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- 4 Material und Umwelt (269)
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Paper des Monats
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Industrial-scale mechanical recycling of plastics has been established for years, but has technical and economic limits. Chemical recycling processes lead back to monomers or to the raw materials, so that in the end new goods can be produced for all areas of application of plastics. The variety of chemical recycling processes is large. The capacities of the plants are still low today. The profitability of the plants is strongly influenced by the price of oil; the profitability limit is currently between 50 and 60 US $ per barrel.
Evolution relies on the availability of genetic diversity for fitness-based selection. However, most deoxyribonucleic acid (DNA) viruses employ DNA polymerases (Pol) capable of exonucleolytic proofreading to limit mutation rates during DNA replication. The relative genetic stability produced by high-fidelity genome replication can make studying DNA virus adaptation and evolution an intensive endeavor, especially in slowly replicating viruses. Here, we present a proofreading-impaired Pol mutant (Y547S) of Marek’s disease virus that exhibits a hypermutator phenotype while maintaining unimpaired growth in vitro and wild-type (WT)-like pathogenicity in vivo. At the same time, mutation frequencies observed in Y547S virus populations are 2–5-fold higher compared to the parental WT virus. We find that Y547S adapts faster to growth in originally non-permissive cells, evades pressure conferred by antiviral inhibitors more efficiently, and is more easily attenuated by serial passage in cultured cells compared to WT. Our results suggest that hypermutator viruses can serve as a tool to accelerate evolutionary processes and help identify key genetic changes required for adaptation to novel host cells and resistance to antiviral therapy. Similarly, the rapid attenuation achieved through adaptation of hypermutators to growth in cell culture enables identification of genetic changes underlying attenuation and virulence, knowledge that could practically exploited, e.g. in the rational design of vaccines.
Quaternary ammonium compounds (QACs) are widely used as active agents in disinfectants, antiseptics, and preservatives. Despite being in use since the 1940s, there remain multiple open questions regarding their detailed mode-of-action and the mechanisms, including phenotypic heterogeneity, that can make bacteria less susceptible to QACs. To facilitate studies on resistance mechanisms towards QACs, we synthesized a fluorescent quaternary ammonium compound, namely N-dodecyl-N,N-dimethyl-[2-[(4-nitro-2,1,3-benzoxadiazol-7-yl)amino]ethyl]azanium-iodide (NBD-DDA). NBD-DDA is readily detected by flow cytometry and fluorescence microscopy with standard GFP/FITC-settings, making it suitable for molecular and single-cell studies. As a proof-of-concept, NBD-DDA was then used to investigate resistance mechanisms which can be heterogeneous among individual bacterial cells. Our results reveal that the antimicrobial activity of NBD-DDA against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa is comparable to that of benzalkonium chloride (BAC), a widely used QAC, and benzyl-dimethyl-dodecylammonium chloride (BAC12), a mono-constituent BAC with alkyl-chain length of 12 and high structural similarity to NBD-DDA. Characteristic time-kill kinetics and increased tolerance of a BAC tolerant E. coli strain against NBD-DDA suggest that the mode of action of NBD-DDA is similar to that of BAC. As revealed by confocal laser scanning microscopy (CLSM), NBD-DDA is preferentially localized to the cell envelope of E. coli, which is a primary target of BAC and other QACs. Leveraging these findings and NBD-DDA‘s fluorescent properties, we show that reduced cellular accumulation is responsible for the evolved BAC tolerance in the BAC tolerant E. coli strain and that NBD-DDA is subject to efflux mediated by TolC. Overall, NBD-DDA’s antimicrobial activity, its fluorescent properties, and its ease of detection render it a powerful tool to study resistance mechanisms of QACs in bacteria and highlight its potential to gain detailed insights into its mode-of-action.
The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve CarbosieveTM SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes.
The development of the microbiologically influenced corrosion ( MIC ) -specific inductively coupled plasma-time of flight-mass spectrometry ( ICP-ToF-MS ) analytical method presented here, in combination with the investigation of steel-MIC interactions, contributes significantly to progress in instrumental MIC analysis. For this, a MIC-specific staining procedure was developed, which ensures the analysis of intact cells. It allows the analysis of archaea at a single cell level, which is extremely scarce compared to other well-characterized organisms. The detection method revealed elemental selectivity for the corrosive methanogenic strain Methanobacterium -affiliated IM1. Hence, the possible uptake of individual elements from different steel samples was investigated and results showed the cells responded at a single-cell level to the different types of supplemented elements and displayed the abilities to uptake chromium, vanadium, titanium, cobalt, and molybdenum from solid metal surfaces. The methods developed and information obtained will be used in the future to elucidate underlying mechanisms, compliment well-developed methods, such as SEM-EDS, and develop novel material protection concepts.
Release of substances from joint grouts based on various binder types and their ecotoxic effects
(2022)
Background: The leaching of substances and the ecotoxic effects of eluates were studied for joint grouts that are based on various types of binders. Eight products, two of them containing either epoxy resin, polybutadiene or polyurethane binders, or modifed cement, were investigated using harmonized leaching tests for construction products in combination with ecotoxicity tests on algae, daphnia, luminescent bacteria, fish eggs and mutagenicity in accordance with CEN/TR 17105. In addition to basic parameters, such as pH, TOC, and inorganic components, organic substances in the eluates were analysed by gas and liquid chromatography in combination with mass spectrometry. Quantitative analyses in combination with ecotoxicity data on selected substances were used to deduce which substances cause the observed ecotoxic effects.
Results: Different patterns of ecotoxic effects were observed in joint grouts with different binder types. The most ecotoxic effects were observed in epoxy resin-based products, followed by polybutadiene-based products. Fewer ecotoxic effects were observed in polyurethane-based products and modifed cements. Some of these showed no ecotoxicity. Some of the substances in the eluates were identified and related to ecotoxic effects. 4-Tert-butylphenol and amines probably contributed to the ecotoxic effects of at least one of the epoxy resin-based renders, whereas cobalt is assumed to contribute to the toxic effect on algae of one of the polybutadiene-based products. However, only some of the leached substances could be identifed, and only some of the ecotoxic effects can be explained by the available information on the composition of eluates and known ecotoxic profiles of the identified substances.
Conclusions: Ecotoxicity tests on eluates from leaching tests indicate whether environmentally hazardous substances can be leached from construction products. Combined ecotoxicity tests and chemical analysis of eluates from EU-wide harmonized leaching tests for construction products can provide information on substances that cause these effects. This supports the identifcation and development of environmentally friendly construction products.
This study confirmed that ecotoxicity tests in accordance with CEN/TR 17105 are a tool well-suited to support the implementation of the European Commission’s zero pollution vision for 2050 and to reduce pollution to levels no longer considered harmful to health and natural ecosystems.
Vaccination is defined as the stimulation and development of the adaptive immune system by administering specific antigens. Vaccines' efficacy, in inducing immunity, varies in different societies due to economic, social, and biological conditions. One of the influential biological factors is gut microbiota. Cross-talks between gut bacteria and the host immune system are initiated at birth during microbial colonization and directly control the immune responses and protection against pathogen colonization. Imbalances in the gut microbiota composition, termed dysbiosis, can trigger several immune disorders through the activity of the adaptive immune system and impair the adequate response to the vaccination. The bacteria used in probiotics are often members of the gut microbiota, which have health benefits for the host. Probiotics are generally consumed as a component of fermented foods, affect both innate and acquired immune systems, and decrease infections. This review aimed to discuss the gut microbiota's role in regulating immune responses to vaccination and how probiotics can help induce immune responses against pathogens. Finally, probiotic-based oral vaccines and their efficacy have been discussed.
Nutrient acquisition strategies of plants regulate water flow and mass transport within ecosystems, shaping earth surface processes. Understanding plant strategies under current conditions is important to assess and predict responses of natural ecosystems to future climate and environmental changes. Nitrogen (N) and potassium (K) (re-)utilization from topsoil and their acquisition from subsoil and saprolite were evaluated in a continental transect, encompassing three study sites – an arid shrubland, a mediterranean woodland, and a temperate rainforest – on similar granitoid parent material in the Chilean Coastal Cordillera. The short-term (<1 year) plant N and K acquisition was traced with 15N and the K analogs rubidium and cesium. To do so, the tracers were either injected into topsoil, subsoil, or saprolite, in the immediate vicinity of eight individual plants per study site and injection depth. The long-term (>decades) K uplift by plants was investigated by the vertical distribution of exchangeable K+ and Na+. Recoveries of 15N and K analogs by arid shrubland plants were similar from topsoil, subsoil, and saprolite. Mediterranean woodland shrubs recovered the tracers primarily from topsoil (i.e., 89 % of recovered 15N and 84 % of recovered K analogs). Forest plants recovered the tracers from topsoil (15N = 49 %, K analogs = 57 %) and partially from greater depth: 38 % of recovered 15N and 43 % of recovered K analogs were acquired from subsoil and saprolite, respectively. Low nutrient accessibility in the topsoil (e.g., because of frequent droughts) drives shrubland plants to expand their N and K uptake to deeper and moister soil and saprolite. Woodland and forest plants dominantly recycled nutrients from topsoil. In the forest, this strategy was complemented by short-term uplift of N and K from depth. The vertical distribution of exchangeable K indicated long-term uplift of K by roots in all three sites. This highlighted that long-term K uplift from depth complements the nutrient budget across the continental transect.
Weather conditions affect biocides on exposed outer surfaces on constructions. Contact with water causes hydrolysis and leaching of substances. Ultraviolet radiation may induce photolysis. As a result, a mixture of biocidal active substances and transformation products can be emitted into the environment. In a semi-field study, leaching of the biocidal active substances terbutryn, diuron, octylisothiazolinone, carbendazim, and selected transformation products was observed for two paints containing either a white or a red pigment. Painted test panels were exposed to natural weathering for about 1.5 years. Runoff samples were analyzed during the course of the experiment.
At the end of the study, residues of biocidal active substances and transformation products were determined in sections of the test panels. Emissions of substances were mainly observed during the first few months of the experiments. Increased emissions of transformation products were observed during periods of increased global radiation and subsequent periods with relatively high amounts of driving rain. Different patterns of transformation products were observed, especially for terbutryn, both for paints containing different pigments and in experiments that were started in different periods of the year, as well as during different periods of the experiments.
Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, EDS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids were used to introduce functional groups for further conjugations. The common crosslinker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter was oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower non-specific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). A binding capacity of 1.8 mg IgG per gram of corundum powder was achieved. The advantages of corundum include the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, convenient handling, and flexible application.
Phosphorus recycling from sewage sludge will be obligatory in Germany from 2029. Phosphorus content determination in sewage sludge is crucial to assess the prescribed recycling rates. Currently, German law regards sample preparation using aqua regia digestion in a microwave or under reflux conditions as well as instrumental phosphorus determination by ICP-OES, ICP-MS, or photometric determination with ammonium molybdate as equivalent. However, it is questionable whether these methods are indeed equivalent regarding phosphorus quantification in sludges near the limit of 20 g/kg for mandatory recycling. To answer this question, 15 sewage sludges of 11 different wastewater treatment plants were investigated with all permitted method (digestion and measurement) combinations. Moreover, one sewage sludge was also examined in an interlaboratory comparison (ILC) with 28 participants. This study shows that the above-mentioned methods differ in some cases significantly but across all method combinations and sludges, phosphorus recovery was between 80 and 121% after normalization to the grand mean (average of 15 sludges between 85 and 111%). The ILC and the examination of 15 sludges produced largely similar results. There is a tendency to higher phosphorus recovery after microwave digestion compared to reflux digestion and ICP-OES measurements determine higher phosphorus contents than ICP-MS and photometric phosphorus determination. As a result, the authors recommend ICP-OES determination of phosphorus in sewage sludge after microwave digestion.
Nine different bacterial isolates were recovered from landfills. Each isolate was obtained in pure culture. As a consortium, the bacteria degrade polyethylene. The complete genome sequence of strain G5 was determined by PacBio sequencing. Using the TYGS for taxonomic classification, strain G5 was assigned to the species Cupriavidus campinensis.
Phosphorus (P) recovery is obligatory for all sewage sludges with more than 20 g P/kg dry matter (DM) from 2029 in Germany. Nine wastewater treatment plants (WWTPs) were chosen to investigate variations of phosphorus contents and other parameters in sewage sludge over the year. Monthly sewage sludge samples from each WWTP were analyzed for phosphorus and other matrix elements (C, N, H, Ca, Fe, Al, etc.), for several trace elements (As, Cr, Mo, Ni, Pb, Sn) and loss of ignition. Among the nine WWTPs, there are four which have phosphorus contents both above and below the recovery limit of 20 g/kg DM along the year. Considering the average phosphorus content over the year, only one of them is below the limit. Compared to other matrix elements and parameters, phosphorus fuctuations are low with an average of 7% over all nine WWTPs. In total, only hydrogen and carbon are more constant in the sludge.
In several WWTPs with chemical phosphorus elimination, phosphorus fuctuations showed similar courses like iron and/or aluminum. WWTPs with chamber flter presses rather showed dilution efects of calcium dosage. As result of this study, monthly phosphorus measurement is highly recommended to determine whether a WWTP is below the
20 g/kg DM limit.
