4 Material und Umwelt
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Organisationseinheit der BAM
- 4 Material und Umwelt (144)
- 4.1 Biologische Materialschädigung und Referenzorganismen (62)
- 4.2 Material-Mikrobiom Wechselwirkungen (24)
- 6 Materialchemie (21)
- 4.0 Abteilungsleitung und andere (17)
- 4.3 Schadstofftransfer und Umwelttechnologien (16)
- 4.5 Kunst- und Kulturgutanalyse (16)
- 4.4 Thermochemische Reststoffbehandlung und Wertstoffrückgewinnung (14)
- 6.2 Material- und Oberflächentechnologien (14)
- 1 Analytische Chemie; Referenzmaterialien (12)
19th and 20th centuries glass paint layers consist of a colour body and a colourless lead silicate flux, in which borax or boric acid was added as further component to improve the paint ability and to reduce the firing temperature for multiple layers of paint. Model glasses were used in laboratory tests to investigate the stability of glass paints with additions of boron oxide. To determine boron in paint layers, a LIBS-system with pulsed NdYAG-laser was used.
Over the past century, a range of synthetic compounds have been produced to improve humanity’s quality of life. These include pharmaceuticals, plastics, and other chemical compounds that possess properties making them potentially harmful when released to the environment (e.g., ecological and health impacts to humans and animals). Per- and polyfluoroalkyl substances (PFAS) are a large group of chemicals used in the formulations of thousands of consumer goods, including aqueous film-forming foams used to suppress aviation fires in training scenarios, non-stick cookware, fast-food wrappers, water-repellent fabrics, medical equipment, and plastic and leather products. Because of the recent regulations and restrictions on the use of long chain (≥C8) PFAS a significant shift in the industry towards short (C4-C7) and ultrashort (C1-C3) chain alternatives has been recognized the last years. Due to the high polarity and water solubility of ultrashort PFAS, the potential for bioaccumulation is low. However, the high persistence of ultrashort-chain PFAS will result in environmental accumulation, especially in aquatic environments, leading to potential risks for aquatic organisms and increased human external exposure through drinking water. Ultrashort PFAS like trifluoroacetic acid (TFA) are low to moderately toxic to a range of organisms. In addition, ultrashort PFAS can penetrate natural and anthropogenic barriers and eventually reach drinking water sources. Because common drinking water treatment techniques do not sufficiently remove them, they may reach human consumption. In the project we are focusing on detecting and removing PFAS, especially ultrashort-chain PFAS from contaminated groundwater. We are designing passive sampling devices, which can collect and monitor the temporal profile of PFAS species in groundwater. This will allow us to analyze PFAS contaminations in German and Israeli groundwater using state-of-the-art and novel analytical techniques and understand the extent of contamination. In addition to quantification, PFAS contaminated groundwater will be treated via a two-stage process to produce PFAS-free drinking water. As ultrashort-chain PFAS are difficult to analyze with the current target (LC-MS/MS) and sum parameter (AOF, EOF) analysis methods, we additionally using gas chromatography – mass spectrometry (GC-MS). Therefore, an analytical method based on GC-MS is in development to analyze the volatile ultrashort-chain PFAS (TFA, PFPrA, TFMS, PFEtS, PFPrS, trifluoroethanol, pentafluoropropanol and hexafluoro isopropanol) directly in contaminated groundwater samples with the headspace technique and in eluates of organic solvents from the developed passive sampler after direct injection. Moreover, a two-stages process is designed to increase the low concentrations found in groundwater using novel membranes processes such as closed-circuit reverse osmosis (CCRO) and mixed matrix composite nanofiltration membranes (MMCM). Next, the rejected streams containing higher concentrations of PFAS will be treated by coagulation, and the remaining PFAS adsorbed onto carbonaceous nanomaterials (CNMs). The DEFEAT-PFAS project will result in the development of novel tools to detect, quantify, and remove PFAS, especially ultrashort-chain PFAS from contaminated groundwater, and will acquire a new understanding of the extent of these contaminations.
