict environmental impact due to leaching. Seventeen treated articles, mainly paints, but also a textile, sealing tapes and sealing masses were investigated by intermittent contact to water to prove suitability of the proposed laboratory test procedure. Parameters that affect leaching of active substances were examined.
Further development of a semi-analytical model to describe laboratory leaching data revealed that the model can be improved if changes of the leachability of substances during the test are supposed and integrated. Six paints and a textile were exposed to weathering to compare results from laboratory and field experiments. Similarities between leaching processes in both test approaches were observed. Generally, emissions of active substances are considerably higher in laboratory tests than from vertically installed test specimens exposed to weathering. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. In addition, the influence of meteorological parameters on leaching processes was investigated. Factors besides the amount of driving rain were identified that effect leaching processes by complex interaction. Relations between laboratory and field data were analysed, and the applicability of the semi-analytical model was tested for field data. Guidance documents for leaching tests under laboratory and field conditions were drafted and discussed with experts on EU Level workshop 3./4. July 2014, BAM, Berlin), and are included in this Report.
Improving resource efficiency at the end-of-life stage is illustrated in this paper by the example of materials recovery from waste, here from residues out of municipal solid waste incineration (MSWI). With mechanical treatment valuable materials like ferrous and non-ferrous metals and secondary construction material can be extracted from MSWI bottom ash. The potential contribution on the resource efficiency will be discussed.
Over the past few decades, there has been an increased frequency and duration of cyanobacterial Harmful Algal Blooms (HABs) in freshwater systems globally. These can produce secondary metabolites called cyanotoxins, many of which are hepatotoxins, raising concerns about repeated exposure through ingestion of contaminated drinking water or food or through recreational activities such as bathing/swimming. An ultra-performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS) multi-toxin method has been developed and validated for freshwater cyanotoxins; microcystins-LR, -YR, -RR, -LA, -LY and -LF, nodularin, cylindrospermopsin, anatoxin-a and the marine diatom toxin domoic acid. Separation was achieved in around 9 min and dual SPE was incorporated providing detection Limits of between 0.3 and 5.6 ng/L of original sample. Intra- and inter-day precision analysis showed relative standard deviations (RSD) of 1.2–9.6% and 1.3 –12.0% respectively. The method was applied to the analysis of aquatic samples (n = 206) from six European countries. The main class detected were the hepatotoxins; microcystin-YR (n = 22), cylindrospermopsin (n = 25), microcystin-RR (n = 17), micro-cystin-LR (n = 12), microcystin-LY (n = 1), microcystin-LF (n = 1) and nodularin (n = 5). For microcystins, the levels detected ranged from 0.001 to 1.51 mg/L, with two samples showing combined levels above the guideline set by the WHO of 1 mg/L for microcystin-LR. Several samples presented with multiple Toxins indicating the potential for synergistic effects and possibly enhanced toxicity. This is the first published pan European survey of freshwater bodies for multiple biotoxins, including two identified for the first
time; cylindrospermopsin in Ireland and nodularin in Germany, presenting further incentives for improved monitoring and development of strategies to mitigate human exposure.
Background: Biocidal products can be sources of active substances in surface waters caused by weathering of treated articles. Marketing and use of biocidal products can be limited according to the European Biocidal Products Regulation if unacceptable risks to the environment are expected. Leaching of active substances from treated articles was observed in field experiments to obtain information on leaching processes and investigate the suitability of a proposed test method.
Results: Leaching under weathering conditions proceeds discontinuously and tends to decrease with duration of exposure. It mainly depends on the availability of water, but is also controlled by transport processes within the materials and stability of the observed substances. Runoff amount proved to be a suitable basis to compare results from different experiments. Concentrations of substances are higher in runoff collected from vertical surfaces compared to horizontal ones, whereas the leached amounts per surface area are higher from horizontal surfaces. Gaps in mass balances indicate that additional processes such as degradation and evaporation may be relevant to the fate of active substances in treated articles. Leached amounts of substances were considerably higher when the materials were exposed to intermittent water contact under laboratory conditions as compared to weathering of vertically exposed surfaces.
Conclusions: Experiences from the field experiments were used to define parameters of a procedure that is now provided to fulfil requirements of the Biocidal Products Regulation. The experiments confirmed that the amount of water which is in contact with exposed surfaces is the crucial parameter determining leaching of substances.