This study will present a new approach to distinguishing writing inks that have the same elemental compositions and visual appearances. The approach is based on displaying the intensity of elemental distributions as heat maps that represent data recorded with a scanning μX-ray fluorescence spectrometer. The heat maps present the data so as to facilitate digitally identifying and distinguishing between inks used to produce, correct, and reink two medieval Torah scrolls. As ritual objects, Torah scrolls had to be written in accordance with exacting standards that evolved over time. This requirement led to successive stages of modifications, sometimes over centuries. Both vitriolic and non-vitriolic inks used to modify Torah scrolls can be visually identical to each other. Furthermore, different non-vitriolic inks usually have an identical elemental composition. The solid material analysis evidence and its presentation as heat maps made it possible to discriminate between original and altered portions of text that in some cases would have been impossible. Our interdisciplinary work brought together conservation, material science, paleog-raphy, and philology to enable the identification of complex stratigraphy in multiple stages of production, correction, and reinking. ©2 0 2 2 Published by Elsevier Masson SAS.
The application of naturally-derived biomolecules in everyday products, replacing conventional synthetic manufacturing, is an ever-increasing market. An example of this is the compatible solute ectoine, which is contained in a plethora of treatment formulations for medicinal products and cosmetics. As of today, ectoine is produced in a scale of tons each year by the natural producer Halomonas elongata. In this work, we explore two complementary approaches to obtain genetically improved producer strains for ectoine production. We explore the effect of increased precursor supply (oxaloacetate) on ectoine production, as well as an implementation of increased ectoine demand through the overexpression of a transporter. Both approaches were implemented on an already genetically modified ectoine-excreting strain H. elongata KB2.13 (ΔteaABC ΔdoeA) and both led to new strains with higher ectoine excretion. The supply driven approach led to a 45% increase in ectoine titers in two different strains. This increase was attributed to the removal of phosphoenolpyruvate carboxykinase (PEPCK), which allowed the conversion of 17.9% of the glucose substrate to ectoine. For the demand driven approach, we investigated the potential of the TeaBC transmembrane proteins from the ectoine-specific Tripartite ATP-Independent Periplasmic (TRAP) transporter as export channels to improve ectoine excretion. In the absence of the substrate-binding protein TeaA, an overexpression of both subunits TeaBC facilitated a three-fold increased excretion rate of ectoine. Individually, the large subunit TeaC showed an approximately five times higher extracellular ectoine concentration per dry weight compared to TeaBC shortly after its expression was induced. However, the detrimental effect on growth and ectoine titer at the end of the process hints toward a negative impact of TeaC overexpression on membrane integrity and possibly leads to cell lysis. By using either strategy, the ectoine synthesis and excretion in H. elongata could be boosted drastically. The inherent complementary nature of these approaches point at a coordinated implementation of both as a promising strategy for future projects in Metabolic Engineering. Moreover, a wide variation of intracelllular ectoine levels was observed between the strains, which points at a major disruption of mechanisms responsible for ectoine regulation in strain KB2.13.
The leaching behavior of scandium (Sc) from bauxite residues can differ significantly when residues of different geological backgrounds are compared. The mineralogy of the source rock and the physicochemical environment during bauxitization affect the association of Sc in the bauxite i.e., how Sc is distributed amongst different mineral phases and whether it is incorporated in and/or adsorbed onto those phases. The Sc association in the bauxite is in turn crucial for the resulting Sc association in the bauxite residue. In this study systematic leaching experiments were performed on three different bauxite residues using a statistical design of experiments approach. The three bauxite residues compared originated from processing of lateritic and karstic bauxites from
Germany, Hungary, and Russia. The recovery of Sc and Fe was determined by ICP-OES measurements. Mineralogical changes were analyzed by X-ray-diffraction and subsequent Rietveld refinement. The effects of various parameters including temperature, acid type, acid concentration, liquid-to-solid ratio and residence time were studied. A response surface model was calculated for the selected case of citric acid leaching of Hungarian bauxite residue. The investigations showed that the type of bauxite residue has a strong influence. The easily leachable fraction of Sc can vary considerably between the types, reaching ~20–25% in German Bauxite residue and ~50% in Russian bauxite residue. Mineralogical investigations revealed that a major part of this fraction was released from secondary phases such as cancrinite and katoite formed during Bayer processing of the bauxite.
The effect of temperature on Sc and Fe recovery is strong especially when citric acid is used. Based on the exponential relationship between temperature and Fe-recovery it was found to be particularly important for the selectivity of Sc over Fe. Optimization of the model for a maximum Sc recovery combined with a minimum Fe
recovery yielded results of ~28% Sc recovery at <2% Fe recovery at a temperature of 60 ◦C, a citric acid normality of 1.8, and a liquid-to-solid ratio of 16 ml/g. Our study has shown that detailed knowledge about the Sc association and distribution in bauxite and bauxite residue is key to an efficient and selective leaching of Sc
from bauxite residues.
Water is generally considered to be an undesirable substance in fuel system, which may lead to microbial contamination. The antibacterial strategies that can turn water into things of value with high disinfection efficacy have been urgently needed for fuel system. Here, we reveal a water-fueled autocatalytic bactericidal pathway comprised by bi-metal micro-electrode system, which can spontaneously produce reactive oxygen species (mainly H2O2 and O2•–) by the electron Fenton-like reaction in water medium without external energy., The respiratory chain component of bacteria and the galvanic corrosion on the coated metals were two electron sources in the system. The specific model of Ag-Ru water-fueled autocatalytic (WFA) microelectrode particles presents extremely high disinfection efficiency (>99.9999%) in less than one hour for three aerobic bacteria (Escherichia coli, Pseudomonas aeruginosa and Bacillus subtilis) in LB media and high disinfection efficiency for the anaerobic bacteria (Desulfovibrio alaskensis) in Postgate E media without natural light irradiation. Overall, the novel WFA Ag-Ru antibacterial material explored in this study has a high potential for sterilizing applications in fuel system and this work provides the potential for the development of non-chemical and water-based antibacterial materials, such as WFA Ag-Ru antibacterial coating on stainless steel.
Numerous non-native tree species are given attention with respect to the reforestation of calamity areas in Europe. Among them, several species may form durable wood which can be used for outdoor applications, but differences in wood durability are expected between original and European growth sites. This study aimed at examining the biological durability against wooddestroying fungi and water permeability of German-grown Dawn redwood (Metasequoia glyptostroboides) and Port Orford cedar (Chamaecyparis lawsoniana). The heartwood of both wood species was assigned to durability class 4 (DC 4, less durable) in soil contact and DC 1–4 (very to less durable) against wood-destroying basidiomycetes. However, according to the Meyer-Veltrup model, their material resistance dose was notably higher compared to the reference species Norway spruce (Picea abies), and the resulting service life of above ground structures should be a multiple of the reference.
Industrial and agricultural waste streams (waste water, sludges, tailings, etc.) which contain high concentrations of NH4+, PO43–, and transition metals are environmentally harmful and toxic pollutants. At the same time, phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate independently from each other. Investigations on the simultaneous removal of multiple components have been carried out only to a limited extent. Here, we report the synthesis routes for Ni- and Co-struvites (NH4MPO4·6H2O, M = Ni2+ and Co2+), which allow for P, ammonia, and metal co-precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites as well as their crystal morphologies and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal amorphous nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the involved metal cation in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size makes precipitation of transition metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially up-cycled as precursor powders for electrochemical or (electro)catalytic applications, which require transition metal phosphates.
Antimicrobial resistance (AMR) is a global health problem with the environment being an important compartment for the evolution and transmission of AMR. Previous studies showed that de-novo mutagenesis and horizontal gene transfer (HGT) by conjugation or transformation – important processes underlying resistance evolution and spread - are affected by antibiotics, metals and pesticides. However, natural microbial communities are also frequently exposed to biocides used as material preservatives, but it is unknown if these substances induce mutagenesis and HGT. Here, we show that active substances used in material preservatives can increase rates of mutation and conjugation in a species- and substance-dependent manner, while rates of transformation are not increased. The bisbiguanide chlorhexidine digluconate, the quaternary ammonium compound didecyldimethylammonium chloride, the metal copper, the pyrethroid-insecticide permethrin, and the azole-fungicide propiconazole increase mutation rates in Escherichia coli, whereas no increases were identified for Bacillus subtilis and Acinetobacter baylyi.
Benzalkonium chloride, chlorhexidine and permethrin increased conjugation in E. coli. Moreover, our results show a connection between the RpoS-mediated general stress and the RecA-linked SOS response with increased rates of mutation and conjugation, but not for all biocides. Taken together, our data show the importance of assessing the contribution of material preservatives on AMR evolution and spread.
Electron microscopy (EM) is the gold standard for the characterisation of the morphology (size and shape) of nanoparticles. Visual observation of objects under examination is always a necessary first step in the characterisation process. Several questions arise when undertaking to identify and count particles to measure their size and shape distribution. In addition to challenges with the dispersion and identification of the particles, more than one protocol for counting particles is in use. This paper focuses on precise rules for the counting of particles in EM micrographs, as this influences the measurement accuracy of the number of particles, thus implicitly affecting the size values of the counted particles. We review and compare four different, commonly used methods for counting, which we then apply in case studies. The impact of the selected counting rule on the obtained final particle size distribution is highlighted. One main aim of this analysis is to support the application of a specific, well-defined counting approach in accordance with regulatory
requirements to contribute to achieving more reliable and reproducible results. It is also useful for the new harmonised measurement procedures for determining the particle size and particle size distribution of nanomaterials.
Background: Host–pathogen interactions can lead to dramatic changes in host feeding behaviour. One aspect of this includes self-medication, where infected individuals consume substances such as toxins or alter their macronutrient consumption to enhance immune competence. Another widely adopted animal response to infection is illness-induced anorexia, which is thought to assist host immunity directly or by limiting the nutritional resources available to pathogens. Here, we recorded macronutrient preferences of the global pest cockroach, Blatta orientalis to investigate how shifts in host macronutrient dietary preference and quantity of carbohydrate (C) and protein (P) interact with immunity following bacterial infection.
Results: We fnd that B. orientalis avoids diets enriched for P under normal conditions, and that high P diets reduce cockroach survival in the long term. However, following bacterial challenge, cockroaches signifcantly reduced their overall nutrient intake, particularly of carbohydrates, and increased the relative ratio of protein (P:C) consumed. Surprisingly, these behavioural shifts had a limited efect on cockroach immunity and survival, with minor changes to immune protein abundance and antimicrobial activity between individuals placed on diferent diets, regardless of infection status.
Conclusions: We show that cockroach feeding behaviour can be modulated by a pathogen, resulting in an illness-induced anorexia-like feeding response and a shift from a C-enriched to a more P:C equal diet. However, our results also indicate that such responses do not provide signifcant immune protection in B. orientalis, suggesting that the host’s dietary shift might also result from random rather than directed behaviour. The lack of an apparent beneft of the shift in feeding behaviour highlights a possible reduced importance of diet in immune regulation in these invasive animals, although further investigations employing pathogens with alternative infection strategies are warranted.
The roles extracellular polymeric substances (EPS) play in mineral attachment and weathering were studied using genetically modified biofilms of the rock-inhabiting fungus Knufia petricola strain A95. Mutants deficient in melanin and/or carotenoid synthesis were grown as air-exposed biofilms. Extracted EPS were quantified and characterised using a combination of analytical techniques. The absence of melanin affected the quantity and composition of the produced EPS: mutants no longer able to form melanin synthesised more EPS containing fewer pullulan-related glycosidic linkages. Moreover, the melanin-producing strains attached more strongly to the mineral olivine and dissolved it at a higher rate. We hypothesise that the pullulan-related linkages, with their known adhesion functionality, enable fungal attachment and weathering. The released phenolic intermediates of melanin synthesis in the Δsdh1 mutant might play a role similar to Fe-chelating siderophores, driving olivine dissolution even further. These data demonstrate the need for careful compositional and quantitative analyses of biofilm-created microenvironments.
Nine different bacterial isolates were recovered from landfills. Each isolate was obtained in pure culture. As a consortium, the bacteria degrade polyethylene. The complete genome sequence of strain G2 was determined by PacBio sequencing. Using the TYGS server for taxonomic classification, strain G2 was assigned to the species Pseudomonas veronii.
For more than 110 years, BAM has been producing reference materials for a wide range of application fields. With the development of new analytical methods and new applications as well as continuously emerging more stringent requirements of laboratory accreditation with regard to quality control and metrological traceability, the demand and requirements for reference materials are increasing. This trend article gives an overview of general developments in the field of reference materials as well as developments in selected fields of application in which BAM is active. This includes inorganic and metal analysis, gas analysis, food and consumer products, and geological samples. In addition to these more traditional fields of application, developments in the areas of optical spectroscopy, particulary fluorescence methods, and nanomaterials are considered.
Cellulose ethers, like methyl cellulose (MC) or hydroxypropyl cellulose (HPC), are widely used in conservation. They also occur as additives and rheology modifiers in various products like dispersions or gels. Do such products release harmful volatile organic compounds (VOC) during their accelerated aging? A mass testing series utilizing the Oddy test of 60 commercial cellulose ethers ranks the products in safe for permanent use (P, no corrosion), only for temporary use (T, slight corrosion), and unsuitable at all (F, heavy corrosion). Results show that 55% of the products passed the test whereas 33% are for temporary use as slight corrosion occurred on at least one metal coupon and only 11% failed the Oddy test. Raman measurements of the corrosion products identified oxides like massicot, litharge, cuprite, and tenorite among carbonates (hydrocerussite, plumbonacrite), and acetates like basic lead acetate, lead acetate trihydrate as well as lead formate as main phases. For example, commercial, industrial Klucel® G (HPC) scored a T rating through slight corrosion on the lead coupon. Basic lead acetate among other phases indicates the presence of acetic acid. Additional measurements of the sample with thermal desorption GC–MS utilizing the BEMMA scheme confirm the high acetic acid outgassing and reveal the presence of a small amount of formaldehyde.
