4 Material und Umwelt
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Kunststoffdichtungsbahnen (KDB) aus PE-HD (Polyethylen hoher Dichte) werden häufig zur Abdichtung von Bauwerken in der Geotechnik verwendet. Diese Produkte werden aus einem Kunststoff mit relativ komplexer Zusammensetzung hergestellt. Um eine Aussage über die Haltbarkeit von KDB aus PE-HD treffen zu können, muss das Materialverhalten berücksichtigt werden. In diesem Zusammenhang sind die wichtigsten Aspekte der Dauerhaftigkeit die Spannungsrissbeständigkeit und die Beständigkeit gegen Oxidation. Verschiedene PE-Sorten weisen eine unterschiedliche Spannungsrissbeständigkeit auf. Um dieser Eigenschaft von PE-HD zu begegnen, werden nur KDB aus sehr hochwertigen Rohstoffen zugelassen. Auf der anderen Seite werden hohe Anforderungen an die umgebenden Schichten, wie Auflager und Schutzschicht gestellt, um möglichst geringe Spannungen zu erzeugen und damit Dehnungen die Dehnungen der KDB gering zu halten. Bestimmte Medien, die bei den betreffenden Prüfungen verwendet werden, dürfen nicht mehr in der EU in Verkehr gebracht werden. Im Folgenden sollen die Zusammenhänge in Kürze dargestellt werden.
Darüber hinaus sollen Diskussionen und Änderungen im Zusammenhang mit der Zulassungsrichtlinie für KDB vorgestellt werden. Der aktuelle Stand der Diskussion im Zusammenhang mit den verwendeten Tensiden in Bezug auf die Spannungsrissprüfung und weiterer Prüfungen wird aufgezeigt. Änderungen der Fremdprüfung von sogenannten Sandschutzmatten, des Standards zur Qualitätsüberwachung (SQÜ) von Kunststoff Dränelementen (KDE) und der Anpassung der Formulierungen zum Überbau der in Abdichtungen verwendeten Produkte werden in Kürze aufgezeigt.
Kunststoffdichtungsbahnen (KDB) aus PE-HD (Polyethylen hoher Dichte) werden häufig zur Abdichtung von Bauwerken in der Geotechnik verwendet. Diese Produkte werden aus einem Kunststoff mit relativ komplexer Zusammensetzung hergestellt. Um eine Aussage über die Haltbarkeit von KDB aus PE-HD treffen zu können, muss das Materialverhalten berücksichtigt werden. In diesem Zusammenhang sind die wichtigsten Aspekte der Dauerhaftigkeit die Spannungsrissbeständigkeit und die Beständigkeit gegen Oxidation. Verschiedene PE-Sorten weisen eine unterschiedliche Spannungsrissbeständigkeit auf. Um dieser Eigenschaft von PE-HD zu begegnen, werden nur KDB aus sehr hochwertigen Rohstoffen zugelassen. Auf der anderen Seite werden hohe Anforderungen an die umgebenden Schichten, wie Auflager und Schutzschicht gestellt, um möglichst geringe Spannungen zu erzeugen und damit Dehnungen die Dehnungen der KDB gering zu halten. Bestimmte Medien, die bei den betreffenden Prüfungen verwendet werden, dürfen nicht mehr in der EU in Verkehr gebracht werden. Im Folgenden sollen die Zusammenhänge in Kürze dargestellt werden.
Darüber hinaus sollen Diskussionen und Änderungen im Zusammenhang mit der Zulassungsrichtlinie für KDB vorgestellt werden. Der aktuelle Stand der Diskussion im Zusammenhang mit den verwendeten Tensiden in Bezug auf die Spannungsrissprüfung und weiterer Prüfungen wird aufgezeigt. Änderungen der Fremdprüfung von sogenannten Sandschutzmatten, des Standards zur Qualitätsüberwachung (SQÜ) von Kunststoff Dränelementen (KDE) und der Anpassung der Formulierungen zum Überbau der in Abdichtungen verwendeten Produkte werden in Kürze aufgezeigt.