In order to estimating the amount and kind of emissions from polymeric sporting tracks a laboratory test was developed in BAM that combines artificial weathering and subsequent batch and column tests [1, 2, 3]. The goal consisted in nvestigating a possible change of emissions into soil and groundwater of a new sporting ground as a function of ageing and egradation of the system. At various stages of the weathering, the samples were removed and subjected to especially designed column extraction tests for the solid samples. Both these extracts and the accumulated rainwater run-off of the weathering device were subjected to analytical tests of their ingredients. The overall aim of the test consisted in developing ontrollable, reproducible, and standardisable conditions and methods of investigation that would allow an estimation of the emissions in the course of outdoor application of about five years.
Arsenolipids (AsL) of the type arsenic-containing fatty acids (AsFA) and hydrocarbons (AsHC) are natural organoarsenic compounds present in high abundance in seafood. Since little is known about their toxicity, there is a significant concern about their health risk. Here we report the synthesis of two new AsL and their identification in fish by liquid chromatography (LC) coupled simultaneously to inductively coupled plasma mass spectrometry (ICP-MS) and to high resolution mass spectrometry (HR-MS). The molecular structure was elucidated on the basis of their exact mass and their product ion mass spectra. One of the synthesized AsL has been already identified in fish samples, meanwhile, the other arsenolipid is reported here as a natural product in fish.
Arsenic and mercury are frequent contaminants in the environment and care must be taken to limit their entrance into the food chain. The toxicity of both elements strongly depends upon their speciation. Total amounts of As and Hg as well as their species were analyzed in muscle and liver of 26 fishes of seven freshwater fish species caught in the River Elbe. The median concentrations of As were 162 mg kg-1 w.w. in liver and 92 mg kg-1 w.w. in muscle. The median concentrations of total Hg were 241 mg kg-1 w.w. in liver and 256 mg kg-1 w.w. in muscle. While this level of Hg contamination of the freshwater fish in the River Elbe is significantly lower than 20 years ago, it exceeds the recommended environmental Quality standard of 20 mg Hg kg-1 w.w. by a factor of 5e50. However, the European maximum level of 500 mg Hg kg-1 for fish for human consumption is rarely exceeded. Arsenic-containing fatty acids and hydrocarbons were determined and partially identified in methanolic extracts of the fish by HPLC coupled in parallel to ICP-MS (element specific detection) and ESI-Q-TOF-MS (molecular structure detection). While arsenobetaine was the dominant As species in the fish, six arsenolipids were detected and identified in the extracts of liver tissue in common bream (Abramis brama), die (Leuciscus idus), asp (Aspius aspius) and northern pike (Esox lucius). Four arsenic-containing fatty acids (AsFA) and two arsenic-containing hydrocarbons (AsHC) are reported in freshwater fish for the first time. With respect to mercury the more toxic MeHgþ was the Major species in muscle tissue (>90% of total Hg) while in liver Hg2þ and MeHgþ were of equal importance. The results Show the high relevance of element speciation in addition to the determination of total element concentrations to correctly assess the burden of these two elements in fish.
Two iron-based molten salts comprising an imidazolium and Schiff base were evaluated as catalysts for removal of carbamazepine (CBZ) from water. The catalysts were fully characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), nuclear magnetic resonance spectroscopy (NMR), electrospray ionisation–mass spectrometry (ESI–MS), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption–desorption isotherms (BET). Additionally, the formation of photo-sensitized oxygen was investigated by spin-trapping using electron spin resonance (ESR). The catalytic activity in heterogeneous oxidation of the micropollutant (CBZ) was also evaluated. The effects of catalyst loading, pH, H2O2 dosage and UV light on the oxidation of the selected compound were investigated. After 15 min of UVA irradiation in the presence of 200 μM H2O2, CBZ was completely removed over both catalysts.
Die VDI-Richtlinie 3925 entstand aus Diskussionen und Fragestellungen, die sich aus der Anwendung unterschiedlichster Methoden zur Bewertung verschiedener
Verfahrenskonzepten aus dem Bereich der Abfallbehandlung ergeben haben. Je nach nachdem, wo der Focus der vorzunehmenden Bewertung liegt, wird sich die Methodik an diese Ziele anpassen oder - falls es die entsprechende Methodik noch nicht geben sollte - sich die Fragestellung anpassen müssen.
Towards the standardization of biochar analysis: the COST action TD1107 interlaboratory comparison
(2016)
Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical–chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.
