4 Material und Umwelt
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- 4 Material und Umwelt (48)
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- 6.1 Oberflächen- und Dünnschichtanalyse (3)
Paper des Monats
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Sugarcane bagasse is commonly combusted to generate energy. Unfortunately, recycling strategies rarely consider the resulting ash as a potential fertilizer. To evaluate this recycling strategy for a sustainable circular economy, we characterized bagasse ash as a fertilizer and measured the effects of co-gasification and co-combustion of bagasse with either chicken manure or sewage sludge: on the phosphorus (P) mass fraction, P-extractability, and mineral P phases. Furthermore, we investigated the ashes as fertilizer for soybeans under greenhouse conditions. All methods in combination are reliable indicators helping to assess and predict P availability from ashes to soybeans. The fertilizer efficiency of pure bagasse ash increased with the ash amount supplied to the substrate. Nevertheless, it was not as effective as fertilization with triple-superphosphate and K<sub>2</sub>SO<sub>4</sub>, which we attributed to lower P availability. Co-gasification and co-combustion increased the P mass fraction in all bagasse-based ashes, but its extractability and availability to soybeans increased only when co-processed with chicken manure, because it enabled the formation of readily available Ca-alkali phosphates. Therefore, we recommend co-combusting biomass with alkali-rich residues to increase the availability of P from the ash to plants.
Rock weathering is a key process in global elemental cycling. Life participates in this process with tangible consequences observed from the mineral interface to the planetary scale. Multiple lines of evidence show that microorganisms may play a pivotal—yet overlooked—role in weathering. This topic is reviewed here with an emphasis on the following questions that remain unanswered: What is the quantitative contribution of bacteria and fungi to weathering? What are the associated mechanisms and do they leave characteristic imprints on mineral surfaces or in the geological record? Does biogenic weathering fulfill an ecological function, or does it occur as a side effect of unrelated metabolic functions and biological processes? An overview of efforts to integrate the contribution of living organisms into reactive transport models is provided. We also highlight prospective opportunities to harness microbial weathering in order to support sustainable agroforestry practices and mining activities, soil remediation, and carbon sequestration.
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 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.