4 Material und Umwelt
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Paper des Monats
- ja (19)
Im Januar 2018 wurde die DIN EN 16516 „Bauprodukte: Bewertung der Freisetzung gefährlicher Stoffe – Bestimmung von Emissionen in die Innenraumluft“ als harmonisierte europäische Prüfnorm veröffentlicht. Für die Etablierung der DIN EN 16516 als neue Referenznorm wurden verschiedene Emissionsprüfungen mit dem Ziel durchgeführt, ein neues Prüfverfahren für Formaldehydemissionen aus Holzwerkstoffen zu erarbeiten. Das übergeordnete Ziel ist die Minimierung des Risikos von Überschreitungen des Innenraumrichtwertes für Formaldehyd. Die Untersuchungen ergaben teilweise hohe Formaldehydemissionen, insbesondere bei höheren Beladungsfaktoren und Temperaturen, sowie bei niedrigen Luftwechselraten. Eine getestete Spanplatte hätte aufgrund ihrer hohen Formaldehydemission nicht auf den deutschen Markt gebracht werden dürfen. Durch vergleichende Untersuchungen konnte ein Umrechnungsfaktor in Höhe von 2,0 für die Umrechnung von Prüfwerten nach DIN EN 717-1 zu DIN EN 16516 abgeleitet werden.
Jährlich entstehen in Brasilien ca. 2 bis 10 Millionen Tonnen Aschen aus der Verbrennung von Zuckerrohrbagasse. Die Aschen enthalten schwankende Zusammensetzungen an mineralischen Nährelementen und könnten daher zu Düngezwecken verwendet werden.
Allerdings ist (i) die Nährstoffverfügbarkeit gering, (ii), die entsprechende Nährstoffzusammensetzung nicht optimal für die Nutzung der Aschen als Düngemittel für die Hauptanbaukulturen in Brasilien und (iii) weisen die Aschen aufgrund häufig schlechter Verbrennungsqualitäten hohe organische Kohlenstoffgehalte auf. Im Rahmen des Forschungsprojekts ASHES („Rückführung von Nährstoffen aus Aschen von thermochemischen Prozessen mit Bagasse bzw. Zuckerrohrstroh“), arbeiten 7 deutsche und 4 brasilianische Partner an der Optimierung der thermochemischen Verwertung von Rückständen aus der Zuckerproduktion in Brasilien, inklusive der Formulierung von optimierten Düngemischungen auf Basis der generierten Aschen. In dieser Veröffentlichung wird die Verarbeitung dieser optimierten Mischungen zu Pellets und Granulaten unter Verwendung verfügbarer regionaler Reststoffe wie Filterkuchen (Vinasse-Presskuchen) sowie Hühnertrockenkot beschrieben. Zur Untersuchung der Handlingeigenschaften wurden die produzierten Pellets und Granulate hinsichtlich ihrer mechanischen Stabilität und des Wasseraufnahmevermögens untersucht. Dafür wurden geeignete Prüfverfahren angepasst und entsprechende Versuche durchgeführt.
A wide range of methods are used to estimate the plant-availability of soil phosphorus (P). Published research has shown that the diffusive gradients in thin films (DGT) technique has a superior correlation to plant-available P in soils compared to standard chemical extraction tests. In order to identify the plantavailable soil P species, we combined DGT with infrared and P K- and L2,3-edge X-ray adsorption near edge structure (XANES) spectroscopy. This was achieved by spectroscopically investigating the dried binding layer of DGT devices after soil deployment. All three spectroscopic methods were able to distinguish between different kinds of phosphates (poly-, trimeta-, pyro- and orthophosphate) on the DGT binding layer. However, infrared spectroscopy was most sensitive to distinguish between different types of adsorbed inorganic and organic phosphates. Furthermore, intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed.