The need for technological progress in bio-diagnostic assays of high complexity requires both fundamental research and constructing efforts on nano-scaled assay recognition elements that can provide unique selectivity and design-enhanced sensitivity features. Nanoparticle induced sensitivity enhancement and its application related to multiplexed capability Surface-Enhanced InfraRed Absorption (SEIRA) assay formats are well suitable for these purposes. The potential of diverse fluorophore–antibody conjugates, being chemisorbed onto low-cost gold nanoparticulate SEIRA substrates, has been explored with respect to their spectral discriminability. These novel biolabels deliver molecular SEIRA fingerprints that have been successfully analyzed by both uni- and multivariate analyzing tools, to discriminate their multiplexing capabilities. We show that this robust spectral encoding via SEIRA fingerprints opens up new opportunities for a fast, reliable and multiplexed high-end screening in biodiagnostics.
Fluorescence lamps contain considerable amounts of rare earth elements (REE). Several recycling procedures for REE recovery from spent lamps have been established. However, despite their economic importance, the respective recycling is scarce so far, with an REE recovery rate of less than 1%. A reliable analysis of REE and other relevant metals like Yttrium is crucial for a thorough and complete recovery process. This applies both to the solid matter and aqueous phase, since most of the recycling processes include wet-chemical steps. We tested seven different reagent mixtures for microwave-assisted digestion of fluorescent lamp shredder, including hydrofluoric acid, perchloric acid, and hydrogen peroxide. We determined the concentrations of 25 of the most relevant rare earth and other trace elements (Al, P, Ti, V, Cr, Fe, Ni, Cu, Ga, Ge, As, Y, Ag, Cd, Sn, Sb, La, Ce, Eu, Gd, Tb, W, Au, Hg, and Pb) 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).
Anticancer drugs (ACDs) exhibit high biological activity, they are cytotoxic, genotoxic, and are constantly released into the environment as a result of incomplete metabolism. Consequently they pose a serious threat to the environment and human health due to their carcinogenic,mutagenic and/or reproductive toxicity properties. Knowledge of their bioavailability, including their sorption to soils and their impact on the soil–groundwater pathway, is crucial for their risk assessment. Laboratory batch and column leaching tests are important tools for determining the release potential of contaminants from soil or waste material. Batch and column tests were carried out with soils differing in physicochemical properties, each spiked with cyclophosphamide (CK) or ifosfamide (IF). Moreover, due to the fact that environmental pollutants may occur as coexisting compounds in the soil themobility evaluation for ACDs in the mixture with metoprolol (MET; β-blocker) as a co-contaminant was performed. In order to assess appropriateness, the batch and column tests were compared. The release depended on the properties of both the soil and the presence of co-contaminants. The faster release was observed for coarse-grained soil with the smallest organic matter content (MS soil: 90% decrease in concentration until liquid-to-solid ratio (L/S) of 0.3 L kg−1 for all tests' layout) than for loamy sand (LS soil: 90% decrease in concentration until ratio L/S of 0.75 L kg−1). ACDs are highly mobile in soil systems. Furthermore, the decrease of mobility of ifosfamide was observed with the presence of a co-contaminant (metoprolol) in both of the soils (in MS soil a decrease of 29%; in LS soil a decrease of 26%). The mobility of cyclophosphamide does not depend on the presence of a contaminant for MS soil, but also exhibits a decrease of 21% in LS soil.
Within a class of agrochemical residues, pesticides are significant concern due to their various adverse effects on people, animals and the environmental systems. Once they entered to food or to the environment, the parent compound is transformed to metabolites which have different toxicity profiles. Activities like food cooking and waste water treatment (WWT) may lead to produce more toxic metabolites than the parent substances.
Online coupling of electrochemistry with liquid chromatography mass spectrometry (EC-HPLC-MS) is one of the most promising and powerful techniques for metabolite studies which exploited widely for pharmaceuticals so far [1]. However, data on the application of EC-HPLC-MS to simulate environmental transformation products, the fate of contaminants and their metabolic pathways are rare. The oxidation of analyte of interest on the EC, separate the metabolites on HPLC and identifying them by MS gives enormous advantages to identify the contaminants transformation products [2]. Thus, applying this technique (EC-MS, EC-HPLC-MS, and HPLC-EC-MS) for transformation products of pesticide residues is urgently needed.