Nine different bacterial isolates were recovered from landfills. Each isolate was obtained in pure culture. As a consortium, the bacteria degrade polyethylene. The complete genome sequence of strain G9 was determined by PacBio sequencing. Using the TYGS server for taxonomic classification, strain G9 was assigned to the species Micromonospora aurantiaca.
Herein we report the synthesis of a zeolitic imidazolate framework (ZIF-8) by an easy “mix and wait” procedure. In a closed vial, without any interference, the mixture of 2-methylimidazole and basic zinc carbonate assembles into the crystalline product with approx. 90% conversion after 70 h. The reaction exhibits sigmoidal kinetics due to the self-generated water which accelerates the reaction.
The environmental impact assessment of materials is usually based on laboratory tests, mostly in combination with models describing the longterm fate of the substances of interest in the targeted environmental compartment. Thus, laboratory tests are the fundamental link to achieve appropriate assessment conclusions which makes it essential to generate consistent results. This just as applies to the leaching of cementitious materials. In Europe, the leaching behavior of monolithic building materials is tested in the Dynamic Surface Leaching Test following the specification CEN/TS 16637–2. An interlaboratory comparison on European level regarding this technical specification showed relatively high intra- and interlaboratory variations for the tested materials (monolithic copper slag and cement stabilized coal fly ash). Therefore the German Committee for Structural Concrete (DAfStb) framed a guideline to specify additional testing conditions for cementitious materials. To assess the possible improvement by this guidelines measures, a round robin test with 11 participants from Germany and the Netherlands was conducted. This work aims to provide insight into the factors to be considered in the testing of alkaline materials, including sample preparation, and highlights crucial procedures and their manifestation in the results. All evaluated parameters showed improved results compared to the earlier round robin test. The relative standard deviations for repeatability (RSDr) and reproducibility (RSDR) of the elements calcium, barium, antimony, chromium, molybdenum and vanadium, which are the parameters evaluated in both round robin tests, were RSDr = 4%, 4%, 2%, 5%, 5%, and 5% respectively (4% in average) for this work, in comparison to the European round robin test with an average RSDr of 29% (17%, 17%, 20%, 40%, 36%, and 42%). The RSDR improved from 41% (30%, 36%, 29%, 57%, 40%, and 56%) to 14% (12%, 8%, 6%, 28%, 15%, and 12%). CO2 ingress during testing and the inaccuracy of eluate analytics for concentrations close to the determination limits were identified as the main sources of error.
Black microcolonial fungi (Ascomycetes from Arthonio-, Dothideo-, and Eurotiomycetes) are stress-tolerant and persistent dwellers of natural and anthropogenic extreme habitats. They exhibit slow yeast-like or meristematic growth, do not form specialized reproduction structures and accumulate the black pigment 1,8-dihydroxynaphthalene (DHN) melanin in the multilayered cell walls. To understand how black fungi live, survive, colonize mineral substrates, and interact with phototrophs genetic methods are needed to test these functions and interactions. We chose the rock inhabitant Knufia petricola of the Chaetothyriales as a model for developing methods for genetic manipulation. Here, we report on the expansion of the genetic toolkit by more efficient multiplex CRISPR/Cas9 using a plasmid-based system for expression of Cas9 and multiple sgRNAs and the implementation of the three resistance selection markers genR (geneticin/nptII), baR (glufosinate/bar), and suR (chlorimuron ethyl/sur). The targeted integration of expression constructs by replacement of essential genes for pigment synthesis allows for an additional color screening of the transformants. The black-pink screening due to the elimination of pks1 (melanin) was applied for promoter studies using GFP fluorescence as reporter. The black-white screening due to the concurrent elimination of pks1 and phs1 (carotenoids) allows to identify transformants that contain the two expression constructs for co-localization or bimolecular fluorescence complementation (BiFC) studies. The co-localization and interaction of the two K. petricola White Collar orthologs were demonstrated. Two intergenic regions (igr1, igr2) were identified in which expression constructs can be inserted without causing obvious phenotypes. Plasmids of the pNXR-XXX series and new compatible entry plasmids were used for fast and easy generation of expression constructs and are suitable for a broad implementation in other fungi. This variety of genetic tools is opening a completely new perspective for mechanistic and very detailed study of expression, functioning and regulation of the genes/proteins encoded by the genomes of black fungi.
The diffusive gradients in thin-films (DGT) technique shows in many publications a superior correlation to the amount of plant-available phosphorus (P) in soil. However, this technique cannot give information on the plant-available P species in soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time.
The halophilic γ-proteobacterium Halomonas elongata DSM 2581T thrives at salt concentrations well above 10 % NaCl (1.7 M NaCl). A well-known osmoregulatory mechanism is the accumulation of the compatible solute ectoine within the cell in response to osmotic stress. While ectoine accumulation is central to osmoregulation and promotes resistance to high salinity in halophilic bacteria, ectoine has this effect only to a much lesser extent in non-halophiles. We carried out transcriptome analysis of H. elongata grown on two different carbon sources (acetate or glucose), and low (0.17 M NaCl), medium (1 M), and high salinity (2 M) to identify additional mechanisms for adaptation to high saline environments. To avoid a methodological bias, the transcripts were evaluated by applying two methods, DESeq2 and Transcripts Per Million (TPM). The differentially transcribed genes in response to the available carbon sources and salt stress were then compared to the transcriptome profile of Chromohalobacter salexigens, a closely related moderate halophilic bacterium. Transcriptome profiling supports the notion that glucose is degraded via the cytoplasmic Entner-Doudoroff pathway, whereas the Embden-Meyerhoff-Parnas pathway is employed for gluconeogenesis. The machinery of oxidative phosphorylation in H. elongata and C. salexigens differs greatly from that of non-halophilic organisms, and electron flow can occur from quinone to oxygen along four alternative routes. Two of these pathways via cytochrome bo' and cytochrome bd quinol oxidases seem to be upregulated in salt stressed cells. Among the most highly regulated genes in H. elongata and C. salexigens are those encoding chemotaxis and motility proteins, with genes for chemotaxis and flagellar assembly severely downregulated at low salt concentrations. We also compared transcripts at low and high-salt stress (low growth rate) with transcripts at optimal salt concentration and found that the majority of regulated genes were down-regulated in stressed cells, including many genes involved in carbohydrate metabolism, while ribosome synthesis was up-regulated, which is in contrast to what is known from non-halophiles at slow growth. Finally, comparing the acidity of the cytoplasmic proteomes of non-halophiles, extreme halophiles and moderate halophiles suggests adaptation to an increased cytoplasmic ion concentration of H. elongata. Taken together, these results lead us to propose a model for salt tolerance in H. elongata where ion accumulation plays a greater role in salt tolerance than previously assumed.
This Special Issue, ‘Measurement of the Environmental Impact of Materials’, is focused on the impact that materials have on the environmental compartments of soil, water and air. Leaching and emission processes, including underlying mechanisms, are a recurring topic in most published articles in the present Special Issue. Contributions have come from three continents and numerous countries (USA, Germany, France, Latvia, Poland, Russia, Japan, Korea and Thailand) indicating the global dimension of the subject.
The diversity of fused filament fabrication (FFF) filaments continues to grow rapidly as the popularity of FFF-3D desktop printers for the use as home fabrication devices has been greatly increased in the past decade. Potential harmful emissions and associated health risks when operating indoors have induced many emission studies. However, the lack of standardization of measurements impeded an objectifiable comparison of research findings. Therefore, we designed a chamber-based standard method, i.e., the strand printing method (SPM), which provides a standardized printing procedure and quantifies systematically the particle emission released from individual FFF-3D filaments under controlled conditions. Forty-four marketable filament products were tested. The total number of emitted particles (TP) varied by approximately four orders of magnitude (1E9 ≤ TP ≤ 1E13), indicating that origin of polymers, manufacturer-specific additives, and undeclared impurities have a strong influence. Our results suggest that TP characterizes an individual filament product and particle emissions cannot be categorized by the polymer type (e.g., PLA or ABS) alone. The user's choice of a filament product is therefore decisive for the exposure to released particles during operation. Thus, choosing a filament product awarded for low emissions seems to be an easily achievable preemptive measure to prevent health hazards.
Pseudomonas fluorescens (Gram-negative) bacteria purchased from Leibniz Institute DSMZ-German Collection of Microorganisms and Cell Cultures were analyzed using high-resolution x-ray photoelectron spectroscopy at near ambient pressure conditions (NAP-XPS), 1500 Pa water vapor atmosphere. Fresh layers of P. fluorescence bacteria were grown on Luria Broth agar plates. Bacteria were taken from the agar plate with a sterile spatula and gently spread on a Si-wafer piece for NAP-XPS analysis. The NAP-XPS spectra of the bacterial envelope of P. fluorescence were obtained using monochromatic Al Kα radiation and include a survey scan and high-resolution spectra of C 1s, N 1s, P 2p, and O 1s as well. The presentation of the C 1s high-resolution spectrum includes the results of peak fitting analysis.
This work presents a spectroscopic study of metallic pigments and metal foils used in reverse glass paintings that were created between 1912 and 1954. Metallic pigments induce a notable sparkling effect by means of the lateral incidence of light, whereas metal foils enhance the gloss and create a glittering effect when the painting is viewed in reflected light. Both effects were desired features especially in modern reverse paintings on glass and applied by artists in manifold creative manner. The paper gives an overview on the composition of the metalfoils and metal pigments in 14 works as determined in situ by X-ray spectrometry. Metal foils made of tin, brass, aluminium and silver were found in nine paintings. Gold imitating Cu-Zn pigments in different hues and with various Cu/Zn net intensity ratios were recorded for six paintings. Silvery pigments were identified mainly as Al pigments, but also as Cu-Zn-Ni alloy in one case. Other uncommon metallic pigments were detected in Arlequin vindicatif (c. 1925) by Floris Jespers, who used not only Cu-Zn and Al pigments, but also brownish Cu and Cu-Zn-Sn pigments. Non-invasive diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) was used to classify the binding media of the metallic pigments. Drying oil and natural resin probably mixed with oil were the most common binding media. A polysaccharide-based binder was found in the silvery Cu-Zn-Ni pigment of Ohne Titel (1954) by Marianne Uhlenhuth.
The use of highly water-soluble phosphorus (P) fertilizers can lead to P fixation in the soil, reducing fertilization efficiency. Waste-derived, low water-solubility sources can potentially increase sugarcane’s P uptake compared to triple superphosphate by reducing adsorption to the soil.
Aims:We aimed to test struvite, hazenite, and AshDec® for their agronomic potential as recycled fertilizers for sugarcane production in a typical tropical soil.We hypothesize that these sources can reduce P fixation in the soil, increasing its availability and sugarcane’s absorption.
Methods: In a greenhouse pot experiment, two consecutive sugarcane cycles, 90 days each, were conducted in a Ferralsol. The recovered sources struvite, hazenite, AshDec®, and the conventional triple superphosphate were mixed in the soil in three P doses (30, 60, and 90 mg kg–1), aside a control (nil-P). At both harvests, sugarcane number of sprouts, plant height, stem diameter, dry mass yield, shoot phosphorus, and soil P fractionation were investigated.
Results: At 90 days, struvite and hazenite performed better for dry mass yield (70.7 and 68.3 g pot–1, respectively) than AshDec® and triple superphosphate (59.8 and 57.4 g pot–1, respectively) and for shoot P, with 98.1, 91.6, 75.6, and 66.3 mg pot–1, respectively. At 180 days, struvite outperformed all treatments for dry mass yield (95.3 g pot–1) and AshDec® (75.5 mg pot–1) for shoot P. Struvite was 38% and hazenite 21% more efficient than triple superphosphate in P uptake, while AshDec® was 6% less efficient. Soil had higher labile P under struvite, hazenite, and AshDec® than triple superphosphate by the end of the first cycle, while only the later increased nonlabile P by the end of the experiment (180 days).
Conclusions:Waste-derived P sources were more efficient in supplying P for sugarcane and delivering labile P in 180 days than triple superphosphate.
Improved Durability of Wood Treated with Nano Metal Fluorides against Brown-Rot and White-Rot Fungi
(2022)
Low-water soluble metal fluorides such as magnesium fluoride (MgF2) and calcium Fluoride (CaF2) were evaluated for decay protection of wood. Initially, the biocidal efficacy of nano metal fluorides (NMFs) against wood destroying fungi was assessed with an in-vitro agar test. The results from the test showed that agar medium containing MgF2 and CaF2 was more efficient in preventing fungal decay than stand-alone MgF2 or CaF2. These metal fluorides, in their nanoscopic form synthesized using fluorolytic sol-gel synthesis, were introduced into the sapwood of Scots pine and beech wood and then subjected to accelerated ageing by leaching (EN 84). MAS 19F NMR and X-ray micro CT images showed that metal fluorides were present in treated wood, unleached and leached. Decay resistance of Scots pine and beech wood treated with NMFs was tested against Wood destroying fungi Rhodonia placenta and Trametes versicolor in accordance with EN 113. Results revealed that mass losses were reduced to below 3% in wood treated with the combination of MgF2 and CaF2.