Copper-based fungicides are routinely used for wood and plant protection, which can lead to an enrichment of copper-tolerant microbial communities in soil. To investigate the effect of such wood preservatives on the soil fungal and bacterial community compositions, five different vineyard and fruit-growing soil environments were evaluated using incubation studies over time. Pine sapwood specimens were impregnated with either water or different biocide treatment solutions containing a mixture of copper, triazoles, and quaternary ammonium compounds (CuTriQAC), a mixture of triazoles and quaternary ammonium compounds (TriQAC), or copper alone (Cu). Specimens were incubated in soil from each sample site for 8, 16, 24, and 32 weeks. The effects of preservative treatment on the modulus of elasticity (MOE) of the wood specimens and on the soil fungal as well as bacterial community composition at the soil-wood interface were assessed by quantitative PCR and amplicon sequencing of the fungal internal transcribed spacer (ITS) region and bacterial 16S rRNA gene. Specimens impregnated with CuTriQAC and Cu showed decreased MOE and reduced fungal and bacterial copy numbers over time compared to those impregnated with water and TriQAC. Fungal but not bacterial community composition was significantly affected by wood preservative treatment. The relative abundance of members of the family Trichocomaceae compared to other genera increased in the presence of the Cu and CuTriQAC treatments at three sites, suggesting these to be Cu-tolerant fungi. In conclusion, the copper-containing treatments resulted in marginally increased MOE, lowered microbial gene copy numbers compared to those in the TriQAC and water treatments, and thus enhanced wood protection against soil microbial wood degradation
A non-invasive methodological approach has been carried out to identify the pigments and classify the binding media of the reverse painting on glass Kreuzabnahme (1914/15) by Carlo Mense.
Mense was a member of the group Rhenish Expressionists around August Macke and got interested in the technique of painting on the reverse side of a glass panel. The studied painting indicates a remarkably painted reverse and front side, which creates a unique visual appearance of the glass. The applied noninvasive, spectroscopic approach includes X-ray fluorescence, VIS spectroscopy, Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy. The measurements revealed inorganic Pigments mixed with drying oil as binder. Together with common pigments, such as lead white, barium sulphate, bone black, cinnabar, chrome yellow, ochre, and viridian, an unusual additional material was found, Strontium white.
This work presents a technical investigation of two Chinese reverse glass paintings from the late 19th and early 20th centuries. A multi-analytical, non-invasive approach (X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Raman spectroscopy) was used to identify the pigments and classify the binding media. The results reveal a combined use of traditional Chinese and imported European materials. Several pigments like cinnabar, lead white, orpiment, carbon black and copper-arsenic green (probably emerald green) were found in both paintings; red lead, artificial ultramarine blue, Prussian blue and ochre appear in at least one of the paintings. The proof of limewash (calcite and small amounts of portlandite) as a backing layer in Yingying and Hongniang indicates that clamshell white was also used for reverse glass paintings. Drying oil was classified as a binding media in most areas of both paintings. However, the orange background of The Archer yielded prominent bands of both proteinaceous and fatty binder.
Treatment and reusing of hazardous wastes have become significant issues of modern societies. Blast furnace sludge (BFS) and electric arc furnace dust (EAFD) are such typical wastes, because they usually contain high amounts of undesirable elements such as zinc (Zn) and lead (Pb).
These elements can cause operational problems in reusing of BFS and EAFD. In this study, the Ferro Duo GmbH and the Federal Institute for Materials Research and Testing have investigated a novel approach for eliminating and/or recovering Zn and Pb from both wastes. Applied was a selective chlorination and volatilization of Zn and Pb as chlorides at temperatures between 500 °C and 1100 °C. Both product obtained, Zn and Pb in the form of ZnCl2 and PbCl2 and the purified solid mineral compound are attractive materials for further use. Hydrochloric acid and iron(II) chloride were used as chlorination agents. Exceptionally high Zn and Pb removal efficiencies of >99.5 % could be achieved with both chlorination agents, whereby iron(II) chloride exhibited better performance.
Test methods for efficacy assessment of antimicrobial coatings are not modelled on a hospital environment, and instead use high humidity (>90%) high temperature (37 ◦C), and no airflow. Therefore, an inoculum will not dry, resulting in an antimicrobial surface exhibiting prolonged antimicrobial activity, as moisture is critical to activity. Liquids will dry quicker in a hospital ward, resulting in a reduced antimicrobial efficacy compared to the existing test, rendering the test results artificially favourable to the antimicrobial claim of the product. This study aimed to assess how hospital room environmental conditions can affect the drying time of an inoculum, and to use this data to inform test parameters for antimicrobial efficacy testing based on the hospital ward. The drying time of different droplet sizes, in a range of environmental conditions likely found in a hospital ward, were recorded (n = 630), and used to create a model to inform users of the experimental conditions required to provide a drying time similar to what can be expected in the hospital
ward. Drying time data demonstrated significant (p < 0.05) variance when humidity, temperature, and airflow were assessed. A mathematical model was created to select environmental conditions for in vitro antimicrobial efficacy testing. Drying time in different environmental conditions demonstrates that experimental set-ups affect the amount of time an inoculum stays wet, which in turn may affect the efficacy of an antimicrobial surface. This should be an important consideration for hospitals and other potential users, whilst future tests predict efficacy in the intended end-use environment.
