Filtern
Dokumenttyp
- Zeitschriftenartikel (11)
- Beitrag zu einem Tagungsband (5)
- Buchkapitel (1)
- Beitrag zu einem Sammelband (1)
- Corrigendum (1)
- Vortrag (1)
- Forschungsbericht (1)
- Forschungsdatensatz (1)
Schlagworte
- Additive Fertigung (5)
- Additive manufacturing (3)
- Combustion Ion Chromatography (3)
- Künstliche Bewitterung (3)
- PFAS (3)
- Thermografie (3)
- 3D Druck (2)
- Active thermography (2)
- Artificial weathering (2)
- Geosynthetics (2)
Organisationseinheit der BAM
- 4 Material und Umwelt (14)
- 4.3 Schadstofftransfer und Umwelttechnologien (14)
- 7 Bauwerkssicherheit (7)
- 7.5 Technische Eigenschaften von Polymerwerkstoffen (7)
- 8 Zerstörungsfreie Prüfung (7)
- 8.0 Abteilungsleitung und andere (7)
- 1 Analytische Chemie; Referenzmaterialien (4)
- 1.7 Organische Spuren- und Lebensmittelanalytik (3)
- 1.1 Anorganische Spurenanalytik (2)
- 1.8 Umweltanalytik (2)
Paper des Monats
- ja (2)
Eingeladener Vortrag
- nein (1)
Einstufung von Aschen und Schlacken aus der Abfallverbrennung im Hinblick auf die weitere Verwertung
(2024)
There are two mirror entries in the European Waste Catalogue for bottom ash and slag from waste incineration: 19 01 11* and 19 01 12. Entry 19 01 11* describes a waste material containing hazardous substances. It was shown that only the hazardous property HP14 (ecotoxic) is of relevance for the classification. If substances with the hazard statement code (HSC) H400, H410, H411, H412 and H413 are present in incineration bottom ash (IBA) above certain level the waste is classified as hazardous, otherwise it is non-hazardous (in this case 19 01 12). It was further shown that only Cu, Zn and Pb compounds have an impact on the classification using a summation rule: 100xΣ c(H410) + 10xΣ c(H411) + Σ c(H412). Limit value is 25 percent. It is obvious that H410 substances have the highest impact. Therefore, the knowledge of the elemental composition of IBA is not sufficient because the content of distinct chemical compounds (with the respective molecular weight) is needed. When the exact speciation is not known a worst-case approach has to be applied. A practical guideline for the estimation of HP14 was developed based on the definition of 4 substance groups: 1. Metals and alloys, 2. Water-soluble substances, 3. Oxides and carbonates and 4. Substances not soluble in weak acids. In substance group 1 only fine Zn powder has the HSC H410. Water-soluble substances are assumed to be H410 substances. Their concentrations are, however, regularly below the cut-off value of 0.1 %. The amount of substance group 3 is estimated by a selective extraction with maleic acid. According to the worst-case approach it is assumed that CuCO3xCu(OH)2 and ZnO represent the respective Cu and Zn species in IBA because these substances have the highest stochiometric factor. Even with this worst-case approach results from operators of IBA treatment plant showed that the limit value of 25 % is not exceeded.
The requirements for utilization of IBA in Germany are defined in the Secondary
Building Materials Decree (Ersatzbaustoffverordnung EBV) which was set into force in August 2023. Leaching methods (batch test or column test) with a liquid-to-solid ratio of 2 l/kg are applied. IBA fulfills the requirements for class HMVA-2. Actually, even a classification of IBA as hazardous (i.e 19 01 11*) would not affect utilization but handling and transport.
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 chemical state of antimony and vanadium species in municipal solid waste incineration bottom ash
(2023)
Due to the large quantity as residual mineral waste, municipal solid waste incineration - bottom ash (MSWI-BA) is an interesting secondary raw material that can be utilized for road construction. However, leaching of chloride, sulfate and potentially hazardous heavy metals from MSWSI-BA into the environment may cause problems in utilization of it in civil engineering. In a previous study, we performed a long-term leaching test of MSWI-BA in a lysimeter for almost six years to investigate the efficiency of the treatment process on the release of hazardous substances. While concentrations of chloride, sulfate and the majority of the heavy metals started to decrease rapidly with progressive liquid-to-solid ratio (L/S), the ecotoxic hazardous elements antimony (Sb) and vanadium (V) behaved differently. To unravel these unusual release behaviors and the oxyanion-formation of Sb and V we will apply HERFD-XANES spectroscopy to analyze their chemical state.
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.
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.
Wie können industriell synthetisierte Schadstoffe aus einer Stoffklasse quantifiziert werden, deren genauer Umfang unbekannt ist und auf mehrere tausend Verbindungen geschätzt wird? Im Falle der per- und polyfluorierten alkylierten Substanzen (PFAS) stellen sich Wissenschaftler*innen weltweit seit über zehn Jahren diese Frage. Neben der etablierten Methodik der Einzelstoffanalytik (engl. target analytic) existieren Summenparameteranalysen zur Quantifizierung
organisch gebundener fluorierter Verbindungen in Umweltmedien und Konsumprodukten. An der Bundesanstalt für Materialforschung und -prüfung (BAM) beschäftigen wir uns mit der Weiterentwicklung von Summenparametermethoden am Beispiel von PFAS-belasteten Umweltkompartimenten wie Böden, Klärschlämmen und Gewässerproben sowie PFAS-haltigen Konsumgütern. In diesem Beitrag stellen wir zwei ausgewählte Fallbeispiele vor und diskutieren die Vor- und Nachteile der Methoden im Vergleich zur Einzelstoffanalytik.
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.
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.
Per- and polyfluoroalkyl substances (PFAS) are a group of more than 4700 anionic and cationic anthrophonic substances which have been used extensively in a variety of products and industries due to their inert chemical stability and resistance to degradation by heat or acids. As a result of continuous use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil and groundwater resources. However, because of the continuous use of fluorinated consumer products, also effluents and sewage sludge from wastewater treatment plants (WWTPs) have been shown to be an important source of PFAS contamination into the aquatic environment. Resulting from recent stricter regulations and restrictions in the last years on the use of long chain (≥C8) PFAS, there is a significant shift in the chemical industry towards production of short (C4-C7) and ultrashort (C1-C3) chain alternatives. With the amendment of the Sewage Sludge Ordinance in 2017 the German legislation banned sewage sludge application on agricultural land, and by 2029/2032 sewage sludge will be completely prohibited from agricultural application. While environmental exposure of organic pollutants like PFAS, pesticides and pharmaceuticals are no longer desirable, phosphorus (P) from sewage sludge must still be used to produce high-quality P-fertilizers for a circular economy. Currently, plant-available P-fertilizers from sewage sludge/wastewater can be produced using a variety of treatment approaches including precipitation, leaching, and thermal treatment. However, the fate of legacy and emerging PFAS compounds during P leaching, precipitation and treatment from sewage sludge and wastewater is for the most parts still unknown.
Im Rahmen des Projekts konnte gezeigt werden, dass Geokunststoffe bei ausreichender Stabilisierung Einsatzdauern von über 100 Jahren besitzen. Es werden keine Stoffe freigesetzt, die für Wasserorganismen schädlich sind. An den Ostseestränden im Gebiet Kaliningrad werden nennenswerte Mengen von Kunststoffresten gefunden, die zum Teil aus Küstenschutzbauwerken stammen. Ursache ist hier jedoch eine verfehlte Materialauswahl. Hauptsächlich stammen die Kunststoffreste am Strand jedoch aus unsachgemäße Abfallbehandlung.