It is concluded that NMFs provide full protection to wood even after it has been leached and can be used as wood preservatives in outdoor environments.
Here, we describe an optimized fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) in soils utilizing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR–CS–GFMAS). To omit the bias of the solid phase extraction (SPE) step commonly used during the analysis of extractable organically bound fluorine (EOF) we optimized a fast and simple SPE-free extraction method. The developed extraction method consists of a liquid-solid extraction using acidified methanol without any additional SPE. Four extraction steps were representative to determine a high proportion of the EOF (>80% of eight extractions). Comparison of the optimized method with and without an additional SPE clean-up step revealed a drastic underestimation of EOF concentrations using SPE. Differences of up to 94% were observed which were not explainable by coextracted inorganic fluoride. Therefore, not only a more accurate but also a more economic as well as ecologic method (bypassing of unnecessary SPE) was developed. The procedural limit of quantification (LOQ) of the developed method was 10.30 μg/kg which was sufficient for quantifying EOF concentrations in all tested samples. For future PFAS monitoring and potential regulative decisions the herein presented optimized extraction method can offer a valuable contribution.
The bipartite interactions between insect hosts and their bacterial gut microbiota, or their bacterial pathogens, are empirically and theoretically well-explored. However, direct, and indirect tripartite interactions will also likely occur inside a host. These interactions will almost certainly affect the trajectory of pathogen virulence evolution, an area that is currently under researched. The interactions within tripartite associations can be competitive, that is, exploitative-competition, interference-competition or apparent-competition. Competitive interactions will be significantly influenced by non-competitive effects, for example, immunopathology, immunosuppression, and microbiota-mediated tolerance. Considering a combination of these interactions and effects, will enable an increased understanding of the evolution of pathogen virulence. This new perspective allows us to identify several novel research questions, which we hope will be a useful framework for future research.
Most of our knowledge on insect cuticular hydrocarbons (CHCs) stems from analytical techniques based on gas-chromatography coupled with mass spectrometry (GC-MS). However, this method has its limits under standard conditions, particularly in detecting compounds beyond a chain length of around C40. Here, we compare the CHC chain length range detectable by GC-MS with the range assessed by silver-assisted laser desorption/ionization mass spectrometry (Ag-LDI-MS), a novel and rarely applied technique on insect CHCs, in seven species of the order Blattodea. For all tested species, we unveiled a considerable range of very long-chain CHCs up to C58, which are not detectable by standard GC-MS technology. This indicates that general studies on insect CHCs May frequently miss compounds in this range, and we encourage future studies to implement analytical techniques extending the conventionally accessed chain length range. Furthermore, we incorporate 3D scanned insect body surface areas as an additional factor for the comparative quantification of extracted CHC amounts between our study species. CHC quantity distributions differed considerably when adjusted for body surface areas as opposed to directly assessing extracted CHC amounts, suggesting that a more accurate evaluation of relative CHC quantities can be achieved by taking body surface areas into account.
The aim of this paper is to present the productive interplay of connoisseurship and material analysis when dealing with drawings by Rembrandt – or previously attributed to him – in the collection of the Klassik Stiftung Weimar. This concerns the more precise determination of the drawing materials used and the reconstruction of the genesis of the drawings discussed. The material analysis allows us to decide whether and how Rembrandt’s inks can be used to determine authorship at all. The “material turn” in drawing studies thus intervenes in the discussion about authorship and opens up a broader production aesthetic perspective. No longer the “style” but rather the handeling becomes the decisive criterion for answering the question “Rembrandt, or not?”
The development of traceable new methodologies to quantify elemental air pollutants in particulate matter (PM) supports modernization of methods used in air quality monitoring networks in Europe. In the framework of the EURAMET EMPIR AEROMET II project, the combination of cascade impactor aerosol sampling and total reflection X-ray fluorescence elemental spectroscopy (TXRF) was investigated. This technique requires a traceable calibration based on reference samples. This paper describes a new, simple and effective method to produce such reference samples using flexible, reusable, and low-cost parylene C shadow masks, fabricated by photolithographic steps. These shadow masks can be used to produce reference samples that mimic the Dekati cascade impactor’s deposition patterns by applying as-prepared micro stencils to 30 mm acrylic substrates and evaporating a reference material (Ti) in arrangements of thin circular dots. The highly flexible direct patterning of acrylic discs with reference material, otherwise impossible with conventional photolithography, allows multiple reusing of the same micro stencils. The aspect ratios of the dots could be repeated with an error less than 4 %. A first set of standard reference samples for the 13 stages of the Dekati cascade impactor was produced and preliminary TXRF measurements of the deposited Ti masses were performed. The centricity of the deposition patterns turned out to be an important parameter for the quality of the TXRF results. The parylene mask technology for the production of reference samples turns out to be a promising new approach for the traceable calibration of TXRF spectrometers for the quantification of element concentrations in environmental aerosol samples but, due to its great versatility, it could be used for several other micropatterning applications on conventional and unconventional substrates.
Buildings exposed to water can release undesirable substances which, once transported to environmental compartments, may cause unwanted effects. These exposure pathways need to be investigated and included in risk assessments to safeguard water quality and promote the sustainability of construction materials. The applied materials, exposure conditions, distribution routes and resilience of receiving compartments vary considerably. This demonstrates the need for a consistent concept that integrates knowledge of emission sources, leaching processes, transport pathways, and effects on targets. Such a consistent concept can serve as the basis for environmental risk assessment for several scenarios using experimentally determined emissions. Typically, a source–path–target concept integrates data from standardized leaching tests and models to describe leaching processes, the distribution of substances in the environment and the occurrence of substances at different points of compliance. This article presents an integrated concept for assessing the environmental impact of construction products on aquatic systems and unravels currently existing gaps and necessary actions. This manuscript outlines a source–path–target concept applicable to a large variety of construction products. It is intended to highlight key elements of a holistic evaluation concept that could assist authorities in developing procedures for environmental risk assessments and mitigation measures and identifying knowledge gaps.
The pressing need for novel bioproduction approaches faces a limitation in the number and type of molecules accessed through synthetic biology. Halogenation is widely used for tuning physicochemical properties of molecules and polymers, but traditional halogenation chemistry often lacks specificity and generates harmful by-products. Here, we pose that deploying synthetic metabolism tailored for biohalogenation represents an unique opportunity towards economically attractive and environmentally friendly organohalide production. On this background, we discuss growth-coupled selection of functional metabolic modules that harness the rich repertoire of biosynthetic and biodegradation capabilities of environmental bacteria for in vivo biohalogenation. By rationally combining these approaches, the chemical landscape of Living cells can accommodate bioproduction of added-value organohalides which, as of today, are obtained by traditional chemistry.
The database gives information on the contamination of the shore of the South-Eastern Baltic with the debris of geosynthetic materials for the period 2018–2020. This new type of coastal pollution enters the natural environment due to the destruction of coastal protection structures and construction activities. The database contains sections:
(1) a list of types of geosynthetic material residues, their photographic images and photographs illustrating examples of finds in natural conditions
[1 List_geosynthetic_debris_SEB],
(2) monitoring data on the contamination of the beach strip with the debris of geotextiles, braids from gabions, geocontainers (big bags), geocells and geogrids for the beaches of the South-Eastern Baltic for the period 2018–2020
[2 Monitoring_geosynthetic_debris_SEB];
(3) statistical distributions of the found geosynthetic debris by size
[3 Scales_geosynthetic_debris_SEB] and (4) results of test surveys on the shores of Lithuania and Poland adjacent to Kaliningrad Oblast.
All data refer to the beaches of the Kaliningrad Oblast (Russia), including the Russian parts of the Vistula and Curonian Spits, but also contains information on a one-time assessment of the pollution of the beaches of the adjacent territories: the Polish shore from the Poland-Russia border on the Vistula Spit to the mouth of the Vistula River, the Lithuanian shore from the border Lithuania-Russia on the Curonian Spit to the border of Latvia-Lithuania. Materials were collected during field surveys within the ERANET-RUS_Plus joint project EI-GEO, ID 212 (RFBR 18-55-76002 ERA_a, BMBF 01DJ18005).
Future nutrient recovery from sewage sludge regarding three different scenarios - German case study
(2022)
Agricultural sewage sludge utilization becomes less important in Germany. In 2017, new fertilizer and waste laws caused the agricultural sewage sludge utilization to collapse by more than a quarter. From 2029, German wastewater treatment plants (WWTPs) must recover phosphorus (P) from sewage sludge if it contains more than 2 wt % P. Agricultural utilization will be prohibited for large WWTPs >100,000 population equivalents (pe) from 2029 and >50,000 pe from 2032. In Germany, each federal state must annually report amounts and quality of agriculturally utilized sewage sludge which was 16% of the total disposal in 2019. The reports of 10 states were evaluated for 2016 and 2017 representing approx. 60% of the total agriculturally used sludge volume. In 2016, 60% of the WWTPs’ sludges exceeded the recovery limit of 2 wt % P which is 70% of the amount of sludge and 85% of the phosphorus load. Other nutrients are not affected by the recovery obligation. However, many P recovery processes recover other nutrients, too. Considering three different scenarios for future German sewage sludge disposal shows that 70–77% of the P load in sewage sludge will probably be recovered in the future. At the same time, this applies for about 0–16% nitrogen, 36–52% of calcium, 31–53% of potassium, and 40–52% of magnesium. However, these recovered nutrients loads can substitute only 1% or less of the commercial fertilizer demand except from phosphorus which is up to 43% of the demand.
Pseudomonas aeruginosa biofilms exhibit an intrinsic resistance to antibiotics and constitute a considerable clinical threat. In cystic fibrosis, a common feature of biofilms formed by P. aeruginosa in the airway is the occurrence of mutants deficient in flagellar motility. This study investigates the impact of flagellum deletion on the structure and antibiotic tolerance of P. aeruginosa biofilms, and highlights a role for the flagellum in adaptation and cell survival during biofilm development. Mutations in the flagellar hook protein FlgE influence greatly P. aeruginosa biofilm structuring and antibiotic tolerance. Phenotypic analysis of the flgE knockout mutant compared to the wild type (WT) reveal increased fitness under planktonic conditions, reduced initial adhesion but enhanced formation of microcolony aggregates in a microfluidic environment, and decreased expression of genes involved in exopolysaccharide formation. Biofilm cells of the flgE knock-out mutant display enhanced tolerance towards multiple antibiotics, whereas its planktonic cells show similar resistance to the WT. Confocal microscopy of biofilms demonstrates that gentamicin does not affect the viability of cells located in the inner part of the flgE knock-out mutant biofilms due to reduced penetration. These findings suggest that deficiency in flagellar proteins like FlgE in biofilms and in cystic fibrosis infections represent phenotypic and evolutionary adaptations that alter the structure of P. aeruginosa biofilms conferring increased antibiotic tolerance.
Tuschenanalyse im P 11702
(2021)
Near-inframed reflectography and imaging X-Ray flourescence analysis reveal that carbon inks of two different compositions were used in the papyrus manuscript Berlin P 11702. in contrast with the writing ink, one of the carbon drawing inks contained a significant addition of iron. This result emphasises the need for routine instrumental ink analysis.
For the first time, fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to detect per- and polyfluoroalkyl substances (PFAS) in various soil and sewage sludge samples. The method can be used to determine the speciation of inorganic and organic fluorides, without pre-treatment of solid samples. Therefore, XANES spectra of several inorganic fluorides as well as selected fluorinated organic compounds were recorded. While inorganic fluorides partially exhibit a variety of sharp spectral features in the XANES spectrum, almost all inspected organofluorine compounds show two distinct broad features at 688.5 and 692.0 eV. Moreover, the peak intensity ratio 688.5 eV/692.0 eV in the PFAS XANES spectrum can be inversely correlated to the chain length of the perfluoro sulfonic acid group. The detection of targeted PFAS by bulk-XANES spectroscopy in combination with linear combination fitting in soils and sewage sludges was not applicable due to the low organic fluorine to total fluorine ratio of the samples (0.01–1.84%). Nonetheless, direct analysis of pure PFAS revealed that analysis of organofluorine species might be achieved in higher concentrated samples. Furthermore, quantitative measurements by combustion ion chromatography (CIC) evaluated as sum parameters extractable organically bound fluorine (EOF) and total fluorine (TF) emphasize that besides soils, sewage sludges are a significant source of organic fluorine in agriculture (154–7209 μg/kg).
Chemical modification of wood applying benzotriazolyl-activated carboxylic acids has proven to be a versatile method for the durable functionalization of its lignocellulosic biopolymers. Through this process, the material properties of Wood can be influenced and specifically optimized. To check the scope and limitations of this modification method, various benzamide derivatives with electron-withdrawing (EWG) or electron-donating (EDG) functional groups in different positions of the aromatic ring were synthesized and applied for covalent modification of Scots pine (Pinus sylvestris L.) sapwood in this study. The bonded amounts of substances (up to 2.20 mmol) were compared with the reactivity constants of the Hammett equation, revealing a significant correlation between the modification efficiency and the theoretical reactivity constants of the corresponding aromatic substitution pattern. The successful covalent attachment of the respective substituted benzamides was proven by attenuated total reflection infrared (ATR-IR) spectroscopy, while the stability of the newly formed ester bond was proven in a standardized leaching test.