Column leaching tests are frequently used and accepted for investigation of release of hazardous substances from solid materials. Independent of differences due to the field of application or national regulations, column tests assume that local equilibrium is established in the experiment which facilitates transfer of results to field conditions. In the process of harmonization and standardization within Europe the question on the influence of flow rate and grain size distribution on the local equilibrium was raised. Thus, a set of experiments using two different masonry materials with varying grain size distribution and flow rate were conducted including stop/flow experiments. Results are compared to a numerical model which takes intraparticle pore diffusion-controlled release of Mo and V into the percolating water into account. Due to the relatively high intraparticle porosity of the materials (24–29%) data and model indicate that initially equilibrium-state conditions prevail followed by rapidly decreasing concentrations. The model fits data for Mo and V reasonably well; however, after the initial decline of concentrations (at L/S > 2) extended tailing is observed especially of elements occurring as oxides, which is not captured by the model.
Wie Länder mit ihren Abfällen umgehen, hängt nicht nur von der Wirtschaftskraft eines Landes ab. Selbst in einem reichen Land wie Australien werden unbehandelte Abfälle einfach deponiert. Im Rahmen der Travelling Conference, einer vom Bundesministerium für Bildung und Forschung (BMBF) geförderten Vortragsreihe, besuchten Fachleute die Länder Südkorea, Vietnam und Australien, um mit Experten vor Ort Fragestellungen aus der Abfallwirtschaft zu diskutieren. Zu den Schwerpunktthemen zählte die Steigerung der Ressourceneffizienz im Spannungsfeld von ökonomischen und umweltpolitischen Interessen. Eine Frage war beispielsweise die Bewertung der Umweltverträglichkeit von mineralischen Abfällen, wenn diese als Ersatzbaustoffe eingesetzt werden. In diesem Beitrag werden Ähnlichkeiten und Unterschiede bei der Entsorgung von Siedlungsabfällen, beim Recycling und bei der Bewertung der Umweltverträglichkeit der Wiederverwertung von Abfällen in den drei besuchten Ländern im Vergleich zu Deutschland aufgezeigt. Dabei ist man sich in Deutschland und den drei besuchten Ländern einig, dass die Abfallbeseitigung auf Deponien ohne Rückgewinnung von Ressourcen oder Energie die schlechteste Abfallentsorgungsoption ist. Einigkeit besteht auch darin, dass die Ziele einer nachhaltigen Abfallwirtschaft der Schutz der menschlichen Gesundheit und der Umwelt sowie die Schonung von Ressourcen sind. In allen drei Ländern werden große Mengen an mineralischen Abfällen erzeugt, die bei Nachweis der Umweltverträglichkeit einen Teil von natürlichem Sand und Kies für die Bauindustrie ersetzen könnten. Ähnlich wie in Deutschland werden recycelte Abfälle im Tiefbau jedoch nur in geringem Maße eingesetzt. Gründe dafür sind fehlende Behandlungsanlagen für mineralische Abfälle und Bedenken im Hinblick auf die Umweltverträglichkeit.
Normativ ist der Holzschutz in Deutschland durch die DIN 68800-Reihe geregelt. Die Normungsarbeit in CEN/TC 38 bildet dafür den Rahmen, der national angepasst und fachspezifisch erweitert wurde. Zusammen mit dem Kommentar ergeben beide ein in Europa einzigartiges Regelkompendium im Holzschutz. In Zukunft wird die Regelsetzung noch stärker durch internationale Zusammenarbeit bestimmt sein. Der interkontinentalen Marktöffnung sollten Verständigungen auf gemeinsame Qualitätsstandards vorausgehen.
Long Term Temperature and Humidity Evolution Forecast in Near Field of Nuclear Waste Container
(2018)
The paper aims to simulate the corrosion environment of nuclear waste containers at different geological disposal periods to obtain temperature and humidity information at the interface between the container and the surrounding environment. The simulated data and calculation results of long term temperature evolution at the surface of nuclear waste (HLW) containers from some typical nuclear countries about the safety disposition were reviewed. Combining different burial patterns, this paper speculated the long term temperature evolution rule for China. According to the study about saturation variation of buffer/backfill material at home and abroad, the humidity evolution of bentonite at the surface of HLW containers was specu- lated. The study showed that the temperature of the container surface increased rapidly at the beginning, and gradually decreased after the climax. For safety reasons, the maximum temperature was designed below 100°C. The saturation of bentonite was af- fected by the mutual influences of the heat released by nuclear waste decay and the infiltration of groundwater. It was dominated by the released heat in the early stage, and later was influenced greatly by the infiltration of groundwater. It is generally believed that the water content at the surface of the container will increase obviously in about 3 years, and will be saturated in about 10 years. The prediction of long-term temperature and humidity evolution will lay a foundation for study of corrosion evolution of nuclear waste containers in China.
