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What Does Ectoine Do to DNA? A Molecular-Scale Picture of Compatible Solute−Biopolymer Interactions
(2020)
Compatible solutes are accumulated in the cytoplasm of halophilic microorganisms. These molecules enable their survival in a high salinity environment. Ectoine is such a compatible solute. It is a zwitterionic molecule which strongly interacts with surrounding water molecules and changes the dynamics of the local hydration shell. Ectoine interacts with biomolecules such as lipids, proteins and DNA. The molecular interaction between ectoine and biomolecules in particular the interaction between ectoine and DNA is far from being understood.
In this paper we describe molecular aspects of the interaction between ectoine and double stranded DNA(dsDNA). Two 20 base pairs long dsDNA fragments were immobilized on a Gold surface via a thiol-tether. The interaction between the dsDNA monolayers with diluted and concentrated ectoine solutions was examined by means of X-ray photoelectron and polarization modulation infrared reflection absorption spectroscopies (PM IRRAS). Experimental results indicate that the ability of ectoine to bind water reduces the strength of hydrogen bonds formed to the ribose-phosphate backbone in the dsDNA. In diluted (0.1 M) ectoine solution, DNA interacts predominantly with water molecules. The sugar-phosphate backbone is involved in the formation of strong hydrogen bonds to water, which with elapsing time leads to a reorientation of the planes of nucleic acid bases. This reorientation destabilizes the hydrogen bonds strength between the bases and leads to a partial dehybridizaiton of the dsDNA. In concentrated ectoine solution (2.5 M), almost all water molecules interact with ectoine. Under this condition ectoine is able to interact directly with DNA. Density functional theory (DFT) calculations demonstrate that the direct interaction involves the nitrogen atoms in ectoine and phosphate groups in the DNA molecule. The results of the quantum chemical calculations Show that rearrangements in the ribose-phosphate backbone, caused by a direct interaction with ectoine, facilitates contacts between O atom in the phosphate group and H atoms in a nucleic acid base. In the PM IRRA spectra, an increase in the number of the IR absorption modes in the base pair frequency region proves that the hydrogen bonds between bases become weaker.
Thus, a sequence of reorientations caused by interaction with ectoine leads to a breakdown of hydrogen bonds between bases in the double helix.
The Brazilian sugarcane industry produced around 173 million tons (Mt) of bagasse in 2018. Bagasse is a by-product of juice extraction for ethanol and sugar production and is combusted in order to generate power, producing up to 10 Mt of ash per year. This ash contains various concentrations of plant nutrients, which allow the ash to be used as a crop fertilizer. However, the concentration and extractability of phosphorus (P), an essential plant nutrient, are low in bagasse ash. To increase the P content, we co-gasified and co-combusted bagasse with P-rich chicken manure. The resulting ash was thermochemically post-treated with alkali additives (Na2SO4 and K2SO4) to increase the availability of P to plants. We aimed to: (i) investigate the effect of thermochemical post-treatment of co-gasification residue and co-combustion ash on P availability to soybeans, (ii) explore the potential of chemical extraction methods (citric acid, neutral ammonium citrate, formic acid, and Mehlich-I) and diffusive gradients in thin films (DGT) to predict the availability of P to soybeans, and (iii) identify the responsible P-phases using X-ray diffraction . We evaluated P availability to soybeans growing in Brazilian Oxisol soil in two independent greenhouse pot experiments. The positive effect of thermochemical treatment on P availability from gasification residue was confirmed through the observation of increased P uptake and biomass in soybean plants. These findings were confirmed by chemical extraction methods and DGT. The gasification residue contained whitlockite as its main P-bearing phase. Thermochemical post-treatment converted whitlockite into highly soluble CaNaPO4. In contrast, co-combustion ash already contained highly soluble Ca(Na,K)PO4 as its main P-bearing phase, making thermochemical post-treatment unnecessary for increasing P availability. In conclusion, increased extractability and availability of P for soybeans were closely connected to the formation of calcium alkali phosphate. Our findings indicate that this combined methodology allows for the prediction of P-fertilization effects of ash.
Stress is a normal part of life for fungi, which can survive in environments considered inhospitable or hostile for other organisms. Due to the ability of fungi to respond to, survive in, and transform the environment, even under severe stresses, many researchers are exploring the mechanisms that enable fungi to adapt to stress. The International Symposium on Fungal Stress (ISFUS) brings together leading scientists from around the world who research fungal stress. This article discusses presentations given at the third ISFUS, held in Sao Jose dos Campos, Sao Paulo, Brazil in 2019, thereby summarizing the state-of-the-art knowledge on fungal stress, a field that includes microbiology, agriculture, ecology, biotechnology, medicine, and astrobiology.
Timber is constantly exposed to environmental influences under outdoor conditions which limits its Lifetime and usability. In order to counteract the damaging processes caused by insects, we have developed a novel and more environmentally friendly method to protect wood materials via covalent modification by organic insecticides. Starting with an important class of synthetic insecticides which are derived from the natural insecticide nicotine, various new carboxylic acid derivatives of imidacloprid were made accessible. These activated neonicotinoids were utilized for the chemical modification of wood hydroxy groups. In contrast to conventional wood preservation methods in which biocides are only physically bound to the surface for a limited time, the covalent fixation of the preservative guarantees a permanent effect against wood pests, demonstrated in standardized biological tests. Additionally, the environmental interaction caused by non-bound neonicotinoids is significantly reduced, since both, a smaller application rate is required and leaching of the active ingredient is prevented. By minimizing the pest infestation, the lifetime of the material increases while preserving the natural appearance of the material.
The application of fracture mechanics to the determination of the fatigue behavior of weldments is discussed with the focus on classic fatigue, i.e., the overall fatigue life and the fatigue strength in terms of an S-N curve and the endurance limit. The following issues are addressed: specific features of short fatigue crack propagation, an adequate initial crack size, multiple crack propagation and its statistical treatment as well as welding residual stresses. As an example, an approach of the authors is applied to the determination of FAT classes for a butt weld with varying weld toe geometry.