An approach to achieve 'zero leakage' is discussed with respect to experience in Germany, where strict regulations for landfill lining and capping Systems have been developed and issued because of large environmental Problems related to landfills that accumulated in the 1970s and 1980s. Using a thick, high-quality high-density Polyethylene (HDPE) geomembrane (GM) that is installed free of residual waves and wrinkles in intimate contact with a compacted clay liner or geosynthetic clay liner of very low permeability, by a qualified, experienced, well-equipped and properly third-party-controlled installer, and which is protected by heavy protection layers designed with respect to the long-term performance of the GM may result in a liner or capping system of practically no leakage. This is demonstrated by analysing results of measurements obtained from permanently installed leak-detection Systems in combination with HDPE GMs. The survey was based on 32 German landfills with 1.276.500 m² of installed GMs.
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.
Antimon (Sb) wird in Industrieprodukten hauptsächlich als Flammschutzmittel in Kunststoff verwendet. Aufgrund solcher Zusätze in Kunststoffen landet etwa die Hälfte von Sb am Ende der Lebensdauer in der Verbrennung fester Siedlungsabfälle und folglich in relevanten Mengen in der erzeugten Bodenasche. Bei Kontakt mit Wasser ist die anfängliche Auslaugbarkeit gering, da Antimonat mit Ca2+ schwerlösliche Verbindungen bilden. Nach der Carnonatisierung der Verbrennungsasche (IBA) während der fortschreitenden Alterung nimmt der pH-Wert in den Sickerwasser ab. Mit abnehmender Ca-Konzentration im Eluat ändert sich das Lösungsgleichgewicht und Antimonate lösen sich auf.
In Deutschland ist beabsichtigt, Sb in IBA mit der geplanten Umsetzung der sogenannten Mantelverordnung (MantelVO, die Bestimmungen zur Verwertung von Mineralabfällen enthält) in naher Zukunft zu regulieren. Die im Entwurf festgelegten Grenzwerte können für IBA kritisch sein und stellen daher ein Risiko für die Verwendung der Mineralfraktion von IBA in den gut etablierten Recyclingwegen dar.
Die Untersuchung altlastverdächtiger Flächen umfasst viele einzelne Schritte von der Probenahme über die Probenvorbehandlung bis hin zur eigentlichen Analyse, die zur Ergebnisunsicherheit beitragen. Beim Vergleich der Ergebnisse mit Bewertungsmaßstäben, um Entscheidungen zur Bewertung von Altlasten zu treffen, sind diese Faktoren zu berücksichtigen. Die Rolle von verschiedenen Unsicherheitskomponenten wird mit Blick auf Elutionsverfahren diskutiert.
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.
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.
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.
Verwertung von Bodenmaterialien - Ergebnisse aus dem UFOPLAN-Vorhaben und Transfer der Ergebnisse
(2019)
Dem Fachbeirat Bodenuntersuchungen des BMBF/UBA wurden Ergebnisse zum UFOPLAN-Forschungsvorhaben „Monitoring zur Verwertung von Bodenmaterial“ vorgestellt. Die potentielle Auswirkung der neuen Regularien in der geplanten Novelle der BBodSchV (4. Referentenentwurf der Mantelverordnung) auf die Erweiterung der Verwertungsmöglichkeiten von Bodenmaterialien wird aufgezeigt. Probleme des Umgangs mit der analytischen Messunsicherheit im Grenzwertbereich und mit der Vergleichbarkeit der zugelassenen Elutionsverfahren werden diskutiert.
Derzeit gibt es intensive Diskussionen über die Entlassung von Deponien aus der Nachsorgephase. Die Deponie müsste dafür nach der Deponieverordnung (DepV) u. a. „insgesamt dauerhaft standsicher" sein. Geokunststoffe erfüllten ihre Funktion über einen Zeitrahmen von lediglich mindestens hundert Jahren. Dies stehe somit im Widerspruch wird argumentiert. Das neue LANUV-Arbeitsblatt 33 schließt daher im Moment eine Entlassung aus der Nachsorge von Deponien faktisch aus, wenn in den Böschungen Geokunststoffprodukte eingesetzt wurden. Auch der Fachbeirat der BAM zur Zulassung von Geokunststoffen, Polymeren und Dichtungskontrollsystemen hat sich daher mit der Thematik beschäftigt. Die aktuelle Situation soll daher auf dieser Grundlage diskutiert werden.