Surface environment changes of nuclear waste container, mainly including oxygen contents, buffer pore water components and pH under the conditions of “borehole” type and “In-floor” type with bentonite buffer/backfill and concrete buffer were summarized. This summarization provides a basic corrosion environment reference for the corrosion evolution re- search of high-level radioactive waste disposal repository in our country.
ABSTRACT: A collection of thioimidazolium salts were synthesized and used as a new class of nonvolatile alkylating agents. Their nonvolatility prevents exposure during use or handling and are thus drastically safer than conventional alkylating agents. We discovered that thioimidazolium Iodide salts cannot release volatile compounds in the solid state, but instead only decompose when molten. Since decomposition proceeds via alkyl iodide elimination, SN2 of iodide on the thioimidazolium cation is constrained in the solid state, and instead can occur only upon melting when ions are mobile. By smart design of these alkylators, the melting point and thus the decomposition temperature of these salts can be increased from 106 to 169 °C and release negligible volatile organic compounds prior to melting. Thioimidazolium-bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids act as a completely nonvolatile and air-stable TFSI-based alkylating agent and can be used for high-throughput Synthesis of TFSI ionic liquids without solvent. Alkyl groups from methyl to dodecyl can be transferred to a nucleophile and the product purified by sublimation of the thione byproduct, which can then be recycled. We also found that thioimidazolium salts with a dodecyl chain are bactericidal, yet can hydrolyze in water to form benign neutral products, and thus wont accumulate in the environment. These results demonstrate that thioimidazolium salts are a designable platform for the pursuit of safer and more environmentally friendly alkylating and antiseptic agents.
Microbial activity and functioning in soils are strongly limited by carbon (C) availability, of which a great proportion is released by living roots. Rhizodeposition and especially root exudates stimulate microbial activity and growth, and may shift the stoichiometric balance between C, N, and P. Thereby, exudates heighten microbial nutrient demand and acquisition of N and P from organic matter, leading to an increase in enzyme production. Aim of this study was to determine environmental controls of extracellular enzyme production, and hence on potential enzyme activities (Vmax) and substrate affinities (Km). To determine the controlling factors, we worked on four spatial scales from the microscale (i.e. rhizosphere) through the mesoscale (i.e. soil depth) and landscape scale (relief positions), and finally to the continental scale (1200 km transect within the Coastal Cordillera of Chile). Kinetics of seven hydrolyzing enzymes of the C, N, and P cycles (cellobiohydrolase, β‑glucosidase, β‑xylosidase, β‑N‑acetylglucosaminidase, leucine‑aminopeptidase, tyrosine‑aminopeptidase, and acid phosphatase) were related to soil texture, C and N contents, pH, and soil moisture via redundancy analysis (RDA). Potential activities of C, N, and P acquiring enzymes increased up to 7-times on the continental scale with rising humidity of sites and C and N contents, while substrate affinities simultaneously declined. On the landscape scale, neither Vmax nor Km of any enzyme differed between north and south slopes. From top- to subsoil (down to 120 cm depth) potential activities decreased (strongest of aminopeptidases under humid temperate conditions with up to 90%). Substrate affinities, however, increased with soil depth only for N and P acquiring enzymes. Affinities of cellobiohydrolase and β‑xylosidase, on the contrary, were 1.5- to 3-times higher in top- than in subsoil. Potential activities of N and P acquiring enzymes and β‑glucosidase increased form bulk to roots. Simultaneously, substrate affinities of N and P acquiring enzymes declined, whereas affinities of β‑glucosidase increased. These trends of activities and affinities in the rhizosphere were significant only for acid phosphatase. The RDA displayed a strong relation of potential activities of C and P acquiring enzymes and β‑N‑acetylglucosaminidase to C and N contents in soil as well as to the silt and clay contents. Aminopeptidase activity was mainly dependent on soil moisture and pH. We conclude that substrate availability for microorganisms mainly determined enzyme activity patterns on the continental scale by the humidity gradient. Patterns on the meso- and microscale are primarily controlled by nutrient limitation, which is induced by a shift of the stoichiometric balance due to input of easily available C by roots in the rhizosphere.
In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is −0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (−2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (−0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.