Per- and polyfluoralkyl surfactants (PFASs) are industrially produced surface chemicals used in daily applications that have gained public and political attention due their unnaturally high appearance in drinking water, nourishments and soils. Their chemical structures exhibit both lipophilic and hydrophilic properties, leading to a highly inert and persistent character. Various PFASs have shown to be bioaccumulative in plants and animals, and some have been characterized as highly toxic when ingested. When exposed to the environment, PFASs slowly get mobilized by natural water resources, leading to contamination of large areas of soil and natural water sources. While PFASs contamination of drinking water has been investigated intensively, perfluoralkyl contamination of soils has been rarely examined as of yet. At the same time, an increasing amount of PFASs contamination sites are being discovered worldwide, calling for a sophisticated strategy towards analytical characterization. Since the number of known PFASs already exceeds 4700, the established sum parameters like extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF) are key elements to fully survey the impact of exposure. Simultaneously, innovative soil remediation strategies are required to contain environmental destruction and to minimize further
spreading of contaminants. Addressing these challenges requires suitable analytical devices that are capable of mobilizing PFASs in the solid as well as in the liquid phase. The use of combustion ion
chromatography (CIC) enables analysis of both immobile and volatile PFASs and allows the detection of both total fluorine (TF) and EOF or AOF of a given soil or aqueous sample. Based on preliminary results, the clean-up of a PFAS contaminated solid matrix is monitored via EOF detection over time.
Additionally, we demonstrate the pH dependency of hydrogen fluoride absorption on active carbon (AC) and found a simple organic additive to be an effective fluoride scavenger. The presented findings can be contributive with regard to future AOF/EOF sum parameter development and application.
Synchrotron XPS in the soft-X-ray regime is suitable for the detection of light elements commonly found in biological samples. Various model systems of biofilms have been developed and characterised at synchrotron- and lab-based facilities. By obtaining the chemical composition at various information depths, the vertical distribution of iodine in an artificial biofilm have been determined.
Im Verbundprojekt R-Rhenania wird eine industrielle Demonstrationsanlage am Standort der Monoverbrennungsanlage Altenstadt der Firma Emter errichtet und im Jahr 2024 den Betrieb aufnehmen. Die vorhandene Rostfeuerung-Monoverbrennung wird so umgebaut, dass ein neues thermochemisches Verfahren integriert werden kann, welches hochwirksame und schadstoffarme Dünger produziert (bis zu 17.000 t/a). Die thermochemischen Produkte werden in Gefäß- und Feldversuchen im ökologischen Landbau auf ihre Düngewirkung getestet. Die Umweltverträglichkeit der Demonstrationsanlage wird untersucht, wie auch die Übertragbarkeit des Verfahrens auf weitere Regionen.
Deciphering microbiological influenced corrosion processes on steel with single cell-ICP-ToF-MS
(2022)
Microbiologically influenced corrosion (MIC) is a highly unpredictable process dictated by the environment, microorganisms, and the respective electron source. Interaction pathways between cells and the metal surface remain unclear. The development of this novel single cell-inductively coupled plasma-time of flight-mass spectrometry analytical method and a MIC-specific staining procedure facilitate the investigation of steel-MIC interactions. With this it is possible to analyze the multi-elemental fingerprint of individual cells. The detection method revealed elemental selectivity for the corrosive methanogenic archaeal strain Methanobacterium-affiliated IM1. The interface between material and environmental analysis thus receives special attention, e.g., when considering MIC on solid steel. Hence, the possible uptake of individual elements from different steel samples is investigated. Results showed the cells responded at a single-cell level to the different types of supplemented elements and displayed the abilities to interact with chromium, vanadium, titanium, cobalt, and molybdenum from solid metal surfaces. The information obtained will be used in the future to elucidate underlying mechanisms and develop possible material protection concepts, thus combining modern methods of analytical sciences with materials research.
References.
ICP-ToF (time of flight) MS enables the analysis of the multi-element fingerprint of single cells. The single cell ICP-ToF-MS is used in the presented poster for the analysis of archaea involved in microbiologically influenced corrosion (MIC) of steel. By means of sc-ICP-ToF-MS, the possible uptake of individual elements from the respective steel is investigated - the information obtained will be used in the future to elucidate underlying mechanisms and develop possible material protection concepts. The work combines modern methods of analytical sciences with materials.