Im Beitrag wurden Ergebnisse von Elutionsuntersuchungen mit PFC kontaminierten Bodenmaterialien vorgestellt. Zum einen waren das Untersuchungen zur Eignung von Säulenversuchen für diese Schadstoffgruppe und zum anderen vergleichende Schüttel- und Säulenversuche für zwei verschiedene Böden mit unterschiedlichen PFC-Kontaminationsquellen.
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.
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.
Im Beitrag wurden erste Ergebnisse eines laufenden UFOPLAN-Vorhabens zu den neuen Kriterien der Verwertungsmöglichkeiten von Bodenmaterialien außerhalb der durchwurzelbaren Bodenschicht nach den §§ 6 bis 8 der Novelle der BBodSchV vorgestellt. Der Schwerpunkt lag auf Untersuchungen der Schadstoffgruppe der PAK. Dabei wurden Probleme der Vergleichbarkeit und Leistungsfähigkeit verschiedener Elutions- und Analyseverfahren der PAK-Analytik diskutiert.
Wie Länder mit ihren Abfällen umgehen, hängt nicht nur von der Wirtschaftskraft eines Landes ab. Selbst in einem reichen Land wie Australien werden unbehandelte Abfälle einfach deponiert. Im Rahmen der Travelling Conference, einer vom Bundesministerium für Bildung und Forschung (BMBF) geförderten Vortragsreihe, besuchten Fachleute die Länder Südkorea, Vietnam und Australien, um mit Experten vor Ort Fragestellungen aus der Abfallwirtschaft zu diskutieren. Zu den Schwerpunktthemen zählte die Steigerung der Ressourceneffizienz im Spannungsfeld von ökonomischen und umweltpolitischen Interessen. Eine Frage war beispielsweise die Bewertung der Umweltverträglichkeit von mineralischen Abfällen, wenn diese als Ersatzbaustoffe eingesetzt werden. In diesem Beitrag werden Ähnlichkeiten und Unterschiede bei der Entsorgung von Siedlungsabfällen, beim Recycling und bei der Bewertung der Umweltverträglichkeit der Wiederverwertung von Abfällen in den drei besuchten Ländern im Vergleich zu Deutschland aufgezeigt. Dabei ist man sich in Deutschland und den drei besuchten Ländern einig, dass die Abfallbeseitigung auf Deponien ohne Rückgewinnung von Ressourcen oder Energie die schlechteste Abfallentsorgungsoption ist. Einigkeit besteht auch darin, dass die Ziele einer nachhaltigen Abfallwirtschaft der Schutz der menschlichen Gesundheit und der Umwelt sowie die Schonung von Ressourcen sind. In allen drei Ländern werden große Mengen an mineralischen Abfällen erzeugt, die bei Nachweis der Umweltverträglichkeit einen Teil von natürlichem Sand und Kies für die Bauindustrie ersetzen könnten. Ähnlich wie in Deutschland werden recycelte Abfälle im Tiefbau jedoch nur in geringem Maße eingesetzt. Gründe dafür sind fehlende Behandlungsanlagen für mineralische Abfälle und Bedenken im Hinblick auf die Umweltverträglichkeit.
Transformation of carbendazim, diuron, octylisothiazolinone and terbutryn was investigated in two paints containing either white titanium dioxide or a red iron oxide pigment.
Test specimens of these coatings on glass were exposed to water contact and UVA-radiation under laboratory conditions. Panels of birch plywood were coated and exposed to natural weather conditions in a field experiment. Concentrations of biocides and transformation products were analysed in leachates from laboratory tests, runoff samples and remaining coatings. Water contact, UVA radiation as well as pigments in the paints affected the pattern and amount of transformation products.