In the present study, a simple approach was used to investigate the effect of UV-exposure on two high density Polyethylene materials (PE-HD), commonly used for storage tanks, on fuel sorption behavior and colonization by microorganisms. The aim was to investigate whether the sorption behavior of the fuels (diesel/biodiesel) and the colonization by microorganisms, frequently occurring in the fuel, is affected and may lead to undesirable or safety-relevant material changes. We showed that the UV-irradiation leads to significant changes of the sorption behavior due to chemi-crystallization and crosslinking. The fuel Sorption is affected by the UV-induced formation of polar carbonyl and hydroxyl groups predominantly occurring at the surface. With respect to microbial colonization behavior for Bacillus subtilis and Pseudomonas aeruginosa, isolated from a contaminated diesel sample, differences of the initial adhesion could be shown depending on the initial type of polyethylene as well as on the degree of UV-induced degradation.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray Absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr).
Fungi that share light-flooded habitats with phototrophs may profit from their excess photosynthetic products. But to cope with sunlight-associated stresses [e.g. high temperatures, UV radiation with associated DNA damage, accumulation of reactive oxygen species (ROS), desiccation and osmotic stresses] it is important for fungi to accurately sense and respond to changes in light. To test the hypothesis that light is an environmental cue that Ascomycota use to coordinate growth, stress responses as well as to establish pathogenic or symbiotic relationships, the photoreceptor (PR) distribution in species from different ecological niches was analysed. The genomes of black [dihydroxynaphthalene (DHN) melanin-containing] fungi from phyllosphere and exposed solid surfaces contain multiple photoreceptors (PRs). The plant pathogen Botrytis cinerea (Leotiomycetes) has a highly sophisticated photosensory and signalling system that helps to avoid light and to locate susceptible hosts. Rock-inhabiting Dothideomycetes and Eurotiomycetes including Knufia petricola possess equal numbers ofPRs along with the same set of protective pigments. This similarity between black fungi from plant and rock surfaces suggests that photoperception and -regulation are important for fungi that receive nutrients through cooperation with phototrophs. Genetic tools for manipulating K. petricola exist and will be used to test this idea.
Biofilms cause complications and high costs in both industry and medicine. Of particular interest are bacterial infections of prosthetic materials, which usually cannot be eliminated due to the high antibiotic resistance known for bacteria forming biofilms. The search for new materials and coatings with lower colonization potential and antibacterial activity is of great importance to reduce biofilm formation. However, there is no standardized procedure to examine the colonization characteristics of bacteria in the Biofilm state in situ. Here, we describe an automated epifluorescence microscopy system for the semi-quantitative analysis of three-dimensional (3D) biofilms on various surfaces. To analyze adherent bacteria, three materials (glass, steel and titanium) were incubated with bacteria in a flow chamber system. After fluorescence staining of the bacteria, automated image capturing, quantification of the bacteria, measurement of the colonized area and determination of the 3D biofilm height were carried out by using novel software.
Furthermore, the materials were examined for their surface topography using white light scanning interferometry. Titanium compared to glass showed a significantly higher number of adherent bacteria.
We argue that this was due to the higher microroughness of titanium. The colonized area was in accordance with the number of adherent bacteria and was also significantly larger on titanium coupons compared to glass. Maximum 3D biofilm height on glass coupons was significantly lower compared to the ones on steel and titanium. This novel method enables the standardized, automated investigation of the colonization with bacteria on different materials. This approach can considerably support the characterization of new material surfaces and their innovative coatings by analyzing the amount of attached Bacteria and thickness of biofilms in situ and eliminates the need of conventional cultivation.
Fluorides are well-known as wood preservatives. One of the limitations of fluoride-based wood preservatives is their high leachability. Alternative to current fluoride salts such as NaF used in wood protection are low water-soluble fluorides. However, impregnation of low water-soluble fluorides into wood poses a challenge. To address this challenge, low water-soluble fluorides like calcium fluoride (CaF2) and magnesium fluoride (MgF2) were synthesized as nanoparticles via the fluorolytic sol−gel synthesis and then impregnated into wood specimens. In this study, the toxicity of nano metal fluorides was assessed by termite mortality, mass loss and visual analysis of treated specimens after eight weeks of exposure to termites, Coptotermes formosanus. Nano metal fluorides with sol concentrations of 0.5 M and higher were found to be effective against termites resulting in 100% termite mortality and significantly inhibited termite feeding. Among the formulations tested, the least damage was found for specimens treated with combinations of CaF2 and MgF2 with an average mass loss less than 1% and visual rating of “1”. These results demonstrate the efficacy of low water-soluble nano metal fluorides to protect Wood from termite attack.
Phosphorus (P) recovery from sewage sludge ash (SSA) is one of the most promising approaches of phosphate rock substitution in mineral fertilizers and might be a sustainable way to secure supply of this raw material in the future. In the current investigation, the process of thermochemical treatment of SSA was applied to SSA coming from selected mono-incineration plants of municipal sewage sludge in Poland (Cracow, Gdansk, Gdynia, Lodz, Kielce and Szczecin).
The Polish SSA was thermochemically converted in the presence of sodium (Na) additives and a reducing agent (dried sewage sludge) to obtain secondary raw materials for the production of marketable P fertilizers. The process had a positive impact on the bioavailability of phosphorus and reduced the content of heavy metals in the obtained products. The P solubility in neutral Ammonium citrate, an indicator of its bioavailability, was significantly raised from 19.7–45.7% in the raw ashes and 76.5–100% in the thermochemically treated SSA. The content of nutrients in the recyclates was in the range of 15.7–19.2% P2O5, 10.8–14.2% CaO, 3.5–5.4% Na2O, 2.6–3.6% MgO and 0.9–1.3% K2O. The produced fertilizer raw materials meet the Polish norms for trace elements covered by the legislation: the content of lead was in the range 10.2–73.1 mg/kg, arsenic 4.8–22.7 mg/kg, Cadmium 0.9–2.8 mg/kg and mercury <0.05 mg/kg. Thus, these products could be potentially directly used for fertilizer production. This work also includes an analysis of the possibilities of using ashes for fertilizer purposes in Poland, based on the assumptions indicated in the adopted strategic and planning documents regarding waste management and fertilizer production.
More sustainable waste management practices are an important element in the Transformation towards a circular economy (CE). Activities in this area should be dedicated to all groups of waste, including those generated in the water and sewage sector. This paper presents the characteristics of sewage sludge ash (SSA) coming from Polish municipal waste incineration plants. Due to the high content of nutrients such as phosphorus (8.01% P2O5), calcium (5.11% CaO) and magnesium (2.75% MgO), the analyzed SSA may constitute a valuable source of raw materials for the fertilizer industry.