The main interest of this study will be investigating the electrochemical oxidative degradation products, simulating to in-vitro metabolites and transformation processes of selected pesticides in food and environmental samples. The parent pesticides’, like carbamates and abamectin, oxidation by EC, product metabolites identification and their fates will be discussed using electrochemistry coupled to HPLC-MS techniques.
Task allocation in social insect colonies is generally organised into an age-related division of labour, termed the temporal polyethism schedule, which may in part have evolved to reduce infection of the colony's brood by pests and pathogens. The temporal polyethism schedule is sensitive to colony perturbations that may lead to adaptive changes in task allocation, maintaining colony homeostasis. Though social insects can be infected by a range of parasites, little is known of how these parasites impact within-colony behaviour and the temporal polyethism schedule. We use honey bees (Apis mellifera) experimentally infected by two of their emerging pathogens, Deformed wing virus (DWV), which is relatively understudied concerning its behavioural impact on its host, and the exotic microsporidian Nosema ceranae. We examined parasite effects on host temporal polyethism and patterns of activity within the colony. We found that pathogens accelerated the temporal polyethism schedule, but without reducing host behavioural repertoire. Infected hosts exhibited increased hyperactivity, allocating more time to self-grooming and foraging-related tasks. The strength of behavioural alterations we observed was found to be pathogen specific; behavioural modifications were more pronounced in virus-treated hosts versus N. ceranae-treated hosts, with potential benefits for the colony in terms of reducing within-colony transmission. Investigating the effects of multiple pathogens on behavioural patterns of social insects could play a crucial role in understanding pathogen spread within a colony and their effects on colony social organisation.
Phosphorus (P) for fertilizer use can be recovered from sewage sludge ash (SSA). To enhance the bioavailability of P and reduce the heavy metal content of SSA, it can be treated thermochemically with Na2CO3 or Na2SO4 at 950 °C in a rotary kiln using dry sewage sludge or lignite as reducing agent. These processes were investigated by thermogravimetry/differential thermal analysis coupled with gas analysis. Reducing conditions in this experimental setup were provided by 2 % hydrogen in the Ar carrier gas. During SSA + Na2CO3 treatment CO2, CO and water were detected in the off-gas. During SSA + Na2SO4 treatment SO2, some CO2 and water were detected. Heavy metal removal was more efficient for SSA + Na2CO3 compared to the sulfate variant. A SSA + Na2SO4 + lignite variant which also formed CO shifted the heavy metal removal to the results obtained with Na2CO3 which was obviously due to the additional reduction potential. However, Zn evaporation was not achieved with the Na2SO4 variants which were most probably due to immobilization as ZnS.
Sewage sludge incineration is extensively practiced in some European countries such as the Netherlands, Switzerland, Austria and Germany. A survey of German sewage sludge ash showed that the recovery potential is high, approx. 19,000 t of phosphorus per year. However, the survey also discovered that the bioavailability of phosphorus in the sewage sludge ash is poor and that more than half of the ashes cannot be used as fertilizers due to high heavy metal content. A new thermochemical process for sewage sludge ash treatment was developed that transforms the ash into marketable fertilizer products. Sewage sludge ash was thermochemically treated with sodium and potassium additives under reducing conditions, whereby the phosphate-bearing mineral phases were transformed into plant available phosphates. High P-bioavailability was achieved with a molar Na/P ratio > 1.75 in the starting materials. Sodium sulfate, carbonate and hydroxide performed comparably as additives for this calcination process. Potassium carbonate and -hydroxide have to be added in a molar K/P ratio > 2.5 to achieve comparable P-solubility. The findings of the laboratory scale investigations were confirmed by an industrial demonstration trial for an ash treatment with sodium sulfate. Simultaneously, the volatile transition metal arsenic (61% removal) as well as volatile heavy metals such as cadmium (80%), mercury (68%), lead (39%) and zinc (9%) were removed via the off-gas treatment system. The product of the demonstration trial is characterized by high bioavailability and a toxic trace element mass fraction below the limit values of the German fertilizer ordinance, thus fulfilling the quality parameters for a P-fertilizer.