Tools for the characterization of secondary raw materials - status of leaching test application
(2018)
Leaching tests are used as tools for the assessment of environmental compatibility of granular waste materials with potential for reuse. The presentation gives an overview on available leaching tests, their field of application and relation to legislation. Furthermore robustness testing to elaborate optimized test conditions as well as performance characteristics from validation studies by BAM are addressed.
Tools for the characterization of secondary raw materials - status of leaching test application
(2018)
Leaching tests are used as tools for the assessment of environmental compatibility of granular waste materials with potential for reuse. The presentation gives an overview on available leaching tests, their field of application and relation to legislation. Furthermore robustness testing to elaborate optimized test conditions as well as performance characteristics from validation studies by BAM are addressed.
Tools for the characterization of secondary raw materials - status of leaching test application
(2018)
Leaching tests are used as tools for the assessment of environmental compatibility of granular waste materials with potential for reuse. The presentation gives an overview on available leaching tests, their field of application and relation to legislation. Furthermore robustness testing to elaborate optimized test conditions as well as performance characteristics from validation studies by BAM are addressed.
Thermo-Desorption Gas Chromatography-Mass Spectrometry (TD-GC-MS) was used to investigate the thermal degradation of two different polyurethanes (PU). PU samples were heated at different heating rates and the desorbed products were collected in a cold injection system and thereafter submitted to GC-MS. Prospects and limitations of the detection and quantification of semi-volatile degradation products were investigated. A temperature dependent PU depolymerization was
found at temperatures above 200 °C proved by an increasing release of 1,4-butanediol and methylene diphenyl diisocyanate (MDI) representing the main building blocks of both polymers. Their release was monitored quantitatively based on external calibration with authentic compounds. Size Exclusion Chromatography (SEC) of the residues obtained after thermodesorption confirmed the initial competitive degradation mechanism indicating an equilibrium of crosslinking and depolymerization as previously suggested. Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry of SEC fractions of thermally degraded PUs provided additional hints on degradation mechanism.
Phosphorus (P) resource availability and quality is declining and recycling P-fertilizers from waste materials are becoming increasingly important. One important secondary P resource is sewage sludge (SSL) where P is often bound as aluminum phosphate (Al-P), iron phosphate (Fe-P) and polyphosphate (poly-P), respectively. Thermal treatment in different ways is a promising way in P recycling to produce highly plant-available P-fertilizers. To investigate mechanisms behind transformation of hardly available P-species toward plant-available P forms we treated a model SSL containing different kinds of defined P sources by low-temperature conversion (LTC) at 500 °C and subsequent thermochemical treatment of the LTC product with Na additives (TCT) at 950 °C, respectively. Pot experiments with ryegrass were carried out to determine the plant availability of P of the different treatments. The poly-P (here pyrophosphates) based fertilizers had a very high plant availability after both thermal treatments. During LTC treatment the plant availability of the Fe-P and Al-P variants increased because of the Formation of Fe(II) phosphates and/or pyro-/polyphosphates. Especially the formation of Al-polyphosphate shows a high plant availability. The subsequent TCT further increased strongly the plant availability of the Fe-P variants because of the formation of highly plant-available CaNaPO4. Thus, a direct TCT without prior LTC probably also produce CaNaPO4 and is recommended for Fe-P based SSL. However, a molar Ca/P ratio of 1 in the fertilizer is favorable for CaNaPO4 formation. Thus, the knowledge on the source of primary P in SSL is essential for choosing the accurate thermal treatment method to produce highly plant-available P-fertilizers from SSL.
Thermal Destruction of PFAS
(2023)
Thermal treatment processes are currently the only full-scale option for thedestruction of per- and polyfluoroalkyl substances (PFAS) in large waste streams. While all organic molecules including PFAS are susceptible to thermal destruction, their decomposition rates are controlled by process variables such as temperature, reaction atmosphere, and residence time. Concerns exist about the formation of products of incomplete destruction and their emission from hazardous waste incinerators. This talk will summarize the current stateof-the-art of thermal PFAS destruction, identify research needs, and showcase future research designed to address critical knowledge gaps.
