4 Material und Umwelt
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Scientific material analysis of the elemental composition of inks from different strata of a manuscript has the potential to complement scholarly observations using palaeography and philology in reconstructing the history of the manuscript’s production, correction and repair.
There are three typologically different classes of black writing inks: soot inks consist of carbon particles.
In this study, nanoscopic particles of magnesium Fluoride (MgF2) and calcium fluoride (CaF2) also known as nano metal fluorides (NMFs), were evaluated for their potential to improve wood durability. Even though these fluorides are sparingly soluble, their synthesis in the form of nano-sized particles turns them into promising candidates for wood preservation. Their distinct property of low-water solubility is proposed to maintain long-lasting protection of treated wood by reducing the leaching of fluoride. Analytical methods were used to characterize the synthesized NMFs and their distribution in treated wood specimens. Transmission electron microscopy images showed that these fluoride particles are smaller than 10 nm. In nano metal fluoride (NMF) treated specimens, aggregates of these particles are uniformly distributed in the wood matrix as confirmed with scanning electron microscopy images and their corresponding energy-dispersive X-ray spectroscopy maps. The fluoride aggregates form a protective layer around the tracheid walls and block the bordered pits, thus reducing the possible flow path for water absorption into wood. This is reflected in the reduced swelling and increased hydrophobicity of wood treated with NMFs. The biocidal efficacy of NMFs was tested against brown-rot fungi (Coniophora puteanaand Rhodonia placenta), white-rot fungus (Trametes versicolor), and termites (Coptotermes formosanus). The fungal and termite tests were performed in accordance with the EN 113 (1996) and EN 117 (2012) standards, respectively. Prior to fungal tests, the NMF treated wood specimens were leached according to the EN 84 (1997)standard. Compared to untreated specimens, the NMF treated wood specimens have a higher resistance to decay caused by brown-rot fungi, white-rot fungus, and termites. Although all NMF treatments in wood reduce the mass loss caused by fungal decay, only the combined treatment of MgF2 and CaF2 has efficacy against both brown-rot fungi and white-rot fungus. Similarly, wood treated with the combined NMF formulation is the least susceptible to attack by C. formosanus.It is proposed that combining MgF2 and CaF2changes their overall solubility to promote the release of fluoride ions at the optimal concentration needed for biocidal efficacy against fungi and termites. In this thesis, it was proven that even after leaching, sufficient fluoride was present to protect NMF treated wood from fungal decay. This shows that NMFs are robust enough for above ground contact outdoor applications of wood, where permanent wetness cannot be avoided according to Use Class 3.2, as per the EN 335 (2013) standard. Also, they pose a low risk to human health and the environment because they are sparingly soluble. Since NMFs significantly reduce the decay of wood, the CO2 fixed in it will be retained for longer than in unpreserved wood. Overall, the novel results of this study show the potential of NMFs to increase the service life of building materials made from non-durable wood.
While studying the socio-geographic history of inks, division 4.5 (Analysis of cultural artefacts and assets) of the BAM (Bundesanstalt für Materialforschung und -prüfung) in Berlin together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques.
Using this protocol, scientists can assist scholars in addressing a rather broad range of historical questions that cannot be answered unequivocally through scholarly research alone. Among these are investigations on collaboration between scribes and scriptoria, on the usage and annotation of manuscripts and on their path through time and space in general. This research can thus help to reconstruct the circumstances of the production of written heritage as well as their history and transmission.
To facilitate the dialogue between the scholars and the scientists a simple optical tool was developed to allow the scholars to perform preliminary ink analysis required for formulation of the question that in turn can be answered by scientific in-depth investigations. In this paper, ink types and their identification method is accompanied by examples of the recent work conducted on parchment manuscripts in the Austrian National Library.
The earliest known recipes for iron gall inks include four basic ingredients: oak galls – pathological growths of oak leaves; metal salts – usually referred to as vitriol; a binder such as gum Arabic; and water. The final product differs in the elemental composition due to the multitude of recipes as well as differences within the composition of the ink’s ingredients. Nowadays, based on the qualitative and semi-quantitative evaluation of X-ray fluorescence data, it is possible to distinguish inks on the basis of the so-called fingerprint model. The first goal of our study was to determine to what extent the type of XRF spectrometer affects the quality of the ink evaluation. We tested two types of spectrometers, semi-stationary machines equipped with polycapillary focusing optics and a handheld spectrometer with a diaphragm collimator and a relatively big interaction spot.
The second goal was to address the issue of whether the ink composition might be affected by storage in a metal container. The presentation will discuss the role of the spectrometer type in the evaluation of a thin layer material such as ink.
We have also learned that the iron-gall ink composition might depend on the type of vessel in which ink was being stored.
Conventional fertilisers have their disadvantages as nutrient release is not synchronised with the demand of plants. Several approaches of "next generation fertilisers" are aiming at controlled nutrient release. Recycling fertilisers are often not soluble in water but fully plant available. They are suitable raw materials for the production of new types of controlled release fertilisers.
Wet-mechanical treatment: Processing of bituminous road construction waste in a jigging machine
(2023)
Jigging machines are used in processing technology in many areas. Examples are the processing of coal, ores, and primary and secondary raw and waste materials. Even small differences in density are offen sufficient for successful sorting. In the work presented here, milled material from road construction waste contaminated with bitumen is to be separated from uncontaminated material. In this way, scarce landfill space could be saved and mineral material be returned to the material cycle.