In Germany, a quantity of more than 10 million metric tons of masonry rubble is generated per year. With regard to a sustainable closed substance cycle waste management, these rest masses have to be recovered if possible. The end-of-life (EOL) phase of masonry includes the planning steps of demolition, processing and application. The choice of the most sustainable solution raises questions regarding material technology, plant engineering, economic efficiency and ecological issues. For this purpose, a methodological concept for a holistic assessment of the EOL phase of masonry is developed within the scope of a doctoral thesis. For the assessment the Cost-Effectiveness Analysis (CEA) is adapted. The assessment concept enables a holistic comparison of different EOL scenarios for masonry while integrating all planning steps. It combines Material Flow Analysis (MFA), Life Cycle Analysis (LCA), Life Cycle Working Environment (LCWE), economic evaluation methods and material testing. In future, various scenarios can be evaluated with regard to the goals of the European and German waste management industry.
Alkaline reactions of paper sludge combustion ash at low temperature (60 °C) were performed using a calcite-rich paper ash (PA 1) and a gehlenite-rich ash (PA 2). Strong alkaline conditions (8, 12, 16 M NaOH) were revealed at reaction times of 1–4 h and 12–24 h. Reactions were performed with pure ashes and in the presence of NaAlO2. The products were characterized by XRD, FTIR, SEM/EDX, gravimetry and chemical analysis. The conversion was found to proceed mainly in the period between 1 and 4 h. Portlandite and hydrogarnet were observed from PA 1 in 8 M NaOH. Onset of formation of Ca4Al2O6CO·311H2O beside Ca(OH)2 could be analyzed after reaction of PA 1 in 12 M and 16 M NaOH. Addition of NaAlO2 favored crystallization of hydrogarnet and Ca4-Al2O6CO·311H2O. For PA 2 gehlenite remained stable, but a high portlandite fraction was observed. Addition of NaAlO2 yielded hydrogarnet beside gehlenite in 8 M NaOH. Higher alkalinities favored crystallization of Ca4Al2O6-CO·311H2O and onset of dissolution of gehlenite. Finally transformation of Ca4Al2O6CO·311H2O into sodium aluminum silicate hydrate was observed. All results were discussed with regard to heavy metal distribution of the initial PA between the alkaline digestion solution and the products. In conclusion suitable applications of the products were proposed.
Die Studie gibt einen Überblick über den Umfang und die Struktur der Gefahrgutbeförderung auf Binnenschiffen und stellt die maßgeblichen sicherheitstechnischen Vorschriften dar. Aus dem Unfallgeschehen läßt sich entnehmen, daß in West-Deutschland jährlich ca. 1200 Binnenschiffsunfälle mit größenordnungsmäßig insgesamt 100 bis 300 m³ Ladungsaustritt verbunden sind, wozu fast ausschließlich Mineralölprodukte gehören, und zumeist ein oder zwei Unfälle den größten Beitrag liefern. Während nach Unfällen häufig mit Erfolg Ölsperren zur Begrenzung von Gewässerverunreinigungen eingesetzt werden können, führen ungeklärte Entsorgungsprobleme zu wesentlich kritischer einzuschätzenden, verdeckten Verunreinigungen der Gewässer. Insbesondere die Entsorgung von Ladungsresten bedarf in technischer, administrativer und wirtschaftlicher Hinsicht einer zufriedenstellenden Klärung wie sie z. B. bei der Bilgenwasserentsorgung existiert.
Determining a pore structure’s mechanical and chemical data on lime rendering exposed
outdoors and including masonry in the laboratory, with regard to their behaviour on moisture
transport and weathering was the objective. In search of clues for a dose-response relation -
i.e. upon a connection between the emission rate of SO2 and NOx on one hand and the degree
of damage to mainly plaster having a lime component on the other - it has been of interest to
what extent their structural characteristics including pore space are modified and so
consequently also physico-technical properties and chemical composition. For determining
corresponding criteria, a widely diversified spectrum of test methods such as to obtain data
concerning porosity and moisture transport, mechanical behaviour, and chemistry as well is
available. A description of the manufacture of plate-shaped rendering specimens with lime
putty, industrially hydrated lime and dolomitic hydrate (the last two also having a cement
admixture) and also hydraulic lime as binding agents is included. First deposition velocity and
absorption rate for SO2 were determined in laboratory tests on these materials in dry and
moist states. After their exposure on outdoor racks at six locations in the Berlin region with
differing SO2 atmospheric contents over at least 5 years, the samples of course show timedependent
modifications of chemical and physical qualities which are especially reflected in
the form of profiles of structure, strength and concentration, e.g. for sulphate. Local climatic
differences, however, partly exert a greater influence on material than emissions. Similar
investigations were performed on samples of comparable composition exposed 4 and 17
years. But the real surprise is furnished by the renderings’ behaviour depending upon
orientation and upon height at a building. Since weathering behaviour and moisture transport
(absorption, storage, release) are directly interdependent, further criteria are necessary for a
critical assessment of a plasters’ pore structure. Starting from sands, plasters were
characterized. The structural parameters were lastly influenced by the respective contents of
sand, binder and mixing water. These results and those gained from bricks naturally find their
expression in masonry sections manufactured there from, and above all in their capillary and
evaporative behaviours, and also when applying different test liquids. Summary and cited
literature is given at the end of this report.