Honeybee symbionts, predominantly bacteria, play important roles in honeybee health, nutrition, and pathogen protection, thereby supporting colony health. On the other hand, fungi are often considered indicators of poor bee health, and honeybee microbiome studies generally exclude fungi and yeasts. We hypothesized that yeasts may be an important aspect of early honeybee biology, and if yeasts provide a mutual benefit to their hosts, then honeybees could provide a refuge during metamorphosis to ensure the presence of yeasts at emergence. We surveyed for yeast and fungi during pupal development and metamorphosis in worker bees using fungal-specific quantitative polymerase chain reaction (qPCR), next-generation sequencing, and standard microbiological culturing. On the basis of yeast presence in three distinct apiaries and multiple developmental stages, we conclude that yeasts can survive through metamorphosis and in naïve worker bees, albeit at relatively low levels. In comparison, known bacterial mutualists, like Gilliamella and Snodgrassella, were generally not found in pre-eclosed adult bees. Whether yeasts are actively retained as an important part of the bee microbiota or are passively propagating in the colony remains unknown. Our demonstration of the constancy of yeasts throughout development provides a framework to further understand the honeybee microbiota.
The evolution of biological complexity is associated with the emergence of bespoke immune systems that maintain and protect organism integrity. Unlike the well-studied immune systems of cells and individuals, little is known about the origins of immunity during the transition to eusociality, a major evolutionary transition comparable to the evolution of multicellular organisms from single-celled ancestors. We aimed to tackle this by characterizing the immune gene repertoire of 18 cockroach and termite species, spanning the spectrum of solitary, subsocial and eusocial lifestyles. We find that key transitions in termite sociality are correlated with immune gene family contractions. In cross-species comparisons of immune gene expression, we find evidence for a caste-specific social defence system in termites, which appears to operate at the expense of individual immune protection. Our study indicates that a major transition in organismal complexity may have entailed a fundamental reshaping of the immune system optimized for group over individual defence.
While sociality is present in a taxonomically diverse number of species, most animals remain solitary (Bourke, 2011). Over the last centuries, this apparent imbalance in social and non-social animals has led to a great deal of research aimed at shedding light on the biotic and abiotic factors explaining the emergence and maintenance of sociality in nature (West et al., 2015).
Among them, microbes were quickly identified as a major problem for the evolution of social life, because frequent contact between group members typically facilitates the transmission of pathogens, high nest fidelity favours the establishment of microbial pathogens close to their social hosts and, finally, because social groups often exhibit limited genetic diversity and thus limited genetic resistance against certain pathogen strains (Schmid-Hempel, 1998; Cremer et al., 2007). However, this long-standing view has changed considerably over the last few years. Recent research indeed revealed that group living may be more effective than solitary living to Limit the risk of infection by pathogenic microbes because group living also allows the development of an additional layer of defence against pathogens in the form of social immunity (Cremer et al., 2007; Cotter and Kilner, 2010). Under strong pressure from pathogens, microbes could therefore promote, rather than hinder, the evolutionary transition from solitary to group Living (Meunier, 2015; Biedermann and Rohlfs, 2017). Moreover, we are increasingly aware that many microbes provide essential benefits to their hosts by performing critical digestive, physiological, and reproductive functions (Engel and Moran, 2013; McFall-Ngai et al., 2013). The need to Access beneficial microbes may thus have played a role in the expression of frequent and tight interactions between conspecifics and ultimately promoted social evolution (Wilson, 1971; Onchuru et al., 2018). Finally, a growing number of studies suggest that microbes could enforce the Aggregation and expression of cooperative behaviours of the hosts to increase their chance of reaching new hosts and may therefore be involved in the evolution of host sociality (Lewin-Epstein et al., 2017) (but see Johnson and Foster, 2018).
The concept of circular economy supports mitigation of climate change and other environmental pressures to the planet. Circulating materials in anthropogenic processes come with the risk of accumulating hazardous substances and compounds. In this concept, waste incineration or waste-to-energy (WtE) is a necessary technology to remove these compounds from the life cycle. In this mini-review, contaminants of major importance in the flue gas from waste incineration plants and their environmental impact are discussed. Air pollution of WtE is often seen as the most relevant environmental impact of this treatment option. The emission values parameter set for different countries is presented and compared. The most stringent legally set of emission values could be found in parts of Europe and South Korea. Japan also permits similar strict values when authorising individual incineration plants. In North America, the values are partially less strict as the best available technologies in Europe suggest being possible. Emerging economies, such as India and China, have shown efforts to improve their environmental protection standards but still have room to improve. This could be set in relation to other industrial emitting processes and therefore could be used to assess the relevance of this industry sector to the national emission inventories.
This work is aimed at exploring the recovery of heavy metals from the fine fraction of solid waste incineration bottom ash.
For this study, wet-discharged bottom ash fine-fraction samples from full-scale treatment plants in Germany and Sweden were analyzed. The potential for the recovery of heavy metal compounds was investigated through wet density-separation with a shaking table. The feed materials were processed without any pre-treatment and the optimum processing conditions were determined by means of design of experiments. Tilt angle and stroke frequency were identified as the most relevant parameters, and the optimum settings were − 7.5° and 266 rpm, respectively. The obtained balanced copper enrichments (and yields) were 4.4 (41%), 6.2 (28%) and 2.4 (23%). A maximum copper enrichment of 14.5 with 2% yield was achieved, providing a concentrate containing 35.9 wt.% relevant heavy metal elements. This included 26.3 wt.% iron, 4.3 wt.% zinc and 3.8 wt.% copper. In conclusion, density separation with shaking tables can recover heavy metals from bottom ash fine fractions. Medium levels of heavy metal enrichment (e.g., for Cu 2.7–4.4) and yield (Cu: 26–41%) can be reached simultaneously.
However, the separation performance also depends on the individual bottom ash sample.
Biocides used as disinfectants are important to prevent the transmission of pathogens, especially during the current antibiotic resistance crisis. This crisis is exacerbated by phenotypically tolerant persister subpopulations that can survive transient antibiotic Treatment and facilitate resistance evolution. Here, we show that E. coli displays persistence against a widely used disinfectant, benzalkonium chloride (BAC). Periodic, persister-mediated failure of disinfection rapidly selects for BAC tolerance, which is associated with reduced cell Surface charge and mutations in the lpxM locus, encoding an enzyme for lipid A biosynthesis.
Moreover, the fitness cost incurred by BAC tolerance turns into a fitness benefit in the presence of antibiotics, suggesting a selective advantage of BAC-tolerant mutants in antibiotic environments. Our findings highlight the links between persistence to disinfectants and resistance evolution to antimicrobials.
Phosphorus (P) resource availability and quality is declining and recycling P-fertilizers from waste materials are becoming increasingly important. One important secondary P resource is sewage sludge (SSL) where P is often bound as aluminum phosphate (Al-P), iron phosphate (Fe-P) and polyphosphate (poly-P), respectively. Thermal treatment in different ways is a promising way in P recycling to produce highly plant-available P-fertilizers. To investigate mechanisms behind transformation of hardly available P-species toward plant-available P forms we treated a model SSL containing different kinds of defined P sources by low-temperature conversion (LTC) at 500 °C and subsequent thermochemical treatment of the LTC product with Na additives (TCT) at 950 °C, respectively. Pot experiments with ryegrass were carried out to determine the plant availability of P of the different treatments. The poly-P (here pyrophosphates) based fertilizers had a very high plant availability after both thermal treatments. During LTC treatment the plant availability of the Fe-P and Al-P variants increased because of the Formation of Fe(II) phosphates and/or pyro-/polyphosphates. Especially the formation of Al-polyphosphate shows a high plant availability. The subsequent TCT further increased strongly the plant availability of the Fe-P variants because of the formation of highly plant-available CaNaPO4. Thus, a direct TCT without prior LTC probably also produce CaNaPO4 and is recommended for Fe-P based SSL. However, a molar Ca/P ratio of 1 in the fertilizer is favorable for CaNaPO4 formation. Thus, the knowledge on the source of primary P in SSL is essential for choosing the accurate thermal treatment method to produce highly plant-available P-fertilizers from SSL.
Spatial Period of Laser-Induced Surface Nanoripples on PET Determines Escherichia coli Repellence
(2021)
Bacterial adhesion and biofilm formation on surfaces are associated with persistent microbial contamination, biofouling, and the emergence of resistance, thus, calling for new strategies to impede bacterial surface colonization. Using ns-UV laser treatment (wavelength 248 nm and a pulse duration of 20 ns), laser-induced periodic surface structures (LIPSS) featuring different submicrometric periods ranging from ~210 to ~610 nm were processed on commercial poly(ethylene terephthalate) (PET) foils. Bacterial adhesion tests revealed that these nanorippled surfaces exhibit a repellence for E. coli that decisively depends on the spatial periods of the LIPSS with the strongest reduction (~91%) in cell adhesion observed for LIPSS periods of 214 nm. Although chemical and structural analyses indicated a moderate laser-induced surface oxidation, a significant influence on the bacterial adhesion was ruled out. Scanning electron microscopy and additional biofilm studies
using a pili-deficient E. coli TG1 strain revealed the role of extracellular appendages in the bacterial repellence observed here.
Fungi are ecologically outstanding decomposers of lignocellulose. Fungal lignocellulose degradation is prominent in saprotrophic Ascomycota and Basidiomycota of the subkingdom Dikarya. Despite ascomycetes dominating the Dikarya inventory of aquatic environments, genome and transcriptome data relating to enzymes involved in lignocellulose decay remain limited to terrestrial representatives of these phyla. We sequenced the genome of an exclusively aquatic ascomycete (the aquatic hyphomycete Clavariopsis aquatica), documented the presence of genes for the modification of lignocellulose and its constituents, and compared differential gene expression between C. aquatica cultivated on lignocellulosic and sugar-rich substrates. We identified potential peroxidases, laccases, and cytochrome P450 monooxygenases, several of which were differentially expressed when experimentally grown on different substrates. Additionally, we found indications for the regulation of pathways for cellulose and hemicellulose degradation. Our results suggest that C. aquatica is able to modify lignin to some extent, detoxify aromatic lignin constituents, or both. Such characteristics would be expected to facilitate the use of carbohydrate components of lignocellulose as carbon and energy sources.
Phosphorus rich sewage sludge ash is a promising source to produce phosphorus recycling fertilizer. However, the low plant availability of phosphorus in these ashes makes a treatment necessary. A thermochemical treatment (800–1000 °C) with alkali additives transforms poorly plant available phosphorus phases to highly plant available calcium alkali Phosphates (Ca,Mg)(Na,K)PO4. In this study, we investigate the use of K2SO4 as additive to produce a phosphorus potassium fertilizer in laboratory-scale experiments (crucible). Pure K2SO4 is not suitable as high reaction temperatures are required due to the high melting point of K2SO4.
To overcome this barrier, we carried out series of experiments with mixtures of K2SO4 and Na2SO4 resulting in a lower economically feasible reaction temperature (900–1000 °C). In this way, the produced phosphorus potassium fertilizers (8.4 wt.% K, 7.6 wt.% P) was highly plant available for phosphorus indicated by complete extractable phosphorus in neutral ammonium citrate solution. The added potassium is, in contrast to sodium, preferably incorporated into silicates instead of phosphorus phases. Thus, the highly extractable phase (Ca,Mg)(Na,K)PO4 in the thermochemical products contain less potassium than expected. This preferred incorporation is confirmed by a pilot-scale trial (rotary kiln) and thermodynamic calculation.
Conventional phosphate fertilizers are usually highly water-soluble and rapidly solubilize when moistened by the soil solution. However, if this solubilization is not in alignment with plants demand, P can react with the soil colloidal phase, becoming less available over time. This is more pronounced in acidic, oxidic tropical soils, with
high P adsorption capacity, reducing the efficiency of P fertilization. Furthermore, these fertilizers are derived from phosphate rock, a non-renewable resource, generating an environmental impact. To assess these concerns, waste-recycled P sources (struvite, hazenite and AshDec®) were studied for their potential of reducing P Fixation by the soil and improving the agronomic efficiency of the P fertilization. In our work, we compared the solubilization dynamics of struvite, hazenite, AshDec® to triple superphosphate (TSP) in a sandy clay loam Ferralsol, as well as their effect on solution pH and on soil P pools (labile, moderately-labile and non-labile) via an incubation experiment. Leaching columns containing 50 g of soil with surface application of 100 mg per column (mg col 1) of P from each selected fertilizer and one control (nil-P) were evaluated for 60 days. Daily leachate samples from the column were analyzed for P content and pH. Soil was stratified in the end and submitted to P
fractionation. All results were analyzed considering p < 0.05. Our findings showed that TSP and struvite promoted an acid P release reaction (reaching pHs of 4.3 and 5.5 respectively), while AshDec® and hazenite reaction was alkaline (reaching pHs of 8.4 and 8.5 respectively). Furthermore, TSP promoted the highest P release among all sources in 60 days (52.8 mg col 1) and showed rapid release dynamic in the beginning, while struvite and hazenite showed late release dynamics and lower total leached P (29.7 and 15.5 mg col 1 P respectively). In contrast, no P-release was detected in the leachate of the AshDec® over the whole trial period. Struvite promoted
the highest soil labile P concentration (7938 mg kg 1), followed by hazenite (5877 mg kg 1) and AshDec® (4468 mg kg 1), all higher than TSP (3821 mg kg 1), while AshDec® showed high moderately-labile P (9214 mg kg 1), reaffirming its delayed release potential.