In Denmark, increasing amounts of woody biomass are being used for the production of renewable energy, resulting in more wood ashes being generated. While these materials have been mainly landfilled, wood ashes may also be utilised for fertilizing and liming purposes on top of soils. Pre-treatments involving hardening or granulation may be carried out prior to soil application. In this study, two Danish wood ash samples were hardened and/or granulated. Lab-hardening induced rapid changes in the shape of the acid neutralisation capacity curve of the ashes. Up-flow column tests, assuming local equilibrium conditions, were employed to investigate the leaching from pre-treated ashes. Granules and loose ashes demonstrated similar leaching behaviours, indicating that similar geochemical processes were governing their leaching. In comparison with untreated fresh ashes, the hardened ashes demonstrated reduced leaching of Ca, Ba, Pb and Zn with concentration levels generally below or close to the analytical limits of quantification; to the contrary, the leaching of As, P, Sb, Si, V and Mg was enhanced in the hardened ashes. The release of alkalinity was reduced by hardening. In general, all granules were barely breakable by finger-pinching and they could withstand one month of continuous leaching, preserving their overall shape. The solubility of phosphorous in neutral ammonium citrate indicated that about 30–51% of the total P content in the ash samples was released, suggesting that the ashes could be potentially valuable as P-fertiliser if applied onto soil.
Biocides are commonly applied to construction materials such as facade renders and paints in order to protect them from microbial spoilage. These renders and paints are exposed to weathering conditions, e.g., sunlight and rain. Pigments are interacting intensively with the spectrum of the incoming light; thus, an effect of paint pigments on phototransformation rates and reaction pathways of the biocides is hypothesized.
In this study, the phototransformation of four commonly used biocides (carbendazim, diuron, octylisothiazolinone (OIT) and terbutryn) in four different paint formulations differing solely in pigments (red and black iron oxides, white titanium dioxide, and one pigment-free formulation) were investigated. Paints surfaces were irradiated under controlled conditions. The results show that biocides degrade most rapidly in the pigment-free formulation. The degradation in the pigment-free formulation followed a first-order kinetic model with the respective photolysis rate constants: kp,Diuron=0.0090 h−1, kp,OIT=0.1205 h−1, kp,Terbutryn=0.0079 h−1.
Carbendazim concentrations did not change significantly. The degradation was considerably lower in the pigment-containing paints. The determination of several phototransformation products of terbutryn and octylisothiazolinone showed different transformation product ratios dependent on the pigment. Consequently, pigments not only reflect the incoming light, but also interact with the biocide photodegradation.
In nature, the cellular environment of DNA includes not only water and ions, but also other components and co-solutes, which can exert both stabilizing and destabilizing effects on particular oligonucleotide conformations. Among them, ectoine, known as an important osmoprotectant organic co-solute in a broad range of pharmaceutical products, turns out to be of particular relevance. In this article, we study the influence of ectoine on a short single-stranded DNA fragment and on double-stranded helical B-DNA in aqueous solution by means of atomistic molecular dynamics (MD) simulations in combination with molecular theories of solution. Our results demonstrate a conformation-dependent binding behavior of ectoine, which favors the unfolded state of DNA by a combination of electrostatic and dispersion interactions. In conjunction with the Kirkwood–Buff theory, we introduce a simple Framework to compute the influence of ectoine on the DNA melting temperature. Our findings reveal a significant linear decrease of the melting temperature with increasing ectoine concentration, which is found to be in qualitative agreement with results from denaturation experiments. The outcomes of our Computer simulations provide a detailed mechanistic rationale for the surprising destabilizing influence of ectoine on distinct DNA structures.
Social insects employ a range of behaviours to protect their colonies against disease, but little is known about how such collective behaviours are orchestrated. This is especially true for the social Blattodea (termites). We developed an experimental approach that allowed us to explore how the social response to disease is co-ordinated by multistep host-pathogen interactions. We infected the eastern subterranean termite Reticulitermes flavipes with the entomopathogenic fungus Metarhizium anisopliae, and then, at different stages of infection, reintroduced them to healthy nestmates and recorded behavioural responses. As expected, termites groomed pathogen-exposed individuals significantly more than controls; however, grooming was significantly elevated after fungal germination than before, demonstrating the importance of fungal status to hygienic behaviour. Significantly, we found that cannibalism became prevalent only after exposed termites became visibly ill, highlighting the importance of host condition as a cue for social hygienic behaviour. Our study reveals the presence of a coordinated social response to disease that depends on stage of infection. Specifically, we show how the host may play a key role in triggering its own sacrifice. Sacrificial self-flagging has been observed in other social insects: our results demonstrate that termites have independently evolved to both recognize and destructively respond to sickness.