Despite the good fertilizing properties of the SSA, in some cases the presence of heavy metals such as cadmium (0.74–1.4 mg/kg dry matter), lead (49.8–99 mg/kg dry matter), mercury (3.93 mg/kg dry matter) and arsenic (4.23–4.43 mg/kg dry matter) and poor bioavailability of P from SSA disqualifies this waste from direct use as a fertilizer. Therefore, it is necessary to look for methods that will allow the municipal SSA to be processed, for example, technologies for the extraction of phosphorus and the production of phosphate fertilizer. This way of SSA management is in the line with the CE assumptions, in which waste becomes a valuable source of secondary raw materials. Fertilizer produced from waste meeting quality, safety and labelling requirements and limits of organic, microbiological and physical contaminants will be able to be traded freely within the European Union (EU) and receive the CE marking. The idea of use of SSA for fertilizer purposes is consistent not only with the objectives of the CE but also with the Polish National Waste Management Plan 2022 and the Municipal Sewage Sludge Strategy 2019–2022, which emphasizes the necessity to maximize the use of biogenic substances contained in wastewater. Therefore, sustainable management of SSA, in particular its storage in a way enabling the recovery of phosphorus, should be promoted.
Currently, sulfate-reducing bacteria (SRB) is regarded as the main culprit of microbiologically influenced corrosion (MIC), mainly due to the low reported corrosion rates of other microorganisms. For example, the highest reported corrosion rate for methanogens is 0.065 mm/yr. However, by investigating methanogen-induced microbiologically influenced corrosion (Mi-MIC) using an in-house developed versatile multiport flow test column, extremely high corrosion rates were observed. We analyzed a large set of carbon steel beads, which were sectionally embedded into the test columns as substrates for iron-utilizing methanogen Methanobacterium IM1. After 14 days of operation using glass beads as fillers for section separation, the highest average corrosion rate of Methanobacterium IM1 was 0.2 mm/yr, which doubled that of Desulfovibrio ferrophilus IS5 and Desulfovibrio alaskensis 16109 investigated at the same conditions. At the most corroded region, nearly 80% of the beads lost 1% of their initial weight (fast-corrosion), resulting in an average corrosion rate of 0.2 mm/yr for Methanobacterium IM1-treated columns. When sand was used as filler material to mimic sediment conditions, average corrosion rates for Methanobacterium IM1 increased to 0.3 mm/yr (maximum 0.52 mm/yr) with over 83% of the beads having corrosion rates above 0.3 mm/yr. Scanning electron images of metal coupons extracted from the column showed methanogenic cells were clustered close to the metal surface. Methanobacterium IM1 is a hydrogenotrophic methanogen with higher affinity to metal than H2. Unlike SRB, Methanobacterium IM1 is not restricted to the availability of sulfate concentration in the environment. Thus, the use of the multiport flow column provided a new insight on the corrosion potential of methanogens, particularly in dynamic conditions, that offers new opportunities for monitoring and development of mitigation strategies. Overall, this study shows under certain conditions methanogenic archaea can cause higher corrosion than SRB, specific quantifications, i.e., maximum, average, and minimum corrosion rates can be determined, and that spatial statistical evaluations of MIC can be carried out.
Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P fertilizers from recycled materials, which often have low plant availability. Specific co-fertilization with ammoniumcan enhance P plant availability in soils amended with these P fertilizers, and thus the yield of plants. To investigate this effect, we performed a pot experiment with maize in slightly acidic soil (pH 6.9) with one water-soluble (triple superphosphate [TSP]) and two water-insoluble (sewage sludge-based and hyperphosphate [Hyp]) P fertilizers and anammoniumsulfate nitrate with or without a nitrification inhibitor (NI). The dry matter yield of maize was significantly increased by the NI with the Hyp (from 14.7 to 21.5 g/pot) and TSP (from 40.0 to 45.4 g/pot) treatments. Furthermore, P uptake was slightly increased in all three P treatments with the NI, but not significantly. Olsen-P extraction and P K-edge micro-X-ray absorption near-edge structure (XANES) spectroscopy showed that apatite-P of the water insoluble P fertilizers mobilized during the plant growth period. In addition, novel nitrogen (N) K-edge micro-XANES spectroscopy and the Mogilevkina method showed that the application of an NI increased the fixation of ammonium in detectable hot spots in the soil. Thus, the delay in the nitrification process by the NI and the possible slow-release of temporarily fixed ammoniumin the soil resulted in a high amount of plant available Ammonium in the soil solution. This development probably decreases the rhizosphere pH due to release of H+ by plants during ammoniumuptake, whichmobilizes phosphorus in the amended soil and increases the dry matter yield of maize. This is especially important for water-insoluble apatite-based P fertilizers (conventional and recycled), which tend to have poor plant availability.
Terrestrial mud volcanoes are unique structures driven by tectonic pressure and fluids from the deep subsurface. These structures are mainly found in active tectonic zones, such as the area near the Los Bajos Fault in Trinidad. Here we report a chemical and microbiological characterization of three mud volcanoes, which included analyses of multiple liquid and solid samples from the mud volcanoes. Our study confirms previous suggestions that at least some of the mud volcano fluids are a mixture of deeper salt-rich water and surficial/precipitation water. No apparent water quality differences were found between sampling sites north and south of a major geological fault line. Microbiological analyses revealed diverse communities, both aerobic and anaerobic, including sulfate reducers, methanogens, carbon dioxide fixing and denitrifying bacteria. Several identified species were halophilic and likely derived from the deeper salt-rich subsurface water, while we also cultivated pathogenic species from the Vibrionaceae, Enterobacteriaceae, Shewanellaceae, and Clostridiaceae. These microorganisms were likely introduced into the mud volcano fluids both from surface water or shallow ground-water, and perhaps to a more minor degree by rain water. The identified pathogens are a major health concern that needs to be addressed.
The suitability of common analytical methods for the determination of active substances from wood preservatives in aged wood samples was investigated during an interlaboratory study. Permethrin, propiconazole and tebuconazole were quantified in 1.5 and 8 year-old wood samples by gas chromatography and liquid chromatography. Generally, the applied Methods yielded reliable results for these samples. However, wood components can coelute with propiconazole and tebuconazole during liquid chromatography. Optimization of separation might be required if UV detection is applied.
