4 Material und Umwelt
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- Bottom ash (6)
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- 4.3 Schadstofftransfer und Umwelttechnologien (29) (entfernen)
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Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (<LOD to 58.1 μg/g). Moreover, the methods were contrasted with the "total hydrolyzable precursor" (THP) assay analyzed using gas-chromatography coupled mass spectrometry (GC-MS), which yielded concentrations of 6:2–10:2 fluorotelomer alcohols (<LOD-568 μg/g) for textile and paper samples. Furthermore, targeted analytical investigation of 25 compounds via liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) was conducted and accounted for significantly lower sum amounts (<LOD-0.98 μg PFAS/g). To estimate the fluorine mass balance of all methods, the fluorine levels of target analytical data were calculated and compared to the sum parameter values and evaluated. Finally, the efficiency of the extraction method was approximated by the recovery analysis of four selected SFP model compounds compared to their TF values, yielding 36.7–74.0% after extraction and 3.8–36.3% after processing the extract for the HOF sum parameter.
The long-term leaching behavior of incineration bottom ash (IBA) was studied with large-scale samples from two German waste incinerators with grate technology. The observation period was up to 281 days. The aging processes proceeded faster in the outdoor storage of the samples. The dominant factor in the leaching behavior is the pH, which starts at values above 12 and decreases to values below 10 (outdoors, <11 indoors). Most heavy metals exhibit minimum solubility in this pH range. The solubility of Sb depends on the prevailing Ca concentration, due to the formation of low-soluble Ca antimonate. The very low sulfate concentrations observed in the leaching tests with fresh IBA could be explained by the presence of ettringite. In the course of the aging reaction, ettringite is transformed into gypsum. The results from batch tests were compared with those from column tests, showing reasonable agreement. Leaching dynamics can be better followed with column tests. All results confirm that the use of IBA is possible under German law.
Das Recycling von gemischten Baustoffen führt neben der Herstellung von Gesteinskörnungen parallel zu einem stärker schadstoffbelasteten Stoffstrom, der circa ein Drittel der ursprünglichen Masse ausmacht. Dieser sogenannte Brechsand endet derzeit in der Deponierung und wird somit der Kreislaufwirtschaft entzogen. Der vorliegende Beitrag untersucht nun die Aufbereitung dieses Materials unter Verwendung einer Setzmaschine im Pilotmaßstab. Hierbei wird die Eignung dieser Technik evaluiert und das Aufbereitungsprodukt als möglicher Ersatzbaustoff untersucht.
Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted
and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but
consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values
of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations.
Half of global material consumption involves mineral material. The circularity is still low so that the enhanced use of secondary building material is required to close loops. Three different secondary building materials are discussed based on exemplary research results: construction and demolition waste (C&D waste), soil-like material, and incineration bottom ash (IBA). Focus was placed on the environmental compatibility of the materials examined mainly by standardized leaching tests. C&D waste was investigated after a wet treatment using a jigging machine, and soil-like material and IBA were characterized with respect to their material composition. Their environmental compatibilities in particular were studied using standard leaching tests (batch tests and column tests).
It was concluded that soil-like material can mostly be utilized even when the precautionary limit values set are exceeded by a factor of less than two. For C&D waste, the fine fraction below 2 mm and the content of brick material is problematic. IBA fulfills quality level “HMVA-2” following German regulations. Improved levels of utilization might be achievable with better treatment technologies.
For the first time, µ-X-ray fluorescence (µ-XRF) mapping combined with fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substances (PFAS) contamination and inorganic fluoride in samples concentrations down to 100 µg/kg fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheet) were investigated. µ-XRF mapping allows for a unique element-specific visualisation at the sample surface and enables localisation of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analysed via fluorine K-edge µ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded µ-XANES spectra. Complementarily, solvent extracts of all samples were target-analysed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg/kg dry weight (dw). All environmentally exposed samples revealed higher concentration of PFAS with a chain length >C8 (e.g. 580 µg/kg dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent from quantified PFAS amounts via target analysis, µ-XRF mapping combined with µ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples.
The most massive design on the Baltic shore used geosynthetic materials, the landslide protection construction in Svetlogorsk (1300 m long, 90,000 m2 area, South-Eastern Baltic, Kaliningrad Oblast, Russian Federation) comprises the geotextile and the erosion control geomat coating the open-air cliff slopes. Due to changes in elastic properties during long-term use in the open air, as well as due to its huge size, this structure can become a non-negligible source of microplastic pollution in the Baltic Sea. Weather conditions affected the functioning of the structure, so it was assessed that geosynthetic materials used in this outdoor (open-air) operation in coastal protection structures degraded over time. Samples taken at points with different ambient conditions (groundwater outlet; arid places; exposure to the direct sun; grass cover; under landslide) were tested on crystallinity and strain at break. Tests showed a 39–85% loss of elasticity of the polymer filaments after 3 years of use under natural conditions. Specimens exposed to sunlight are less elastic and more prone to fail, but not as much as samples taken from shaded areas in the grass and under the landslide, which were the most brittle.
Industrial-scale mechanical recycling of plastics has been established for years, but has technical and economic limits. Chemical recycling processes lead back to monomers or to the raw materials, so that in the end new goods can be produced for all areas of application of plastics. The variety of chemical recycling processes is large. The capacities of the plants are still low today. The profitability of the plants is strongly influenced by the price of oil; the profitability limit is currently between 50 and 60 US $ per barrel.
This Special Issue, ‘Measurement of the Environmental Impact of Materials’, is focused on the impact that materials have on the environmental compartments of soil, water and air. Leaching and emission processes, including underlying mechanisms, are a recurring topic in most published articles in the present Special Issue. Contributions have come from three continents and numerous countries (USA, Germany, France, Latvia, Poland, Russia, Japan, Korea and Thailand) indicating the global dimension of the subject.
The database gives information on the contamination of the shore of the South-Eastern Baltic with the debris of geosynthetic materials for the period 2018–2020. This new type of coastal pollution enters the natural environment due to the destruction of coastal protection structures and construction activities. The database contains sections:
(1) a list of types of geosynthetic material residues, their photographic images and photographs illustrating examples of finds in natural conditions
[1 List_geosynthetic_debris_SEB],
(2) monitoring data on the contamination of the beach strip with the debris of geotextiles, braids from gabions, geocontainers (big bags), geocells and geogrids for the beaches of the South-Eastern Baltic for the period 2018–2020
[2 Monitoring_geosynthetic_debris_SEB];
(3) statistical distributions of the found geosynthetic debris by size
[3 Scales_geosynthetic_debris_SEB] and (4) results of test surveys on the shores of Lithuania and Poland adjacent to Kaliningrad Oblast.
All data refer to the beaches of the Kaliningrad Oblast (Russia), including the Russian parts of the Vistula and Curonian Spits, but also contains information on a one-time assessment of the pollution of the beaches of the adjacent territories: the Polish shore from the Poland-Russia border on the Vistula Spit to the mouth of the Vistula River, the Lithuanian shore from the border Lithuania-Russia on the Curonian Spit to the border of Latvia-Lithuania. Materials were collected during field surveys within the ERANET-RUS_Plus joint project EI-GEO, ID 212 (RFBR 18-55-76002 ERA_a, BMBF 01DJ18005).