Das mechanische Recycling von Kunststoffen ist seit Jahren großtechnisch etabliert, hat aber technische und ökonomische Grenzen. Durch Verfahren des chemischen Recyclings gelangt man zurück zu Monomeren oder den Rohstoffen, so dass am Ende wieder Neuware für alle Einsatzgebiete von Kunststoffen entsteht. Die Vielfalt von chemischen Recyclingverfahren ist groß. Die Kapazitäten der Anlagen sind heute noch gering und die Wirtschaftlichkeit wird stark vom Ölpreis beeinflusst.
Die Rentabilitätsgrenze liegt derzeit bei einem Preis zwischen 50 und 60 US-$ pro Barrel.
The physical and chemical analysis of aerosols using reliable and physically traceable methods is important for the thorough investigation of airborne particles to support a better understanding of their origin as well as their health and climate impacts. Within the European Metrology Research AeroMet project,the aim of hysikalisch–Technische Bundesanstalt’s (PTB) X-ray spectrometry group is to develop and establish traceable and reliable X-ray methods to measure the elemental mass deposition per unit area, the elemental composition,and the chemical binding state of particulate matter supported by a flat substrate. This approach can substantially contribute to support quantitative analytical methods during on-site measurement campaigns where portable Instrumentation is employed by qualifying suitable calibration samples for commercial analytical X-ray instruments and by investigating samples collected during the field campaign.
Lack of long-time stability of dsDNA-based supramolecular assemblies is an important issue that hinders their applications. In this work, 20 base pairs long dsDNA fragments [(dCdG)20
65%] composed of 65% dCdG and 35% dAdT nucleotides were tethered via a thiol to the surface of a gold electrode. The selfassembled (dCdG)20
-65% monolayer was immersed in solutions
containing ectoine, a compatible solute. Electrochemical results showed that these monolayers were stable for one month. In situ IR spectroscopy indicated that ectoine interacts weakly with the phosphate-ribose backbone, dehydrating the phosphate groups and stabilizing the A-DNA conformation. This structural reorganization led to a reorientation of nucleic acid base pairs and a local disruption of the double-helix structure. However, the conformation and orientation of the dsDNA fragment was stable in the
Materials that confer antimicrobial activity, be that by innate property, leaching of biocides or design features (e.g., non-adhesive materials) continue to gain popularity to combat the increasing and varied threats from microorganisms, e.g., replacing inert surfaces in hospitals with copper. To understand how efficacious these materials are at controlling microorganisms, data is usually collected via a standardised test method. However, standardised test methods vary, and often the characteristics and methodological choices can make it difficult to infer that any perceived antimicrobial activity demonstrated in the laboratory can be confidently assumed to an end-use setting. This review provides a critical analysis of standardised methodology used in academia and industry, and demonstrates how many key methodological choices (e.g., temperature, humidity/moisture, airflow, surface topography) may impact efficacy assessment, highlighting the need to carefully consider intended antimicrobial end-use of any product.
Stormwater from urban areas can transport biocidally active substances and related transformation products from buildings into the environment. The occurrence of these substances in urban runoff depends on the availability of water, and on ultraviolet radiation exposure that causes photolytic reactions. In a systematic laboratory study, painted test specimens were exposed to either ultraviolet radiation, water contact, or a combination of both. Leaching of the biocidally active substances carbendazim, diuron, octylisothiazolinone, terbutryn, and selected transformation products of terbutryn and diuron were observed under various exposure conditions. Remaining concentrations of these substances in the paint were quantified. It was demonstrated that the distribution of active substances and transformation products in eluates and in the coatings themselves differs with exposure conditions. Strategies for environmental monitoring of biocide emissions need to consider the most relevant transformation products. However, environmental concentrations of biocidally active substances and transformation products depend on earlier exposure conditions. As a consequence, monitoring data cannot describe emission processes and predict expected leaching of biocidally active substances from buildings if the data are collected only occasionally.
Condensation particle counters (CPCs) are widely used for the measurement of aerosol particle number concentrations in the size range from approximately 3 nm to 3 μm. For an SI-traceable calibration of the size-dependent counting efficiency, which is advisable on a regular basis and required in several applications, Faraday cup aerosol electrometers (FCAEs) are considered to be a suitable SI-traceable reference.While the volumetric aerosol inlet flowrate and the electrical current measurement in FCAEs can be related to respective SI references, inter-comparison exercises for FCAEs are still performed on a regular basis to establish reliable uncertainty budgets and to further investigate the influences of designs and operational parameters on comparability. This is strongly demanded in the international community of metrological institutes and aerosol calibration facilities around the world, which provide CPC calibrations. In the present study, the performance of FCAEs was investigated,using Ag test aerosol particles with a 30 nm particle diameter by varying the inlet flowrates from 0.5 l min−1 to 4 l min−1. From our experimental results, significant deviations were observed in FCAE currents at sample flowrates smaller than 1.5 l min−1. It is recommended that these discrepancies should be quantified before an FCAE is used for CPC calibration at low sample flowrates and small particle sizes in the sub-30 nm size range.
In 2018 municipal solid waste (MSW) incineration in Europe produced nearly 19 Mt of bottom ash (BA); only 46 %-wt. was treated, often in poorly performing plants, leaving behind 10 Mt of untreated and unrecovered BA, destined to landfill. This work was based on the inventory of BA across Europe, and on the hypothesis to achieve complete BA valorisation through two assumptions: treating 100% BA and minimizing the loss of valuable fractions due to technical limitations of state-of-the-art processes in comparison to advanced innovative processes. The research involved three phases: characterization of potential secondary raw materials (metals and mineral fraction) currently lost from untreated (the surplus compared to treatment capacity) and unrecovered BA (the fine fraction) through material flow analysis; environmental assessment (energy balance and net GHG emissions) of complete BA valorisation; investigation of the economic feasibility of complete BA Valorisation through state-of-the-art technologies. The resulting 2.14 Mt loss of valuable materials included 1 Mt Mineral fraction and 0.97 Mt ferrous metals, mostly from untreated BA, and 0.18 Mt non-ferrous metals, mostly from unrecovered BA. The energy balance and GHGs emissions required by the treatment of the currently untreated and unrecovered fractions of BA resulted in energy and GHGs emissions savings. Economic profitability was driven by iron and copper recycling and avoided landfill fees. Profitability was achieved by two thirds of considered countries (average values: NPV 83 M€, ROI 20%, payback time 11 years) with BA mass flow exceeding 0.02 Mt.
The steel industry is an important engine for sustainable growth, added value, and high-quality employment within the European Union. It is committed to reducing its CO2 emissions due to production by up to 50% by 2030 compared to 1990′s level by developing and upscaling the technologies required to contribute to European initiatives, such as the Circular Economy Action Plan (CEAP) and the European Green Deal (EGD). The Clean Steel Partnership (CSP, a public–private partnership), which is led by the European Steel Association (EUROFER) and the European Steel Technology Platform (ESTEP), defined technological CO2 mitigation pathways comprising carbon direct avoidance (CDA), smart carbon usage SCU), and a circular economy (CE). CE ap-proaches ensure competitiveness through increased resource efficiency and sustainability and consist of different issues, such as the valorization of steelmaking residues (dusts, slags, sludge) for internal recycling in the steelmaking process, enhanced steel recycling (scrap use), the use of secondary carbon carriers from non-steel sectors as a reducing agent and energy source in the steelmaking process chain, and CE business models (supply chain analyses). The current paper gives an overview of different technological CE approaches as obtained in a dedicated workshop called “Resi4Future—Residue valorization in iron and steel industry: sustainable solutions for a cleaner and more competitive future Europe” that was organized by ESTEP to focus on future challenges toward the final goal of industrial deployment.
The clothes moth Tineola bisselliella is one of a few insects that can digest keratin, leading to the destruction of clothing, textiles and artwork. The mechanism of keratin digestion is not yet fully understood, partly reflecting the lack of publicly available genomic and transcriptomic data. Here we present a high-quality gut transcriptome of T. bisselliella generated from larvae reared on keratin-rich and keratin-free diets. The overall transcriptome consists of 428,221 contigs that were functionally annotated and screened for candidate enzymes involved in keratin utilization. As a mechanism for keratin digestion, we identified cysteine synthases, cystathionine β-synthases and cystathionine γ-lyases. These enzymes release hydrogen sulfite, which may reduce the disulfide bonds in keratin. The dataset also included 27 differentially expressed contigs with trypsin domains, among which 20 were associated with keratin feeding. Finally, we identified seven collagenases that were upregulated on the keratin-rich diet. In addition to this enzymatic repertoire potentially involved in breaking down keratin, our analysis of poly(A)-enriched and poly(A)-depleted transcripts suggested that T. bisselliella larvae possess an unstable intestinal microbiome that may nevertheless contribute to keratin digestion
Basic oxygen furnace slags (BOFS) are by-products of the steelmaking process. Several researchers have studied the production of Portland cement clinker and metallic iron from BOFS via a reductive treatment.
In this study, we applied a carbothermal reduction of BOFS in a technical-scale electric arc furnace and characterised the clinker-like products. Those clinker-like non-metallic products (NMPs) had a chemical and mineralogical composition comparable to clinker for ordinary Portland cement (OPC) and contained large elongated alite crystals as major component. The pure NMPs reacted more slowly and achieved a lower degree of hydration compared with commercial OPC.
If the reactivity of the products can be further increased by employing specific adaptations, it can be used as a full clinker substitute for OPC. Nevertheless, it is also an option to use the material without further modifications as a cement component or concrete addition, which contributes to the strength development in both cases.
Background
A European inter-laboratory test with 29 participating laboratories investigated whether a battery of four ecotoxicological tests is suitable for assessing the environmental compatibility of construction products. For this purpose, a construction product was investigated with the dynamic surface leaching test (DIN CEN/TS 16637-2) and the percolation test (DIN CEN/TS 16637-3). The eluates were produced centrally by one laboratory and were tested by the participants using the following biotests: algae test (ISO 8692), acute daphnia test (ISO 6341), luminescent bacteria test (DIN EN ISO 11348), and fish egg test (DIN EN ISO 15088). As toxicity measures, EC50 and LID values were calculated.
Results
Toxic effects of the eluates were detected by all four biotests. The bacteria test was by far the most sensitive, followed by the algae test and the daphnia test; the fish egg test was the least sensitive for eluates of both leaching tests. The toxicity level of the eluates was very high in the bacteria, daphnia, and algae test, with lowest ineffective dilution values of LID = 70 to LID = 13,000 and corresponding EC50 values around or even below 1 volume percent. The reproducibility (approximated by interlaboratory variability) of the biotests was good (< 53%) to very good (< 20%), regardless of the toxicity level of the eluates. The reproducibility of the algae test was up to 80%, and thus still acceptable.
Conclusion
It can be confirmed that the combination of leaching and ecotoxicity tests is suitable to characterize with sufficient reproducibility the environmental impact posed by the release of hazardous substances from construction products.
Metagenomic datasets of air samples collected during episodes of severe smoke-haze in Malaysia
(2021)
Transboundary emissions of smoke-haze from land and forest fires have recurred annually during the dry period (June to October, over the past few decades) in South East Asia. Hazardous air quality has been recorded in Malaysia during these episodes. Agricultural practices such as slash-and-burn of biomass and peat fires particularly in Sumatera and Kalimantan, Indonesia, have been implicated as the major causes of the haze. Past findings have shown that a diversity of microbes can thrive in air including in smoke-haze polluted air. In this study, metagenomic data were generated to reveal the diversity of microorganisms in air during days with and without haze. Air samples were collected during non-haze (2013A01) and two haze (2013A04 and 2013A05) periods in the month of June 2013. DNA was extracted from the samples, subjected to Multiple Displacement Amplification and whole genome sequencing (Next Generation Sequencing) using the HiSeq 2000 Platform. Extensive bio-informatic analyses of the raw sequence data then followed. Raw reads from these six air samples were deposited in the NCBI SRA databases under Bioproject PRJNA662021 with accession numbers SRX9087478, SRX9087479 and SRX9087480.
Over the last few years, the Federal Institute for material research (BAM, Berlin) together with the Centre for the Study of Manuscript Cultures (CSMC, University of Hamburg) have initiated a systematic material investigation of black inks produced from Late Antiquity to the Middle Ages (ca. fourth century CE–fourteenth/fifteenth centuries CE), aimed primarily at extending and complementing findings from previous sporadic studies. Part of this systematic investigation has focused on Egyptian Coptic manuscripts, and the present preliminary study is one of its outputs. It centres on a corpus of 45 Coptic manuscripts—43 papyri and 2 ostraca—preserved at the Palau-Ribes and Roca-Puig collections in Barcelona. The manuscripts come from the Monastery of Apa Apollo at Bawit, one of the largest monastic settlements in Egypt between the Late Antiquity and the Early Islamic Period (sixth–eighth centuries CE). The composition of their black inks was investigated in situ using near-infrared reflectography (NIRR) and X-ray fluorescence (XRF). The analyses determined that the manuscripts were written using different types of ink: pure carbon ink; carbon ink containing iron; mixed inks containing carbon, polyphenols and metallic elements; and iron-gall ink. The variety of inks used for the documentary texts seems to reflect the articulate administrative system of the monastery of Bawit. This study reveals that, in contrast to the documents, written mostly with carbon-based inks, literary biblical texts were written with iron-gall ink. The frequent reuse of papyrus paper for certain categories of documents may suggest that carbon-based inks were used for ephemeral manuscripts, since they were easy to erase by abrasion.