In Europe, nearly 19 Mt/y of bottom ash (BA) are produced. Of this quota, only 46 %wt. was treated, often in poorly performing plants, leaving behind 10 Mt of untreated and unrecovered BA, destined to landfill. The resulting 2.14 Mt loss of valuable materials included 1 Mt mineral fraction and 0.97 Mt ferrous metals, mostly from untreated BA, and 0.18 Mt non-ferrous metals, mostly from unrecovered BA. For the coarser fractions, the main obstacle to BA being used as recycling aggregate is the content of salts and potential toxic elements (PTEs), concentrated in a layer that coats BA particles. For the fine BA fractions, usually underexploited and landfilled, it is estimated that up to 0.95 Mt/y of ferrous and non-ferrous metals are not recovered in Europe.
During the workshop, the key results of BASH Treat project will be presented: the results of 2 industrial tests performed in BA treatment plants in Germany and Sweden; a novel dry treatment for the removal of salts and PTEs from BA coarse particles; a wet process for the recovery of heavy metal compounds from the fine fraction; a technical-economic assessment of the EU potential for the optimization of BA management.
In addition to previously reported results on the simulated aging of polystyrene samples (PS) containing 1 wt. % hexabromocyclododecane (HBCD), we present the first results of our investigations of polypropylene (PP)-samples containing 0.1 wt. % BDE-209. All studied polymer samples were exposed to a defined weathering schedule in a climate chamber in accordance to regulation EN ISO 4892-3:2006.For the determination of BDE-209 in the collected rain water samples derived from the used climate chamber, the samples were prepared in accordance with a validated protocol. Before the analyses, each sample was spiked with 2 µL of isotopically labeled BDE-209 (13C10-BDE-209) to serve as internal standard (ISTD) in the performed stable isotope dilution analysis. Subsequently the samples were extracted with isooctane, the obtained aliquots of the extracts were concentrated to 200 µL and 2 µL of the resulting solution were injected to the GC/MS for quantification.
Additionally, the total bromine contents are monitored for the aged and untreated samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as well as X-ray fluorescence analysis (XRF) as non-destructive and rapid method. Furthermore, results from surface analysis using environmental scanning electron microscopy (ESEM) for morphological characterization of the aged and untreated samples were presented and discussed. In general, the resulting data from the accelerated aging will be compared to those from the natural weathering experiments (“atmospheric exposure”, in soil).
The atmospheric exposure was performed by placing the samples on a weathering rack, which is aligned in SW direction (in a 45° angle to the horizon). The weathering data were regularly recorded by Deutscher Wetterdienst at this site. The surfaces of the test specimens (aged and stored references) were analyzed by ESEM as well as by LA-ICP-MS and by XRF. The surface of PS and PP specimens aged outdoors present the aging under real conditions and allow the comparison to the accelerated aged specimens by means of the weathering chamber. This way, we explore the efficiency of the accelerated aging procedure, which provides the advantage of well-defined and reproducible conditions compared to natural weathering, as a tool for testing different plastic materials.
Additionally “in soil” experiments were conducted in-door in a well characterized testing soil. The soil (boulder-clay, sand with 12 % loam, particle size in total 0.2-4 mm) is filled in a free-draining concrete basin inside of an air-conditioned room. In this manner, TOC, water capacity and humidity are recorded parameters. To assure a washing out process from the samples by the raining water, the target water content is calculated to 8%. The actual humidity is measured by a tensiometer, assuring the duration of the raining period. The water content is additionally monitored by weight of the basin, capturing water from raining periods. The correct humidity is a fundamental parameter for biological activity. Samples of PS resp. PP were of dimension 10x1cm and 5 specimens were placed up to the half in the soil per basin. Microbial activity of the soil, monitored by the reference polyurethane, sets HBCD resp. BDE-209 of the samples free and will be leached from the samples by raining water. Thereafter these will be captured by passive samplers placed in a distinct distance to the samples in the soil. The “in soil” experiments are complementary to the weathering experiments due to the biological activity in the soil. These experiments simulate the fate of the brominated flame retardants in the biosphere.
Wastewater contains a diverse array of organic and inorganic compounds and its complex composition strongly depends on the location and the connected dischargers. However, municipal wastewater as a carrier of feces and urine generally contains considerable amounts of the main nutrients nitrogen and phosphorus. The latter is in the focus of the discussions about the recovery potential of wastewater due to the relatively high mass flows of phosphorus in wastewater and the finite nature and decreasing quality of phosphate rock reserves. But due to the presence of the whole periodic table of elements, wastewater might contain further valuable components of interest for recovery including those defined as critical raw materials by the European Commission. Phosphorus and most of the other critical raw materials are fixed in the sewage sludge and after incineration in the sewage sludge ash (SSA). This is accompanied by high concentration factors from wastewater via sludge to ash. However, the mass fractions of the majority of elements in sewage sludge are comparable to those of the earth crust, indicating no relative enrichment. Nevertheless, enrichment factors of 100 or higher are given for phosphorus, copper, zinc, cadmium, silver, tin, lead and the platinum group elements indicating an anthropogenic input. An economic value of sewage sludge was estimated to $460,-/t calculated on the basis of the respective market prices for high purity elements – a theoretical value. A German survey of sewage sludge ashes showed that the mass fractions and the mass flows of most of the elements present in SSA are probably too low for an economic recovery. In most cases the mass flows are rather small compared to the imports and the chemical forms are not suitable for recovery. An exception is phosphorus that is present in high mass fractions up to 13% and that bears a high substitution potential. If the application of P-recovery technologies lead to a further concentration of valuable elements e.g. as by-products in side streams of the process, it would probably make also the recovery of other elements of economic interest.
Waste, Evaluation Methods
(2019)
It is difficult to decide which waste management system fulfills best predefined sustainability goals such as maximum materials and energy recovery, least environmental impact, and lowest societal cost. Such decisions are based on many parameters. However, several evaluation methods exist with different scope and output, and the application of one or more evaluation methods provides an objective comparison of alternatives.