We present here our methodological approach applied to the study of Egyptian inks in Late Antiquity. It is based on an interdisciplinary strategy, bringing together a variety of disciplines from humanities and natural sciences, and it aims at systematically collecting a statistically relevant amount of data regarding the composition of the inks. The application of a wellestablished, non-invasive protocol that includes near-infrared imaging and X-ray fluorescence spectroscopy for in situ measurements enables the identification and characterisation of inks dating from the end of Late Antiquity onwards. However, sometimes this method limits our understanding when characterising more ancient inks. Trying to overcome these limitations, the potential of a new device for the characterisation of organic compounds is here explored by conducting preliminary tests on mock samples.
In this work, we present the results from 77 codicological units that include some of the earliest manuscripts of our corpus that presently lists 159 units.
Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from - 2018.3 ± 2.2 kJ mol-1 to - 2030.5 ± 2.1 kJ mol-1 and standard entropy from 137.2 ± 1.0 J mol-1 K-1 to 148.6 ± 1.0 J mol-1 K-1 from sodium endmember b-CaNaPO4 to potassium endmember b0-CaKPO4.
Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase b-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases c-Ca(Na0.4K0.6)PO4 and c-Ca Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.
Based on recently published research on leaching control mechanisms in electric arc furnace (EAF) slags, it is assumed that a FeO/SiO2 ratio of around one leads to low leached V and Cr concentrations. This ratio influences the mineral phase composition of the slag toward higher amounts of spinel and a lower solubility of calcium silicate phases by suppressing the formation of magnesiowuestite and highly soluble calcium silicate phases. To evaluate this hypothesis, laboratory and scaled up tests in an EAF pilot plant were performed on slag samples characterized by elevated V and Cr leaching and a high FeO/SiO2 ratio. Prior to the melting experiments, the optimum FeO/SiO2 ratio was calculated via FactSageTM. In the melting experiments, the ratio was adjusted by adding quartz sand, which also decreased the basicity (CaO/SiO2) of the slag. As a reference, remelting experiments without quartz sand addition were conducted and additionally, the influence of the cooling rate of the slag was examined. The remelted (without quartz sand) and the remelted modified slags (with quartz sand) were analyzed chemically and mineralogically and the leaching behavior was investigated. The modification of the slags yielded a minimized release of V and Cr, supporting the hypothesis that the FeO/SiO2 ratio influences the mineralogy and the leaching behavior.
For osmoadaptation the halophilic bacterium Halomonas elongata synthesizes as its main compatible solute the aspartate derivative ectoine. H. elongata does not rely entirely on synthesis but can accumulate ectoine by uptake from the surrounding environment with the help of the osmoregulated transporter TeaABC. Disruption of the TeaABC-mediated ectoine uptake creates a strain that is constantly losing ectoine to the medium. However, the efflux mechanism of ectoine in H. elongata is not yet understood. H. elongata possesses four genes encoding mechanosensitive channels all of which belong to the small conductance type (MscS). Analysis by qRT-PCR revealed a reduction in transcription of the mscS genes with increasing salinity. The response of H. elongata to hypo- and hyperosmotic shock never resulted in up-regulation but rather in downregulation of mscS transcription. Deletion of all four mscS genes created a mutant that was unable to cope with hypoosmotic shock. However, the knockout mutant grew significantly faster than the wildtype at high salinity of 2 M NaCl, and most importantly, still exported 80% of the ectoine compared to the wildtype. We thus conclude that a yet unknown system, which is independent of mechanosensitive channels, is the major export route for ectoine in H. elongata.
Uranium and thorium species in phosphate rock and sewage sludge ash based phosphorus fertilizers
(2020)
Phosphorus (P) is an essential element for all forms of life and is thus often applied as phosphate rock-based P-fertilizers in agriculture to enable continuous farming. However, these P-fertilizers contain also hazardous uranium (U) and thorium (Th), up to 660 and 220 mg/kg, respectively. On the contrary, novel P-fertilizers made from sewage sludge (ash) contain only low mass fractions of U and Th. In addition to the total amount of U and Th in P-fertilizers, their mobility and bioavailability is important, which depends to a large extent on their chemical state, especially oxidation state and chemical bonding. Thus, we analyzed their chemical state in various P-fertilizers by U and Th L3-edge HERFD-XANES spectroscopy. Phosphate rocks and sewage sludge-based P-fertilizers contain mainly U(IV) compounds which have only a low bioavailability. In contrast, acidic treatment of phosphate rock to produce super phosphates lead to an oxidation to U(VI) compounds (including formation of uranium phosphates) with a strongly increased bioavailability. On the contrary, all analyzed P-fertilizers contain Th in form of strongly insoluble phosphates and oxides with a low bioavailability. Additionally performed water extractions and Diffusive Gradients in Thin-films (DGT) experiments support these findings.
Microcolonial black fungi are a group of ascomycetes that exhibit high stress tolerance, yeast-like growth and constitutive melanin formation. They dominate a range of hostile natural and man-made environments, from desert rocks and salterns to dishwashers, roofs and solar panels. Due to their slow growth and a lack of genetic tools, the underlying mechanisms of black fungi’s phenotypic traits have remained largely unexplored. We chose to address this gap by genetically engineering the rock-inhabiting fungus Knufia petricola (Eurotiomycetes, Chaetothyriales), a species that exhibits all characteristics of black fungi. A cell biological approach was taken by generating K. petricola strains expressing green or red fluorescent protein variants. By applying: (1) traditional gene replacement; (2) gene editing and replacement via plasmid-based or ribonucleoprotein (RNP)-based CRISPR/Cas9, and (3) silencing by RNA interference (RNAi), we constructed mutants in the pathways leading to melanin, carotenoids, uracil and adenine. Stable single and double mutants were generated with homologous recombination (HR) rates up to 100%. Efficient, partially cloning-free strategies to mutate multiple
genes with or without resistance cassettes were developed. This state-of-the-art genetic toolkit, together with the annotated genome sequence of strain A95, firmly established K. petricola as a model for exploring microcolonial black fungi.
Currently, corrosion rates (CR) and/or corrosion products (CP) obtained for methanogen-induced microbiologically influenced corrosion (Mi-MIC) on carbon steel are mainly analyzed from static-incubations. By using a multiport-flow-column, much higher CRs (0.72 mm/yr) were observed, indicating static-incubations are not suitable for determining the corrosive potential of Mi-MIC. With the combination of various analytical methods (ToF-SIMS/SEM-EDS/SEM-FIB) and contrary to previously published data, we observed that CPs contained phosphorus, oxygen, magnesium, calcium and iron but lacked carbon-related species (e.g. siderite). Overall, siderite nucleation is disrupted by methanogens, as they convert aqueous bicarbonate into carbon dioxide for methanogenesis resulting in increased localized corrosion.