An approach to achieve “zero leakage” is discussed with respect to the experience in Germany, where strict regulations for landfill lining and capping systems have been developed and issued because of large environmental problems related to landfills that accumulated in the 1970’s and 1980’s. These regulations for landfills and geosynthetics which are used in landfill liner and capping systems are shortly described. The main certification requirements for the products as well as conclusions for their use are presented. Using a thick, high quality HDPE geomembrane (GMB), which is installed free of residual waves and wrinkles in intimate contact with a compacted clay liner (CCL) or geosynthetic clay liner (GCL) of very low permeability, by a qualified, experienced, well equipped and properly third‐party controlled installer and which are protected by heavy protection layers designed with respect to long‐term performance of the GMB, may result in a liner or capping system of practically no leakage. This is demonstrated by analyzing results of measurements obtained from permanently installed leak detection systems in combination with HDPE GMBs.
An approach to achieve “zero leakage” is discussed with respect to the experience in Germany, where strict regulations for landfill lining and capping systems have been developed and issued because of large environmental problems related to landfills that accumulated in the 1970’s and 1980’s. These regulations for landfills and geosynthetics which are used in landfill liner and capping systems are shortly described. The main certification requirements for the products as well as conclusions for their use are presented. Using a thick, high quality HDPE geomembrane (GMB), which is installed free of residual waves and wrinkles in intimate contact with a compacted clay liner (CCL) or geosynthetic clay liner (GCL) of very low permeability, by a qualified, experienced, well equipped and properly third‐party controlled installer and which are protected by heavy protection layers designed with respect to long‐term performance of the GMB, may result in a liner or capping system of practically no leakage. This is demonstrated by analyzing results of measurements obtained from permanently installed leak detection systems in combination with HDPE GMBs.
Designing the performance of geogrids in reinforce soil constructions usually does not consider long-term behavior and possible failure modes of junctions between longitudinal and transverse ribs. How could behavior of junctions be included? To which extend is it necessary? On the conference Geo-Chicago 2016, Swan and Yuan presented an ultimate limit state equation for the short-term material resistance of junctions. We discuss limitations and suggest improvements to include long-term behavior of junctions. Nevertheless, the approach applies only to a specific mode of shear-tensile failure of junctions and only to strictly rigid geogrids. A new design concept presented in the same year by Jacobs on the conference GeoAmerica for the special case of the anchorage of geogrids, which reinforce capping system on long and steep slopes of landfills, tried to overcome these drawbacks. We discuss the aspects of this concept related to the long-term behavior of junctions and the interplay between the load applied to junctions and the flexibility of longitudinal ribs. This interplay and the long-term junction strength determine the long-term behavior of geogrids.
Designing the performance of geogrids in reinforce soil constructions usually does not consider long-term behavior and possible failure modes of junctions between longitudinal and transverse ribs. How could behavior of junctions be included? To which extend is it necessary? On the conference Geo-Chicago 2016, Swan and Yuan presented an ultimate limit state equation for the short-term material resistance of junctions. We discuss limitations and suggest improvements to include long-term behavior of junctions. Nevertheless, the approach applies only to a specific mode of shear-tensile failure of junctions and only to strictly rigid geogrids. A new design concept presented in the same year by Jacobs on the conference GeoAmerica for the special case of the anchorage of geogrids, which reinforce capping system on long and steep slopes of landfills, tried to overcome these drawbacks. We discuss the aspects of this concept related to the long-term behavior
of junctions and the interplay between the load applied to junctions and the flexibility of longitudinal ribs. This interplay and the long-term junction strength determine the long-term behavior of geogrids.