There are viral, fungal, bacterial and trypanosomal pathogens that negatively impact the individual and superorganismal health of the western honey bee. One fungal pathogen, Ascosphaera apis , affects larvae and causes the disease chalkbrood. A previous genome analysis of As. apis revealed that its genome encodes for RNA interference genes, similar to other fungi and eukaryotes. Here, we examined whether As. apis -targeting double-stranded RNA species could disrupt the germination of As. apis.
We observed that when spores were co-incubated with As. apis -targeting dsRNA, fewer spores were activated for germination, suggesting an uptake of exogenous genetic material at the very onset of germination and consequent damage to essential transcripts needed for germination. Overall, these results indicate that the causative agent of chalkbrood disease, As. apis , can be successfully targeted using an RNAi-based strategy.
Plant resource acquisition strategies were ecosystem-specific with distinct mutualism with arbuscular mycorrhizal (AM) fungi. Root traits indicated conservative resource economics in the arid shrubland, but an acquisitive and self-sufficient (“do-it-yourself”) acquisition strategy in the semiarid coastal matorral, resulting in large carbon (C) investments (green). Forest plants with conservative root traits seem to intensively outsource their acquisition to AM fungi, compensating for lower uptake capacities of conservative roots (red line). High allocations of freshly assimilated C into AM fungal storage compounds illustrated the relevance of AM fungi as C sink, especially in the semiarid matorral.
The main obstacle to bottom ash (BA) being used as a recycling aggregate is the content of salts and potential toxic elements (PTEs), concentrated in a layer that coats BA particles. This work presents a dry treatment for the removal of salts and PTEs from BA particles. Two pilotscale abrasion units (with/without the removal of the fine particles) were fed with different BA samples. The performance of the abrasion tests was assessed through the analyses of particle size and moisture, and that of the column leaching tests at solid-to-liquid ratios between 0.3 and 4.
The results were: the particle-size distribution of the treated materials was homogeneous (25 wt % had dimensions <6.3 mm) and their moisture halved, as well as the electrical conductivity of the leachates. A significant decrease was observed in the leachates of the treated BA for sulphates (44%), chlorides (26%), and PTEs (53% Cr, 60% Cu and 8% Mo). The statistical analysis revealed good correlations between chloride and sulphate concentrations in the leachates with Ba, Cu, Mo, and Sr, illustrating the consistent behavior of the major and minor components of the layer surrounding BA particles. In conclusion, the tested process could be considered as promising for the improvement of BA valorization.
The existence of microbial activity hotspots in temperate regions of Earth is driven by soil heterogeneities, especially the temporal and spatial availability of nutrients. Here we investigate whether microbial activity hotspots also exist in lithic microhabitats in one of the most arid regions of the world, the Atacama Desert in Chile. While previous studies evaluated the total DNA fraction to elucidate the microbial communities, we here for the first time use a DNA separation approach on lithic microhabitats, together with metagenomics and other analysis methods (i.e., ATP, PLFA, and metabolite analysis) to specifically gain insights on the living and potentially active microbial community. Our results show that hypolith colonized rocks are microbial hotspots in the desert environment. In contrast, our data do not support such a conclusion for gypsum crust and salt rock environments, because only limited microbial activity could be observed. The hypolith community is dominated by phototrophs, mostly Cyanobacteria and Chloroflexi, at both study sites. The gypsum crusts are dominated by methylotrophs and heterotrophic phototrophs, mostly Chloroflexi, and the salt rocks (halite nodules) by phototrophic and halotolerant endoliths, mostly Cyanobacteria and Archaea. The major environmental constraints in the organic-poor arid and hyperarid Atacama Desert are water availability and UV irradiation, allowing phototrophs and other extremophiles to play a key role in desert ecology.
This study details a theoretical analysis of leaky and waveguide modes in biperiodic all-dielectric holograms. By tuning diffraction orders and subsequently confining local density of optical states at two distinct resonance wavelengths, we present a new class of highly sensitive refractive index biosensing platforms that are capable of resolving 35.5 to 41.3 nm/RIU of spectral shift for two separate biological analytes.
Bauprodukte und Einrichtungsgegenstände für Innenräume, wie Bodenbeläge und Wandpaneele, sollen das Wohlbefinden und die Gesundheit der Raumnutzerinnen und -nutzer nicht durch das Ausdünsten von Geruchsstoffen stören. Mit der Geruchsprüfung nach ISO 16000-28 „Innenraumluft - Bestimmung der Geruchsstoffemissionen aus Bauprodukten mit einer Emissionsprüfkammer“ wird der Produktgeruch zu einer messbaren Größe. So kann z. B. die empfundene Intensität, also die Stärke eines Geruchseindruckes, mit Hilfe eines Vergleichsmaßstabes von Probandinnen und Probanden ermittelt werden. Im hier vorgestellten Projekt werden Vorschläge zur Weiterentwicklung der Methode vorgestellt, um im Ergebnis die Reproduzierbarkeit der Messergebnisse weiter zu verbessern. Dabei werden vor allem das Probenpräsentationssystem und die Bewertungsmethodik für die empfundene Intensität bei der Bewertung von Bauprodukten gemäß AgBB-Schema betrachtet, da diese einen wesentlichen Einfluss haben.
Phase formation and evolution was investigated in the CaO–SiO2 system in the range of 70–80 mol% CaO. The samples were container-less processed in an aerodynamic levitation system and crystallization was followed in situ by synchrotron x-ray diffraction at the beamline P21.1 at the German electron synchrotron (DESY). Modification changes of di- and tricalcium silicate were observed and occurred at lower temperatures than under equilibrium conditions. Despite deep sample undercooling, no metastable phase formation was observed within the measurement timescale of 1 s. For the given cooling rates ranging from 300 K s−1 to about 1 K s−1, no decomposition of tricalcium silicate was observed. No differences in phase evolution were observed between reducing and oxidizing conditions imposed by the levitation gas (Ar and Ar + O2). We demonstrate that this setup has great potential to follow crystallization in refractory oxide liquids in situ. For sub-second primary phase formation faster detection and for polymorph detection adjustments in resolution have to be implemented.
Emission testing of volatile organic compounds (VOC) from materials and products is commonly based on emission test chamber measurements. To ensure the comparability of results from different testing laboratories, their measurement performance must be verified. For this purpose, Bundesanstalt für Materialforschung und -prüfung (BAM) organizes an international proficiency test (round robin test, RRT) every two years using well-characterized test materials (one sealant, one furniture board, and four times a lacquer) with defined VOC emissions. The materials fulfilled the requirements of homogeneity, reproducibility, and stability. Altogether, 36 VOCs were included of which 33 gave test chamber air concentrations between 13 and 83 µg/m3. This is the typical concentration range to be expected and to be quantified when performing chamber tests. Three compounds had higher concentrations between 326 and 1105 µg/m3. In this paper, the relative standard deviations (RSD) of BAM round robin tests since 2008 are compared and the improvement of the comparability of the emission chamber testing is shown by the decrease of the mean RSD down to 28 % in 2018. In contrast, the first large European interlaboratory comparison in 1999 showed a mean RSD of 51 %.
Bacteria generally interact with the environment via processes involving their cell-envelope. Thus, techniques that may shed light on their surface chemistry are attractive tools for providing an understanding of bacterial interactions. One of these tools is Al Kα-excited photoelectron spectroscopy (XPS) with its estimated information depth of <10 nm. XPS-analyses of bacteria have been performed for several decades on freeze-dried specimens in order to be compatible with the vacuum in the analysis chamber of the spectrometer. A limitation of these studies has been that the freeze-drying method may collapse cell structure as well as introduce surface contaminants. However, recent developments in XPS allow for analysis of biological samples at near ambient pressure (NAP-XPS) or as frozen hydrated specimens (cryo-XPS) in vacuum. In this work, we have analyzed bacterial samples from a reference strain of the Gram-negative bacterium Pseudomonas fluorescens using both techniques. We compare the results obtained and, in general, observe good agreement between the two techniques. Furthermore, we discuss advantages and disadvantages with the two analysis approaches and the output data they provide. XPS reference data from the bacterial strain are provided, and we propose that planktonic cells of this strain (DSM 50090) are used as a reference material for surface chemical analysis of bacterial systems.
There is an ongoing debate on European scale concerning the criticality of phosphorus. In Switzerland and Germany, phosphorus recovery from phosphorus-rich waste streams will become obligatory. Sewage sludge ash is rich in phosphorus and may become an important secondary feedstock. Thermochemical treatment of sewage sludge ash with sodium sulphate under reducing conditions was shown to remove heavy metals from the solid product and produce the fully plant available crystalline phase CaNaPO4. Pilot-scale experiments in a rotary kiln were carried out at temperatures between 750 and 1000 °C and were compared to laboratory-scale experiments with crucibles. Process upscaling was successfully demonstrated but a series of differences were noticed: In comparison to laboratory-scale, solubility of phosphorus in samples from pilot-scale experiments was lower at all chosen treatment temperatures because of shorter retention time and incomplete decomposition of sodium sulphate. X-ray diffraction analysis revealed remaining phase fractions of whitlockite (Ca3-x(Mg,Fe)x(PO4)2) and sodium sulphate from the starting materials in products and thus indicated incomplete reaction. In contrast to the results of laboratory-scale experiments, the crystalline phase CaNaPO4 was clearly absent in the products from the rotary kiln but instead a Mg-bearing phase (Ca,Mg)NaPO4 was formed. Laboratory-scale experiments confirmed (Ca,Mg)NaPO4 is an intermediate phase between whitlockite and CaNaPO4. However, both crystalline phases are characterized by high plant availability. It was shown that heavy metal removal increased at higher temperatures whereas solubility and thus plant availability of phosphorus already reached its maxima at temperatures of 950 °C in pilot-scale and 875 °C in laboratory-scale experiments.
The ISO 16000-6 standard describes a method for the determination of volatile organic compounds (VOCs) in indoor and test chamber air by sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (GC/MS). It also gives directions to adapt this methodology to very volatile organic compounds (VVOCs). Indeed, toxicologically based guideline values are being implemented for these compounds and it becomes necessary to measure them. But a comprehensive and robust measurement method is lacking. This work highlights the points that still need to be explored towards the standardisation of a suitable procedure: investigations on sorbent combinations, the suitability of chromatography columns and the use of gaseous standards are required. The biggest challenge remains in the fact that strong sorbents adsorb water together with VVOCs. Water may impair the analysis and the optimal approach to eliminate it is still to be found and integrated into the sampling strategy.
In the transition from carbon to iron-gall inks, the two documents from the Egyptian Museum and Papyrus Collection in Berlin with shelfmarks P 13500 and P 13501 discussed in this work present an important case. Their inks appear brownish, although they date back to the fourth and third century BCE, when carbon inks are believed to have been commonly if not exclusively used. Using imaging micro-X-ray fluorescence and infrared reflectography, we discovered that the inks in both documents contain a significant amount of copper in addition to carbon. Comparing the extant recipes for black writing inks and the experimental evidence, we suggest that these inks are a transition between the pure carbon and the iron-gall inks. Such inks may have been quite common before the production of iron-gall ink was clearly understood and established.
Gypsum is widely used in the construction sector and its worldwide consumption has been increasing for several decades. Depending on the life-time of the used gypsum products, an increase of gypsum in construction and demolition waste follows. Especially against the background of a circular economy, the recycling of waste gypsum is of growing importance. However, the use of recycled gypsum makes only sense if it is environmentally friendly. Therefore, an evaluation of the environmental impacts of an industrial-scale processing for the recycling of post-consumer gypsum waste was conducted. The evaluation was performed with an established life cycle assessment software. Original data provided by industry and complementary data from a database for life cycle assessments were used for the calculations. Two scenarios for recycled gypsum with different transportation distances were calculated. These results are compared with results of the environmental evaluation of gypsum derived from coal-fired power plants (FGD gypsum) and natural gypsum. The results show that utilization of recycled gypsum can be environmentally advantageous compared to the use of natural gypsum or FGD gypsum, especially in the impact categories land transformation and resource consumption (abiotic depletion potential). For most environmental impact categories the specific transportation distances have a strong influence.
Quantitative chemical analysis of airborne particulate matter (PM) is vital for the understanding of health effects in indoor and outdoor environments, as well as for enforcing EU air quality regulations. Typically, airborne particles are sampled over long time periods on filters, followed by lab-based analysis, e.g., with inductively coupled plasma mass spectrometry (ICP-MS). During the EURAMET EMPIR AEROMET project, cascade impactor aerosol sampling is combined for the first time with on-site total reflection X-ray fluorescence (TXRF) spectroscopy to develop a tool for quantifying particle element compositions within short time intervals and even on-site. This makes variations of aerosol chemistry observable with time resolution only a few hours and with good size resolution in the PM10 range. The study investigates the proof of principles of this methodological approach. Acrylic discs and silicon wafers are shown to be suitable impactor carriers with sufficiently smooth and clean surfaces, and a non-destructive elemental mass concentration measurement with a lower limit of detection around 10 pg/m3 could be achieved. We demonstrate the traceability of field TXRF measurements to a radiometrically calibrated TXRF reference, and the results from both analytical methods correspond satisfactorily.