Pseudomonas aeruginosa MPAO1 is the parental strain of the widely utilized transposon mutant collection for this important clinical pathogen. Here, we validate a model system to identify genes involved in biofilm growth and biofilm-associated antibiotic resistance. Our model employs a genomics-driven workflow to assemble the complete MPAO1 genome, identify unique and conserved genes by comparative genomics with the PAO1 reference strain and genes missed within existing assemblies by proteogenomics. Among over 200 unique MPAO1 genes, we identified six general essential genes that were overlooked when mapping public Tn-seq data sets against PAO1, including an antitoxin. Genomic data were integrated with phenotypic data from an experimental workflow using a user-friendly, soft lithography-based microfluidic flow chamber for biofilm growth and a screen with the Tn-mutant library in microtiter plates. The screen identified hitherto unknown genes involved in biofilm growth and antibiotic resistance. Experiments conducted with the flow chamber across three laboratories delivered reproducible data on P. aeruginosa biofilms and validated the function of both known genes and genes identified in the Tn-mutant screens. Differential Protein abundance data from planktonic cells versus biofilm confirmed the upregulation of candidates known to affect biofilm formation, of structural and secreted proteins of type VI secretion systems, and provided proteogenomic evidence for some missed MPAO1 genes. This integrated, broadly applicable model promises to improve the mechanistic understanding of biofilm formation, antimicrobial tolerance, and resistance evolution in biofilms.
Low-molecular-weight organic acids (LMWOAs) are crucial for the mobilization and acquisition of mineral phosphorus by plants. However, the role of LMWOAs in mobilizing organic phosphorus, which is the predominant phosphorus form in at least half of the world’s ecosystems, especially in humid climates, is unclear. The mechanisms of phosphorus mobilization by LMWOAs depend on climate, mainly precipitation, and shape the phosphorus nutrition strategies of plants. We disentangled the impact of roots and associated microorganisms on mechanisms of phosphorus cycling mediated by LMWOAs by studying soils along an ecosystem-sequence (ecosequence) from arid shrubland (~70 mm yr-1), and Mediterranean woodland (~370 mm yr-1) to humid-temperate forest (~1470 mm yr-1). Phosphorus speciation in soil was examined by X-ray absorption near edge structure analysis (XANES). LMWOAs were quantified as biological rock-weathering and organic phosphorus mobilization agents and compared to kinetics of acid phosphatase as a proxy for organic phosphorus mineralization. Calcium-bound phosphorus in topsoils decreased from 126 mg kg-1 in the arid shrubland, to 19 mg kg-1 in the Mediterranean woodland and was undetectable in the humid-temperate forest. In contrast, organic phosphorus in topsoils in close root proximity (0–2 mm distance to roots) was absent in the arid shrubland but raised to 220 mg kg-1 in the Mediterranean woodland and to 291 mg kg-1 in the humid-temperate forest. The organic phosphorus content in topsoils was 1.6 to 2.4 times higher in close root proximity (0–2 mm distance to roots) compared to bulk soil (4–6 mm distance to roots) in the Mediterranean woodland and humid-temperate forest, showing intensive phosphorus bioaccumulation in the rhizosphere. Redundancy analysis (RDA) revealed that LMWOAs were explained by the content of hydroxyapatite and variscite phosphorus-species in the arid shrubland, indicating that LMWOAs contribute to mineral weathering in this soil. LMWOA contents, phosphatase activity, and microbial biomass carbon correlated strongly with organic phosphorus in the humid-temperate forest soil, which implies a high relevance of LMWOAs for organic phosphorus recycling. In the Mediterranean woodland soil, however, oxalic acid correlated with organic phosphorus in the topsoil (suggesting phosphorus recycling), whereas in the subsoil malic and citric acid were correlated with primary and secondary phosphorus minerals (implying mineral weathering). We conclude that phosphorus acquisition and cycling depend strongly on climate and that the functions of LMWOAs in the rhizosphere change fundamentally along the precipitation gradient. In the arid shrubland LMWOAs facilitate biochemical weathering (rock eating), while in the humid-temperate forest their functions change towards supporting organic phosphorus recycling (vegetarian).
The polyphyletic group of black fungi within the Ascomycota (Arthoniomycetes, Dothideomycetes, and Eurotiomycetes) is ubiquitous in natural and anthropogenic habitats. Partly because of their dark, melanin-based pigmentation, black fungi are resistant to stresses including UV- and ionizing-radiation, heat and desiccation, toxic metals, and organic pollutants. Consequently, they are amongst the most stunning extremophiles and poly-extreme-tolerant organisms on Earth. Even though ca. 60 black fungal genomes have been sequenced to date, [mostly in the family Herpotrichiellaceae (Eurotiomycetes)], the class Dothideomycetes that hosts the largest majority of extremophiles has only been sparsely sampled. By sequencing up to 92 species that will become reference genomes, the “Shed light in The daRk lineagES of the fungal tree of life” (STRES) project will cover a broad collection of black fungal diversity spread throughout the Fungal Tree of Life. Interestingly, the STRES project will focus on mostly unsampled genera that display different ecologies and life-styles (e.g., ant- and lichen-associated fungi, rock-inhabiting fungi, etc.). With a resequencing strategy of 10- to 15-fold depth coverage of up to ~550 strains, numerous new reference genomes will be established. To identify metabolites and functional processes, these new genomic resources will be enriched with metabolomics analyses coupled with transcriptomics experiments on selected species under various stress conditions (salinity, dryness, UV radiation, oligotrophy). The data acquired will serve as a reference and foundation for establishing an encyclopedic database for fungal metagenomics as well as the biology, evolution, and ecology of the fungi in extreme environments.
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.
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.
Growing awareness of the impact of monoterpenes on climate, atmospheric chemistry, and indoor air quality has necessitated the development of measurement standards to globally monitor and control their emissions. For National Metrology Institutes to develop such standards, it is essential that they demonstrate measurement equivalence for assigned values at the highest levels of accuracy. This report describes the results of a pilot comparison for 4 key monoterpene species: α-pinene, 3-carene, R-limonene and 1,8-cineole, at a nominal amount-of-substance fraction of 2.5 nmol mol-1. The objective of this comparison is to evaluate participant capabilities to measure trace-level monoterpenes using their own calibration techniques.