The production of secondary materials from waste materials requires, in most cases, significantly lower energy amounts than the primary material production of raw materials. Along with lower energy demand, the greenhouse gas emissions produced are also lower. The duty of a modern waste management system should therefore be to collect and sort the waste materials in a way that the highest amounts of single material fractions with the highest qualities can be generated. In this contribution, the greenhouse gas balances of the theoretical treatment of the household waste, if collected as mixed waste in sanitary landfills, in waste incineration plants, or in mechanical-biological treatment plants, are compared to the existing separate waste collection and treatment in Germany in 2014. The results show that the treatment of the mixed collected household waste in sanitary landfills would lead to a significant release of greenhouse gases. The treatment in MBTs with the recovery of valuables and the further disposal of the biologically stabilized fraction on landfills, as well as the treatment of the high calorific fraction (also called refuse derived fuel – RDF) in RDF plants, coal-fired power plants, or cement kilns, would lead to small amounts of avoided greenhouse gas emissions. The thermal treatment in waste incineration plants would lead to moderate amounts of avoided greenhouse gases. Only with the actually practiced separate collection and treatment of household waste were significant amounts of greenhouse gas emissions avoided. In total, this is approximately 5.5 million tons of carbon dioxide equivalents for approximately 45.5 million tons of separate collected and treated household waste in Germany in 2014.
Weather conditions affect biocides on exposed outer surfaces on constructions. Contact with water causes hydrolysis and leaching of substances. Ultraviolet radiation may induce photolysis. As a result, a mixture of biocidal active substances and transformation products can be emitted into the environment. In a semi-field study, leaching of the biocidal active substances terbutryn, diuron, octylisothiazolinone, carbendazim, and selected transformation products was observed for two paints containing either a white or a red pigment. Painted test panels were exposed to natural weathering for about 1.5 years. Runoff samples were analyzed during the course of the experiment.
At the end of the study, residues of biocidal active substances and transformation products were determined in sections of the test panels. Emissions of substances were mainly observed during the first few months of the experiments. Increased emissions of transformation products were observed during periods of increased global radiation and subsequent periods with relatively high amounts of driving rain. Different patterns of transformation products were observed, especially for terbutryn, both for paints containing different pigments and in experiments that were started in different periods of the year, as well as during different periods of the experiments.
Aim. The European biocidal products regulation requires environmental risk assessments for biocidal products under service conditions. This is only possible, if processes that lead to biocide emissions into the environment are understood and can be reasonably predicted.
Actual emissions due to leaching result from different processes that are affected by material properties and environmental conditions. Transformation of biocides can affect emissions considerably.
Leaching and possible transformation of the film preservatives carbendazim, diuron, OIT and terbutryn in paints was observed under laboratory and field conditons in order to investigate the influence of different factors, e.g. water contact and radiation on biocide emissions. The paints contained either white titanium dioxide or a red iron oxide pigment to check whether pigments affect leaching processes.
Methods. Test specimens of a water-based styrene acrylic dispersion paint on glass were exposed to UVA-radiation in a UV weathering device and/or exposed to water contact by immersion events on the basis of the European standard EN 16105. Plywood panels were coated and exposed to natural weather conditions in a semi-field experiment. Concentrations of biocides and transformation products were analysed in leachates from laboratory tests, runoff samples and remaining coatings.
Results. The impact of weathering conditions on transformation processes differs for the investigated active substances. Water contact, radiation as well as pigments in the paints determine the pattern and amount of transformation products on coatings, leachates and runoff water. Observations from laboratory and field experiments were compared. It proved that results from laboratory tests support understanding of data from field experiments.
Detailed knowledge on the fate of active substances under environmental conditions supports manufacturers to develop safe applications of film preservatives and authorities to evaluate its environmental impact.
Microplastics are increasingly entering marine, limnic and terrestrial ecosystems worldwide, where they sorb hydrophobic organic contaminants. Here, the sorption behavior of the fuel-related water contaminants benzene, toluene, ethyl benzene and xylene (BTEX) and four tertiary butyl ethers to virgin and via UV radiation aged polypropylene (PP) and polystyrene (PS) pellets was investigated. Changes in material properties due to aging were recorded using appropriate polymer characterization methods, such as differential scanning calorimetry, Fourier transform infrared spectroscopy, gel permeation chromatography, X-ray photoelectron spectroscopy, and microscopy.