Frass (fine powdery refuse or fragile perforated wood produced by the activity of boring insects) of larvae of the European house borer (EHB) and of drywood termites was tested as a natural and novel feedstock for 3D-printing of wood-based materials. Small particles produced by the drywood termite Incisitermes marginipennis and the EHB Hylotrupes bajulus during feeding in construction timber, were used. Frass is a powdery material of particularly consistent quality that is essentially biologically processed wood mixed with debris of wood and faeces. The filigree-like particles flow easily permitting the build-up of woodbased structures in a layer wise fashion using the Binder Jetting printing process. The Quality of powders produced by different insect species was compared along with the processing steps and properties of the printed parts. Drywood termite frass with a Hausner Ratio HR = 1.1 with ρBulk = 0.67 g/cm3 and ρTap = 0.74 g/cm3 was perfectly suited to deposition of uniformly packed layers in 3D printing. We suggest that a variety of naturally available feedstocks could be used in environmentally responsible approaches to scientific material sciences/additive manufacturing.
A new facility has been developed which allows for a stable and reproducible production of ambient-like model aerosols (PALMA) in the laboratory. The set-up consists of multiple aerosol generators, a custom-made flow tube homogeniser, isokinetic sampling probes, and a system to control aerosol temperature and humidity. Model aerosols containing elemental carbon, secondary organic matter from the ozonolysis of α-pinene, inorganic salts such as ammonium sulfate and ammonium nitrate, mineral dust particles,and water were generated under different environmental conditions and at different number and mass concentrations. The aerosol physical and chemical properties were characterised with an array of experimental methods, including scanning mobility particle sizing, ion chromatography, total reflection X-ray fluorescence spectroscopy and thermo-optical analysis. The facility is very versatile and can find applications in the calibration and performance characterisation of aerosol instruments monitoring ambient air. In this study, we performed, as proof of concept, an intercomparison of three different commercial PM (particulate matter) monitors (TEOM1405, DustTrak DRX 8533 and Fidas Frog) with the gravimetric reference method under three simulated environmental scenarios. The results are presented and compared to previous field studies. We believe that the laboratory-based method for simulating ambient aerosols presented here could provide in the future a useful alternative to time-consuming and expensive field campaigns, which are often required for instrument certification and calibration.
This paper focuses on the scandium speciation in bauxite residues of different origin. Insights into mineralchemical similarities and differences of these materials will be presented and links to their natural geological background discussed. The presented research should provide fundamental knowledge for the future development of efficient and viable technologies for Sc-recovery from bauxite residues derived from different bauxites and accumulating at different localities. In total, five bauxite residues were investigated which originated from Greece, Germany, Hungary and Russia (North Ural & North Timan) using a combination of different analytical tools. Those included: laser ablation inductively coupled plasma mass spectrometry, X-ray absorption near Edge structure (XANES) spectroscopy, μ-Raman spectroscopy as well as scanning electron microscopy and electron microprobe analyses. X-ray fluorescence and inductively coupled plasma mass spectrometry were used to determine the overall chemical composition. The investigated samples were found to exhibit a relatively homogenous distribution of Sc between the larger mineral particles and the fine-grained matrix except for Al-phases like diaspore, boehmite and gibbsite. These phases were found to be particularly low in Sc. The only sample where Sc mass fractions in Al-phases exceeded 50 mg/kg was the Russian sample from North Ural. Fe-phases such as goethite, hematite and chamosite (for Russian samples) were more enriched in Sc than the Al-phases.
In fact, in Greek samples goethite showed a higher capacity to incorporate or adsorb Sc than hematite. Accessory minerals like zircon, rutile/anatase and ilmenite were found to incorporate higher mass fractions of Sc (>150 mg/kg), however, those minerals are only present in small amounts and do not represent major host phases for Sc. In Russian samples from North Ural an additional Ca–Mg rich phase was found to contain significant mass fractions of Sc (>500 mg/kg). μ-XANES spectroscopy was able to show that Sc in bauxite residue occurs adsorbed onto mineral surfaces as well as incorporated into the crystal lattice of certain Fe-phases. According to our observations the bauxite type, i.e. karstic or lateritic, the atmospheric conditions during bauxitization, i.e. oxidizing or reducing, and consequently the dominant Sc-bearing species in the primary Bauxite influence the occurrence of Sc in bauxite residues. In karstic bauxites, underlying carbonate rocks can work as a pH-barrier and stabilize Sc. This prevents the Sc from being mobilized and removed during bauxitization. Hence, karstic bauxites are more prone to show a Sc enrichment than lateritic bauxites. Reducing conditions during bauxitization support the incorporation of Sc into clay minerals such as chamosite, which can dissolve and reprecipitate during Bayer processing causing Sc to be redistributed and primarily adsorb onto mineral surfaces in the bauxite residue. Oxidizing conditions support the incorporation of Sc into the crystal lattice of Fe-oxides and hydroxides, which are not affected in the Bayer process. The genetic history of the bauxite is therefore the major influential factor for the Sc occurrence in bauxite residues.
Antimicrobials can exert specific physiological effects when used in combination that are different from those when applied alone. While combination effects have been extensively mapped for antibiotic-antibiotic combinations, the combination effects of antibiotics with antimicrobials used as biocides or antiseptics have not been systematically investigated. Here, we investigated the effects of combinations of antibiotics (meropenem, gentamicin, and ciprofloxacin) and substances used as biocides or antiseptics [octenidine, benzalkonium chloride, cetrimonium bromide, chlorhexidine, Povidone-iodine, silver nitrate (AgNO3), and Ag-nanoparticles] on the planktonic growth rate of Pseudomonas aeruginosa. Combination effects were investigated in growth experiments in microtiter plates at different concentrations and the Bliss interaction scores were calculated. Among the 21 screened combinations, we find prevalent combination effects with synergy occurring six times and antagonism occurring 10 times. The effects are specific to the antibiotic-biocide combination with meropenem showing a tendency for antagonism with biocides (6 of 7), while gentamicin has a tendency for synergy (5 of 7). In conclusion, antibiotics and biocides or antiseptics exert physiological combination effects on the pathogen P. aeruginosa. These effects have consequences for the efficacy of both types of substances and potentially for the selection of antimicrobial resistant strains in clinical applications with combined exposure (e.g., wound care and coated biomaterials).
Geosynthetic materials are applied in measures for coastal protection. Weathering or any damage of constructions, as shown by a field study in Kaliningrad Oblast (Russia), could lead to the littering of the beach or the sea (marine littering) and the discharge of possibly harmful additives into the marine environment. The ageing behavior of a widely used geotextile made of polypropylene was studied by artificial accelerated ageing in water-filled autoclaves at temperatures of 30 to 80 °C and pressures of 10 to 50 bar. Tensile strength tests were used to evaluate the progress of ageing, concluding that temperature rather than pressure was the main factor influencing the ageing of geotextiles. Using a modified Arrhenius equation, it was possible to calculate the half-life for the loss of 50% of the strain, which corresponds to approximately 330 years. Dynamic surface leaching and ecotoxicological tests were performed to determine the possible release of contaminants. No harmful effects on the test organisms were observed.
In 2018, the production of Municipal SolidWaste (MSW) in EU-28 reached 250.6 Mt, with the adoption of different management strategies, involving recycling (48 wt %), incineration and thermal valorization (29 wt %) and landfilling (23 wt %). This work was based on the analysis of the baseline situation of MSW management in EU-28 in 2018, considering its progress in 2008–2018, and discussed the possible improvement perspectives based on a framework involving incineration and recycling as the only possible alternatives, specifically evaluating the capability of already-existing incineration plants to fulfill the EU needs in the proposed framework. The results of the assessment showed two main crucial issues that could play a pivotal role in the achievement of Circular Economy action plan targets: the need to increase the recycling quotas for specific MSW fractions through the separate collection, and therefore the improvement of definite treatment process chains; the optimization of the recovery of secondary raw materials from incineration bottom ash, involving the Recycling of ferrous and nonferrous metals and the mineral fraction. Both issues need to find an extensive application across all member states to decrease the actual differences in the adoption of sustainable MSW management options.
Formaldehyde is considered as carcinogenic and is emitted from particleboards and plywood used in toy manufacturing. Currently, the flask method is frequently used in Europe for market surveillance purposes to assess formaldehyde release from toys, but its concordance to Levels measured in emission test chambers is poor. Surveillance laboratories are unable to afford laborious and expensive emission chamber testing to comply with a new amendment of the European Toy Directive; they need an alternative method that can provide reliable results. Therefore, the application of miniaturised emission test chambers was tested. Comparisons between a 1 m3 emission test chamber and 44 mL microchambers with two particleboards over 28 days and between a 24 L desiccator chamber and the microchambers with three puzzle samples over 10 days resulted in a correlation coefficient r2 of 0.834 for formaldehyde at steady state. The correlation between the results obtained in microchambers vs. flask showed a high variability over 10 samples (r2: 0.145),
thereby demonstrating the error-proneness of the flask method in comparison to methods carried out under ambient parameters. An exposure assessment was also performed for three toy puzzles: indoor formaldehyde concentrations caused by puzzles were not negligible (up to 8 µg/m3), especially when more conservative exposure scenarios were considered.
Social immune behaviors are described in a great variety of insect societies and their role in preventing emerging infectious diseases has become a major topic in insect research. The social immune system consists of multiple layers, ranging from the synthesis of external immune molecules to the coordination of individual behaviors into sophisticated collective defensive tasks. But our understanding of how complex group-level behavioral defenses are orchestrated has remained limited. We sought to address this gap in knowledge by investigating the relationship between the external activity of an important immune effector molecule in termites, Gram negative binding protein 2 (GNBP-2) and collective grooming and cannibalism. We reasoned that as an external enzyme capable of degrading entomopathogenic fungi, GNBP-2 can facilitate the spread of pathogenic molecules in the colony, and thus serve to trigger collective defenses in a manner analogous to pathogen-associated molecular signatures (PAMPs) of the individual immune system. To test whether GNBP-2 could play a role in regulating social immune behavior, we experimentally inhibited its fungicidal activity using the glycomimetic molecule, D-d-gluconolactone (GDL) and recorded collective behavioral responses to an infected nestmate. Contrary to expectations, GNBP-2 inhibition did not influence the rate or intensity of grooming of either control or fungus-infected
nestmates. By contrast, we found that the probability of being harmed through defensive cannibalistic behaviors was significantly reduced by the inhibition of GNBP-2. Our findings indicate that the regulation of collective immune behaviors may depend in part on the external secretion of an enzyme originating from the individual immune system, but that other cues are also necessary.
Natural building materials for interior fitting and refurbishment - What about indoor emissions?
(2021)
Indoor air quality can be adversely affected by emissions from building materials, consequently having a negative impact on human health and well-being. In this study, more than 30 natural building materials (earth dry boards and plasters, bio-based insulation materials, and boards made of wood, flax, reed, straw, etc.) used for interior works were investigated as to their emissions of (semi-) volatile organic compounds ((S)VOC), formaldehyde, and radon. The study focused on the emissions from complete wall build-ups as they can be used for internal Partition walls and the internal insulation of external walls. Test chambers were designed, allowing the compounds to release only from the surface of the material facing indoors under testing Parameters that were chosen to simulate model room conditions. The emission test results were evaluated using the AgBB evaluation scheme, a procedure for the health-related evaluation of construction products and currently applied for the approval of specific groups of building materials in Germany.
Seventeen out of 19 sample build-ups tested in this study would have passed this scheme since they generally proved to be low-emitting and although the combined emissions of multiple materials were tested, 50% of the measurements could be terminated before half of the total testing time.
Due to their ability to penetrate, deteriorate and discolour stone surfaces, rock-inhabiting black fungi represent a remarkable issue for cultural heritage conservation. Black microcolonial fungi (MCF) can also adapt to different environmental conditions, by converting from yeast-like morphology to a peculiar meristematic development with swollen cells (torulose hyphae, TH), to extremely thin structures (filamentous hyphae, FH). Furthermore, black MCF produce protective pigments: melanin, dark pigment particularly evident on light stone surfaces, and carotenoids. Black fungi produce melanin in critical, oligotrophic conditions as well as constitutively. Melanin function is mostly related to stress resistance and the ability of fungi to generate appressorial turgor to actively penetrate plant cells in pathogenic species. An involvement of melanins in stone surface penetration has been suggested, but not experimentally proved. In this work, we tested the role of hyphal melanisation in penetration mechanisms on the model black fungus Knufia petricola A95 in lab conditions. The wild-type and three mutants with introduced targeted mutations of polyketide-synthases (melanin production) and/or phytoene dehydrogenase (carotenoid synthesis) were inoculated on artificial carbonate pellets (pressed Carrara marble powder) of different porosity. After 5, 10, 17 and 27 weeks, hyphal penetration depth and spread were quantified on periodic acid Schiff-stained cross-sections of the pellets, collecting measurements separately for TH and FH. Droplet assay of the mutants on different media were conducted to determine the role of nutrients in the development of different fungal morphologies. In our in vitro study, the hyphal penetration depth, never exceeding 200 μm, was proven to be consistent with observed penetration patterns on stone heritage carbonate substrates. Pellet porosity affected penetration patterns of TH, which developed in voids of the more porous pellets, instead than actively opening new passageways. Oppositely, the thin diameter of FH allowed their penetration independently of substrate porosity. Instead, the long-hypothesized crucial role of melanin in black MCF hyphal penetration should be rejected. TH were developed within the pellets also by melanin deficient strains, and melanized strains showed an endolithic component of non-melanized TH. FH were non-melanized for all the strains, but deeply penetrated all pellet types, with higher penetration depth probably related to their potential exploratory (nutrient-seeking) role, while TH may be more related to a resistance to surface stress factors. In the melanin deficient strains, the absence of melanin caused an increased penetration rate of FH, hypothetically related to an earlier necessity to search for organic nutrients.