The ISO 16000 standard series provide guidelines for emission measurements of volatile organic compounds (VOCs) from building materials. However, polymer-based consumer products such as toys may also release harmful substances into indoor air. In such cases, the existing standard procedures are unsuitable for official control laboratories due to high costs for large emission testing chambers. This paper aims at developing and comparing alternative and more competitive methods for the emission testing of consumer products. The influence of the emission chamber size was investigated as smaller chambers are more suited to the common size of consumer products and may help to reduce the costs of testing. Comparison of the performance of a 203 l emission test chamber with two smaller chambers with the capacity of 24 l and 44 ml, respectively, was carried out by using a polyurethane reference material spiked with 14 VOCs during the course of 28 days. The area-specific emission rates obtained in the small chambers were always similar to those of the 203 l reference chamber after a few hours. This implies that smaller chambers can provide at least useful numbers on the extent of polymer-based consumer product emissions into indoor air, thereby supporting meaningful exposure assessments.
The feasibility of microbial hydrogen consumption to mitigate the hydrogen embrittlement (HE) under different cathodic potentials was evaluated using the Devanathan-Stachurski electrochemical test and the hydrogen permeation efficiency h. The hydrogen permeation efficiency h in the presence of strain GA-1 was lower than that in sterile medium. The cathodic potential inhibited the adherence of strain GA-1 to AISI 4135 steel surface, thereby reducing the hydrogen consumption of strain GA-1. The adherent GA-1 cells were capable of consuming ‘cathodic hydrogen’ and reducing the proportions of absorbed hydrogen, indicating that it is theoretically possible to control HE by hydrogen-consuming microbes.
The hydrogen permeation current increase was noticed for carbon steel in 0.5 mol/L NaCl solution under strong anodic potentials, which is contrary to the common understanding. Hydrogen permeation under cathodic potentials has been widely studied because of possible hydrogen embrittlement failures of high strength steels in seawater, but investigations of anodic polarization on hydrogen permeation are fairly rare, as the hydrogen evolution reaction shall be retarded. To corroborate the observed phenomenon, experiments were conducted using both as-received and vacuum-annealed sheet specimens. It was verified that the observed phenomena originated from the released hydrogen in traps by metal dissolution under anodic polarization.
New antibacterial agents are urgently required to fight the emergence of antibiotic-resistant bacteria. We recently synthesized the first thioimidazolium ionene, which has antibacterial properties and can degrade in various media. This dual functionality is crucial in order to limit the environmental impact of these biocides. We have found that our polymer is stronger than benzalkonium chloride (BAC) against Pseudomonas aeruginosa and also readily degrades in the presence of base, while remaining stable in acidic environments. These results highlight a new emerging class of antibacterial degradable polymers.
In this work, we characterise the performance of a Sharp optical aerosol sensor model GP2Y1010AU0F. The sensor was exposed to different environments: to a clean room, to a controlled atmosphere with known aerosol size distribution and to the ambient atmosphere on a busy city street. During the exposure, the output waveforms of the sensor pulses were digitised, saved and a following offline analysis enabled us to study the behaviour of the sensor pulse-by-pulse. A linear response of the sensor on number concentration of the monosized dispersed PSL particles was shown together with an almost linear dependence on particle diameters in the 0.4 to 4 micrometer range.
The gathered data about the sensor were used to predict its response to an ambient atmosphere, which was observed simultaneously with a calibrated optical particle counter.
How the rock-inhabiting fungus K. petricola A95 enhances olivine dissolution through attachment
(2020)
Free-living and mycorrhizal fungi are able to enhance the weathering of rock and other solid substrates. Deciphering the exact mechanisms of these natural processes requires their experimental simulation. Moreover, by performing these simulations with genetically amenable rock-weathering fungi, one can knock-out certain fungal traits and consequently identify their weathering-relevant function. Here, the effect of the rock-inhabiting fungus, Knufia petricola A95, on the dissolution kinetics of an Fe-bearing olivine (Mg1.86Fe0.19SiO4) is investigated at 25 °C and pH 6 using reproducible batch and mixed flow experiments. The availability of a melanin-deficient mutant (ΔKppks) of K. petricola A95, which produces more extracellular polymeric substances (EPS) than the wild type (WT), enables the comparative study of the role of melanin and EPS in olivine dissolution. In abiotic dissolution experiments, the olivine dissolution rate decreased considerably over time at pH 6 but not at pH 3.5. This inhibition of abiotic olivine dissolution at pH 6 was most likely caused by the in-situ oxidation of ferrous Fe and/or the precipitation of ferric hydroxides at the olivine surface. In corresponding biotic experiments at pH 6, both the wild type K. petricola and its melanin-deficient mutant ΔKppks solubilised and bound significant amounts of Fe released by olivine dissolution. Fe oxidation and precipitation were thus prevented and olivine dissolution proceeded faster than in the abiotic experiments. By sequestering Fe directly at the olivine surface, the attached wild type K. petricola cells were particularly efficient at preventing the oxidation of Fe at the mineral surface: the slowdown of olivine dissolution almost completely disappeared. The attachment capacity of these wild type cells is most likely mediated by wild type-specific EPS. Our presented experimental systems allow the oxidation of mineral-released Fe and include a rock-inhabiting fungus, thus simulating chemical, physical and biological conditions that set dissolution rates in a way that is relevant to natural ecosystems.
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.
The growth rate of single bacterial cells is continuously disturbed by random fluctuations in biosynthesis rates and by deterministic cell-cycle events, such as division, genome duplication, and septum formation.
It is not understood whether, and how, bacteria reject these growth-rate disturbances. Here, we quantified growth and constitutive protein expression dynamics of single Bacillus subtilis cells as a function of cell-cycle progression. We found that, even though growth at the population level is exponential, close inspection of the cell cycle of thousands of single Bacillus subtilis cells reveals systematic deviations from exponential growth.
Newborn cells display varying growth rates that depend on their size. When they divide, growth-rate Variation has decreased, and growth rates have become birth size independent. Thus, cells indeed compensate for growth-rate disturbances and achieve growth-rate homeostasis. Protein synthesis and growth of single cells displayed correlated, biphasic dynamics from cell birth to division. During a first phase of variable duration, the absolute rates were approximately constant and cells behaved as sizers. In the second phase, rates increased, and growth behavior exhibited characteristics of a timer strategy. These findings demonstrate that, just like size homeostasis, growth-rate homeostasis is an inherent property of single cells that is achieved by cell-cycle-dependent rate adjustments of biosynthesis and growth.