Pellets were exposed to water containing BTEX and the ethers at 130-190 mg/L for up to two weeks.
Aqueous sorbate concentrations were determined by headspace gas chromatography. Sorption to the polymers was correlated with the sorbate's Kow and was significant for BTEX and marginal for the ethers.
Due to substantially lower glass transition temperatures, PP showed higher sorption than PS. Aging had no effect on the sorption behavior of PP. PS sorbed less BTEX after aging due to an oxidized surface layer.
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.
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.
Since it was realized that sites contaminated with metals and radionuclides needed treatment, various remediation methods have been and are being developed. Depending on the size of the contaminated site and urgency of intervention, conventional or recently introduced techniques have been used. Conventional techniques include excavation and removal for treatment of soil and contaminants, or the so-called “pump-and-treat” method, in which contaminated groundwater is removed from the ground by pumping and treated in a treatment plant on the surface. It has the advantage of using proven techniques and is easy to control, and the treated groundwater can be reinjected into the ground or discharged in rivers or lakes. Novel methods include permeable reactive barriers, biomineralization, and electrokinetic remediation.
Sustainability has become the conscientious and future-oriented principle of modern resource management and environmental protection because caring for the future is tantamount to providing manageable and healthy surroundings for ourselves. For the foreseeable future, geotechnical and environmental engineers must therefore be concerned with ensuring a healthy balance between extraction, processing, manufacturing, utilization, recycling, and disposal of materials and products.
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.
Dem Fachbeirat Bodenuntersuchungen des BMBF/UBA wurden Ergebnisse aus BISp-Forschungsvorhaben zur Untersuchung der Stofffreisetzung aus Sportböden auf Kunststoffbasis sowie zur Modellierung des Schadstofftransfers auf dem Pfad Boden-Grundwasser vorgestellt. Dabei wurde auch auf die derzeitigen gesetzlichen Regelungen auf EU Ebene und die vorhandenen Anforderungen in der Normung eingegangen. Der verbliebene Forschungsbedarf wurde aufgezeigt und dabei auch die Problematik der Bildung von Mikroplastik im Zusammenhang mit Sportböden thematisiert.
The analysis of the presence and content of substances that are toxic to aquatic life in waste is essential for classification of waste with regard to hazard property (HP) 14 ‘ecotoxic’. For the determination of HP14 classified copper (Cu) and zinc (Zn) compounds in various municipal solid waste incineration bottom ashes (IBA) and one fly ash (FA) from Germany we applied X-ray absorption near-edge structure (XANES) spectroscopy in combination with linear combination fitting. The analysis showed that approx. 50–70% of Cu in the IBA are Cu(I) compounds and elemental Cu(0), but these compounds were not equally distributed in the different IBA. In contrast, the majority (approx. 50–70%) of Zn in all IBA is elemental zinc, which originates from brass or other alloys and galvanized metals with a large content of zinc in the waste. The FA contain higher mass fraction on Zn and other toxic elements, but similar Cu and Zn species. Additional performed selective extraction at a pH of 4 with an organic acid of some IBA showed that the ecotoxic Zn fraction is mainly elemental zinc and zinc oxide. In contrast, for the ecotoxic Cu fraction within the IBA no specific compound could be identified. Furthermore, the XANES analysis showed that the HP14 properties of especially Cu in IBA is overestimated with current best-practice guidelines for sample processing for the current substance-related approach with the 0.1% cut-off rule for each substance. However, it should be considered whether it would not be better from an environmental point of view to take the ecotoxicologically leachable copper and zinc as a reference value.