Die im In- und Ausland vorliegenden Forschungsarbeiten zur Kostenabschätzung der immissionsbedingten Materialschäden beruhen auf zwei ökonomischen Bewertungsverfahren. Bewertungsgrundlage des einen Verfahrens sind die in Labor- und Freibewitterungsversuchen ermittelten physikalisch-chemischen Dosis-Wirkungs-Beziehungen zwischen dem Schadstoffgehalt der Luft und den schadensanfälligen Materialien. Die andere Methode geht von den Unterschieden im Instandsetzungverhalten in Abhängigkeit vom Standort (Industrie-, Stadt- und Landatmosphäre) der Sachgüter aus.
Die ökonomische Bewertung der immissionsbedingten Materialschäden der Sachgütergruppen Freileitungsmaste, Brücken der Bundesautobahnen, Eisenbahnbrücken und -fahrleitungsmaste, fernmeldetechnische Einrichtungen der Deutschen Bundespost, Industrieanlagen, Wohngebäude und Denkmäler basiert auf sogenannten „Stock-at-risk“-Informationen, Dosis-Wirkungs-Funktionen der der Atmosphäre ausgesetzten Werkstoffe und auf in der Praxis vorliegenden Erfahrungswerten über Zeitintervalle der Erneuerung der Korrosionsschutzsysteme und Bauteile. In jenen Fällen, in denen der immissionsbedingte Anteil am Gesamtschaden noch nicht eindeutig nachgewiesen werden konnte, werden die Forschungslücken aufgezeigt bzw. Modellrechnungen durchgeführt.
Mit der überarbeiteten Version der Vergabegrundlagen des Umweltzeichens Blauer Engel für Bürogeräte mit Druckfunktion (RAL-UZ 171:2012) wurde für die Partikelemission ein Prüfverfahren und ein Prüfwert eingeführt. Dies ergänzt die zahlreichen anderen Kriterien, die bereits Voraussetzungen für die Vergabe des Blauen Engels an Bürogeräte mit Druckfunktion waren. Die Anwendung des Prüfwertes für Partikelemissionen wurde von der Jury Umweltzeichen in 2012 zunächst nur für Geräte unterhalb 250 l Volumen - sogenannte Tischgeräte - beschlossen. Für größere Geräte (> 250 l, sogenannte Standgeräte) wurde eine Dokumentation des Messergebnisses im Rahmen des Prüfberichtes festgelegt. Ein Grund für diese Unterscheidung war die Tatsache, dass zu diesem Zeitpunkt für die Standgeräte keine für eine sinnvolle Festlegung eines Prüfwerts ausreichende Zahl an Messwerten und keine Erfahrungen aus entsprechenden Emissionsprüfungen vorlagen. Notwendig zur beabsichtigten Festlegung des Prüfwerts für die Partikelemission aus großen Bürogeräten war deshalb die systematische Erfassung und Bewertung der durch die anerkannten Prüfinstitute nach Inkrafttreten der RAL-UZ 171 ermittelten Ergebnisse. Dies wurde in diesem Forschungsprojekt durchgeführt. Das Forschungsprojekt befasste sich des Weiteren mit der Ermittlung und Beurteilung der Qualität der Partikelemissionsprüfungen auf Basis der zur Verfügung stehenden Prüfberichte in beiden Größenkategorien. Im Ergebnis stellte sich heraus, dass die Qualität der Prüfungen der Partikelemission insgesamt mit einer Fehlerquote von 3 % ungültiger Prüfungen sehr gut war. Ein weiteres Ergebnis ist, dass keine prüfmethodischen oder qualitätsrelevanten Gründe gegen die Anwendung des bestehenden Prüfwerts auf große Bürogeräte sprechen.