Almost 500 municipal solid waste incineration plants in the EU, Norway and Switzerland generate about 17.6 Mt/a of incinerator bottom ash (IBA). IBA contains minerals and metals. Metals are mostly separated and sold to the scrap market and minerals are either disposed of in landfills or utilised in the construction sector. Since there is no uniform regulation for IBA utilisation at EU level, countries developed own rules with varying requirements for utilisation. As a result from a cooperation network between European experts an up-to-date overview of documents regulating IBA utilisation is presented. Furthermore, this work highlights the different requirements that have to be considered. Overall, 51 different parameters for the total content and 36 different parameters for the emission by leaching are defined. An analysis of the defined parameter reveals that leaching parameters are significantly more to be considered compared to total content parameters. In order to assess the leaching behaviour nine different leaching tests, including batch tests, up-flow percolation tests and one diffusion test (monolithic materials) are in place.
A further discussion of leaching parameters showed that certain countries took over limit values initially defined for landfills for inert waste and adopted them for IBA utilisation. The overall utilisation rate of IBA in construction works is approximately 54 wt%. It is revealed that the rate of utilisation does not necessarily depend on how well regulated IBA utilisation is, but rather seems to be a result of political commitment for IBA recycling and economically interesting circumstances.
The potential release of hazardous substances from polymer-based products is currently in the focus of environmental policy. Environmental simulations are applied to expose such products to selected aging conditions and to investigate release processes. Commonly applied aging exposure types such as solar and UV radiation in combination with water contact, corrosive gases, and soil contact as well as expected general effects on polymers and additional ingredients of polymer-based products are described. The release of substances is based on mass-transfer processes to the material surfaces. Experimental approaches to investigate transport processes that are caused by water contact are presented. For tailoring the tests, relevant aging exposure types and release quantification methods must be combined appropriately. Several studies on the release of hazardous substances such as metals, polyaromatic hydrocarbons, flame retardants, antioxidants, and carbon nanotubes from polymers are summarized exemplarily. Differences between natural and artificial exposure tests are discussed and demonstrated for the release of flame retardants from several polymers and for biocides from paints. Requirements and limitations to apply results from short-term artificial environmental exposure tests to predict long-term environmental behavior of polymers are presented.
Over the past two decades, per- and polyfluoroalkyl substances (PFASs) have emerged as worldwide environmental contaminants, calling out for sophisticated treatment, decomposition and remediation strategies. In order to mineralize PFAS pollutants, the incineration of contaminated material is a state-of-the-art process, but more cost-effective and sustainable technologies are inevitable for the future. Within this review, various methods for the reductive defluorination of PFASs were inspected. In addition to this, the role of mechanochemistry is highlighted with regard to its major potential in reductive defluorination reactions and degradation of pollutants. In order to get a comprehensive understanding of the involved reactions, their mechanistic pathways are pointed out. Comparisons between existing PFAS decomposition reactions and reductive approaches are discussed in detail, regarding their applicability in possible remediation processes. This article provides a solid overview of the most recent research methods and offers guidelines for future research directions.
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.
Potential use of incineration bottom ash in construction – Evaluation of the environmental impact
(2020)
Knowledge of the long-term leaching behavior of potentially harmful substances is crucial for the assessment of the environmental compatibility of reusing municipal solid-waste incineration bottom ash (MSWI BA) in construction, i.e., as a road base layer.
BA fractions obtained from wet-processing aiming at the improvement of environmental quality were used to investigate the mobility of relevant substances. Eluates from laboratory-scaled leaching procedures (column percolation and lysimeters) were analyzed to learn about the long-term release of substances. Unsaturated conditions and artificial rainwater (AR) were used in the lysimeter tests to simulate field conditions. In addition, batch test eluates were generated at usual liquid-to-solid ratios (L/S) for compliance testing purposes. A variety of cations and anions was measured in the eluates.
The wet treatment reduces the leaching of chloride and particularly sulfate by more than 60%. The release of typical contaminants for the treated MSWI BA such as the heavy metals Cu and Cr was well below 1% in the conducted leaching tests.
An increase in the Sb concentration observed in the lysimeter experiments starting at L/S 0.75 L/kg and in the column experiment at L/S 4 L/kg is assumed to be related to decreasing concentrations of Ca and thus to the dissolution of sparingly soluble calcium antimonate. The same leaching mechanism applies with V, but the concentration levels observed are less critical regarding relevant limit values. However, on the long term the behavior of Sb could be problematic for the application of MSWI BA in construction.
Many organizations in Europe collect data and perform research on municipal solid waste and the secondary raw materials that can be produced from them through recycling, urban mining, or landfill mining.However, the information generated and presented thereby is often highly aggregated, while research activities are many a time isolated. Both reduce the usability of the data and information generated. In order to better structure the knowledge generation on secondary raw materials production from municipal solid waste, we suggest to learn from the traditional raw materials mining Industry how to perform an integrated assessment and reporting of anthropogenic resources. This is exemplarily shown for the case of the anthropogenic resource municipal solid waste incineration bottom ash and airpollution control residues. A network of expert institutions from countries throughout Europe was build up to compile the information on legal and technological aspects for the recovery of different secondary raw materials from these residues, including construction minerals, metals, and salts. We highlight in our article the strength of the combined knowledge of an expert network not only on legal and technological, but also local and site-specific aspects of the recovery of secondary raw materials. By doing so, we hope to kick-off a discussion for how to organize and implement a structure for a better management of knowledge on anthropogenic resources, in order to provide a sustainable supply of secondary raw materials for a greener and more circular economy.
In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically Bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples fromriver Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum Parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 μg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14–0.81% of TF (determined using CIC) and EOF 0.04–0.28% of TF (determined using HR-CSGFMAS).
The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in Risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct.
Municipal solid waste incineration (MSWI) is one of the leading technologies for municipal solid waste (MSW) treatment in Europe. Incineration bottom ash (IBA) is the main solid residue from MSWI, and its annual European production is about 20 million tons. The composition of IBA depends on the composition of the incinerated waste; therefore, it may contain significant amounts of ferrous and non-ferrous (NFe) metals as well as glass that can be recovered. Technologies for NFe metals recovery have emerged in IBA treatment since the 1990s and became common practice in many developed countries. Although the principles and used apparatus are nearly the same in all treatment trains, the differences in technological approaches to recovery of valuable components from IBA – with a special focus on NFe metals recovery – are summarized in this paper.