Nonporous corundum powder was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices.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). As a proof of concept, IgG was extracted with protein A from crude human plasma. 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.
Since nowadays people spend most of their time indoors, a healthy environment is essential. Volatile organic compounds (VOCs) emitted from furniture and building materials are reported to cause health complaints. Therefore, the usage of low emitting materials will improve the indoor air quality. Quantitative VOC emission testing is usually conducted in emission test chambers under specified controlled conditions as described in DIN 16000-9 and DIN EN 16516.
For reasons of quality control/quality assurance (QC/QA) and for a better comparability of test results from different laboratories, suitable emission reference materials (ERM) are needed. Here, it is important to have a homogenous material with known emission rates over a specific time. Different approaches can be found in literature, inter alia polymer films loaded with the target compound to be released again, or a lacquer material to which a VOC mixture is added. After curing of the lacquer, the material can be loaded into a test chamber. Drawback of those approaches are their relatively fast decreasing emission profiles. For QC/QA purposes according to the test standards, VOC sources with constant emission profiles are desirable.
The EU-funded research project MetrIAQ “Metrology for the determination of emissions of dangerous substances from building materials into indoor air” is working on a multi-component ERM with an envisaged instability of ≤ 10 % in the emission rate over at least 14 days.
Within a doctoral thesis porous materials are impregnated with VOCs. Supercritical CO2 is used as solvent. Thus, the impregnated material does not contain any solvent that may show a measurable amount of emission in the emission test chamber. Furthermore, CO2 has the benefits to have a good availability and low costs. For the selection of porous materials several properties like the pore size, the surface, and the interaction with the components in the atmosphere need to be considered. The impregnation method is optimised while the different porous materials are tested. For the selection of porous materials the pores need to be large enough for the VOC molecules, further influence of the pore size is tested.
Aluminum is an often-used building material in modern architecture. In recent years buildings from the 1950th and 1960th are increasingly subject of conservation works including the aluminum parts. Typical surface damages are signs of corrosion caused by weathering processes or scratches in the anodized layer due to extensive wear. To repair damaged aluminum surfaces, there are usually two options: smaller areas are repaired by using a touch-up pen, for larger damages it is necessary to remove the anodized layer completely. Both possibilities are disadvantageous for the objects; the touch-up pen often does not match the color together with an insufficient corrosion protection, while newly anodized layers often differ in color and gloss from the original surface.
For this reason, a research project was initiated to develop a mobile method to repair anodized aluminum parts. The first step focusses on the mobile anodization process by using the electrolyte with a gel substrate. Different cathodic materials are to be tested together with appropriate cooling material. The anodized area should be isolated to protect undamaged areas. Examinations of the produced layers are conducted by using Keyence microscope, eddy current testing and ESEM analysis. Further steps are to transform the coloring and sealing process for mobile application. Color could be applied by using a brush or by spray while the sealing process could be performed with water vapor. An heatable putty knife could be used, if heating up the area will be necessary. Once the application process is developed, the anodization will be tested on samples with artificial damages, fixed in horizontal and vertical positions. The stability of the anodized surface will be examined by accelerated ageing in a climate chamber and outdoor weathering.
The electrolyte (diluted sulfuric acid) was combined with a gel binder to enable a mobile application. Several thickening agents were tested concerning their conductivity and stability in acid systems. Anodization tests with different cathodic material and shapes were conducted. The temperature during anodization was controlled and adjusted if necessary. The anodized area was restricted by using either a lacquer, an adhesive or a removable silicon barrier. The fist results show the feasibility of the method on enclosed areas. The achieved thickness was measured by eddy current testing and the structure was controlled by ESEM analysis. The examinations show a connection between thickness and porosity of the anodized layers and the temperature during the application process.
Next steps are testing mobile coloring and sealing methods followed by mobile anodization on artificial damaged areas.