Small-scale variations in mineral chemistry, textures, and platinum group element (PGE) mineralization were investigated in the Lower and Middle Group chromitite layers LG6, LG6a, MG1, MG2, and MG2 II from vertical drill core profiles at the Thaba mine in the northwestern limb of the Bushveld Complex. We present detailed geochemical profiles of chromite composition and chromite crystal size distribution curves to shed light on the processes of chromite accumulation and textural modification as well as mineralization. Multiple samples within each layer were assayed for PGE concentrations, and the respective platinum group mineral association was determined by mineral liberation analysis (MLA).
There is strong evidence for postcumulus changes in the chromitites. The crystal size distribution curves suggest that the primary chromite texture was coarsened by a combination of adcumulus growth and textural equilibration, while compaction of the crystal mush played only a minor role. Mineral compositions were also modified by postcumulus processes, but because of the very high modal amount of chromite and its local preservation in orthopyroxene oikocrysts, that phase retained much primary information. Vertical variations of chromite composition within chromitite layers and from one layer to another do not support the idea of chromite accumulation from crystal-rich slurries or crystal settling from a large magma chamber. Instead, we favor a successive buildup of chromitite layers by repeated injections of relatively thin layers of chromite-saturated magmas, with in situ crystallization occurring at the crystal mush-magma interface. The adcumulus growth of chromite grains to form massive chromitite required addition of Cr to the layers, which we attribute to downward percolation from the overlying magma.
The PGE concentrations are elevated in all chromitite layers compared to adjacent silicate rocks and show a systematic increase upward from LG6 (avg 807 ppb Ir + Ru + Rh + Pt + Pd + Au) to MG2 II (avg 2,062 ppb).
There are also significant internal variations in all layers, with enrichments at hanging and/or footwalls. The enriched nature of chromitites in PGEs compared to host pyroxenites is a General feature, independent of the layer thickness. The MLA results distinguish two principal groups of PGE mineral associations: the LG6, LG6, and MG1 are dominated by the malanite series, laurite, and PGE sulfarsenides, while the MG2 and MG2 II layers are characterized by laurite and PGE sulfides as well as Pt-Fe-Sn and PGE-Sb-Bi-Pb alloys. Differences in the PGE associations are attributed to postcumulus alteration of the MG2 and MG2 II layer, while the chromitites below, particularly LG6 and LG6a, contain a more pristine association.
Draft standards for the determination of organic pollutants in the solid matter of environmental matrices such as sludge, treated biowaste and soil have been basically developed in the framework of the European standardization project HORIZONTAL. A research project financed by the German Federal Environment Agency was initiated to finalize some of these CEN standard drafts, since fully validated standard procedures are crucial for the evaluation of their reliability in the context of implementation in legislation on environmental health.
Approach: Appropriate test materials (< 2mm particle size) were prepared and homogenized from contaminated soils, sludge and treated biowaste containing polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), dioxins, furans and dioxin-like-PCB and served, along with reference solutions, as the basis for international interlaboratory comparisons. Performance data of three analytical standard procedures were obtained by the statistical evaluation of results received from 11 to 29 participants per test material.
Results: The overall variation coefficients of reproducibility (between-lab standard deviations) for the sum parameters were roughly between 10 and 35 %. The variation coefficients of repeatability (within-lab standard deviations) range between 3 % and 8 % and show no trend considering the substance groups or matrices.
The highest coefficients of reproducibility were found for the analysis of PAHs, which were between 26 and 35 %, depending on the matrix, whereas 7-17 % reproducibility was observed for toxicity equivalents (TEQ) comprising dioxins, furans and dl-PCB.
Conclusions: Overall, the results confirm that the procedures described in the Technical Specifications are fit for purpose for all three matrices and that the feasibility of the HORIZONTAL approach, to cover several matrices with one standard per analyte, was thereby proven.
Tempeh is a common food in Indonesia, produced by fungal fermentation of soybeans using Rhizopus sp., as well as Aspergillus oryzae, for inoculation. Analogously, for economic reasons, mixtures of maize and soybeans are used for the production of so-called tempeh-like products. For maize, a contamination with the mycoestrogen zearalenone (ZEN) has been frequently reported. ZEN is a mycotoxin which is known to be metabolized by Rhizopus and Aspergillus species. Consequently, this study focused on the ZEN transformation during tempeh fermentation. Five fungal strains of the genera Rhizopus and Aspergillus, isolated from fresh Indonesian tempeh and authentic Indonesian inocula, were utilized for tempeh manufacturing from a maize/soybean mixture (30:70) at laboratory-scale. Furthermore, comparable tempeh-like products obtained from Indonesian markets were analyzed. Results from the HPLC-MS/MS analyses show that ZEN is intensely transformed into its metabolites alpha-zearalenol (alpha-ZEL), ZEN-14-sulfate, alpha-ZEL-sulfate, ZEN-14-glucoside, and ZEN-16-glucoside in tempeh production. alpha-ZEL, being significantly more toxic than ZEN, was the main metabolite in most of the Rhizopus incubations, while in Aspergillus oryzae fermentations ZEN-14-sulfate was predominantly formed. Additionally, two of the 14 authentic samples were contaminated with ZEN, alpha-ZEL and ZEN-14-sulfate, and in two further samples, ZEN and alpha-ZEL, were determined. Consequently, tempeh fermentation of ZEN-contaminated maize/soybean mixture may lead to toxification of the food item by formation of the reductive ZEN metabolite, alpha-ZEL, under model as well as authentic conditions.
Microorganisms perform multiple metabolic functions that shape the global cycling of elements, health and disease of their host organisms, and biotechnological processes. The rates, at which different metabolic activities are performed by individual cells, can vary between genetically identical cells within clonal populations. While the molecular mechanisms that result in such metabolic heterogeneity have attracted considerable interest, the environmental conditions that shape heterogeneity and its consequences have received attention only in recent years. Here, we review the environmental drivers that lead to metabolic heterogeneity with a focus on nutrient limitation, temporal fluctuations and spatial structure, and the functional consequences of such heterogeneity. We highlight studies using single-cell methods that allow direct investigation of metabolic heterogeneity and discuss the relevance of metabolic heterogeneity in complex microbial communities.