The use of ashes from municipal solid waste incineration as secondary building materials is an important pillar for the circular economy in Germany. However, leaching of potential toxic elements from these materials must be at environmentally acceptable levels. Normally, a three-month ageing period immobilizes most hazardous heavy metals, but antimony (Sb) and vanadium (V) showed previously unusual leaching. In order to clarify the mechanisms, we analyzed the Sb and V species in various bottom and fly ashes from municipal waste incineration by XANES spectroscopy. Antimony oxidizes from Sb(+ III) species used as flame retardants in plastics to Sb(+ V) compounds during waste incineration. However, owing to the similarity of different Sb(+ V) compound in the Sb K- and L-edge XANES spectra, it was not possible to accurately identify an exact Sb(+ V) species. Moreover, V is mainly present as oxidation state + V compound in the analyzed ashes. However, the coarse and magnetic fraction of the bottom ashes contain larger amounts of V(+ III) and V(+ IV) compounds which might enter the waste incineration from vanadium carbide containing steel tools. Thus, Sb and V could be critical potential toxic elements in secondary building materials and long-term monitoring of the release should be taken into account in the future.
Throughout their life cycle—from production, via usage, through to disposal—materials and products interact with the environment (water, soil, air). At the same time, they are exposed to environmental influences and, through their emissions, have an impact on the environment, people, and health. Accelerated experimental testing processes can be used to predict the long-term environmental consequences of innovative products before these actually enter the environment.
The aim of this Special Issue of the journal Materials is to publish original research and review articles as well as short communications tackling the problem of reliable environmental measurement methods and reporting exemplary case studies.
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.
Aschen und Schlacken aus der thermischen Abfallbehandlung enthalten eine Vielzahl von Schwermetallverbindungen. Für Antimon, Chrom, Kupfer, Molybdän und Vanadium werden in der neuen Ersatzbaustoffverordnung (Bundesregierung, 2021) Eluatgrenzwerte für die Verwertung festgelegt. Aschen und Schlacken werden aus der Abfallverbrennungsanlage nass ausgetragen und vor einer Verwertung in der Regel mehrere Wochen gelagert. Dabei finden hydraulische Reaktionen statt und enthaltenes CaO wird zu einem Großteil in Calciumcarbonat umgewandelt. Während wässrige Eluate von frischen Aschen pH-Werte von 12 und höher aufweisen, sind die Eluate nach einigen Wochen weniger stark alkalisch. Die gemessenen Schwermetallkonzentrationen sind daher dann auch deutlich niedriger, mit Ausnahme von Antimon (Sb) und Vanadium (V). Hier steigen die Konzentration mit der Lagerungsdauer. Grund sind sinkende Konzentrationen von Ca-Ionen, die sonst zu einer Ausfällung von Antimonaten und Vanadaten führen. Zu hohe Eluatwerte von Sb und V können jedoch durch Sorption an Eisenoxidverbindungen gemindert werden. Dazu wurden Sorptionsexperimente mit verschiedenen Eisenoxidverbindungen durchgeführt.
Aschen und Schlacken aus der thermischen Abfallbehandlung enthalten eine Vielzahl von Schwermetallverbindungen. Für Antimon, Chrom, Kupfer, Molybdän und Vanadium werden in der neuen Ersatzbaustoffverordnung Eluatgrenzwerte für die Verwertung festgelegt. Aschen und Schlacken werden aus der Abfallverbrennungsanlage nass ausgetragen und vor einer Verwertung in der Regel mehrere Wochen gelagert. Dabei finden hydraulische Reaktionen statt und enthaltenes CaO wird zu einem Großteil in Calciumcarbonat umgewandelt. Während wässrige Eluate von frischen Aschen pH-Werte von 12 und höher aufweisen, sind die Eluate nach einigen Wochen weniger stark alkalisch. Die gemessenen Schwermetallkonzentrationen sind daher dann auch deutlich niedriger, mit Ausnahme von Antimon (Sb) und Vanadium (V). Hier steigen die Konzentration mit der Lagerungsdauer. Grund sind sinkende Konzentrationen von Ca-Ionen, die sonst zu einer Ausfällung von Antimonaten und Vanadaten führen. Zu hohe Eluatwerte von Sb und V können durch Sorption an Eisenoxidverbindungen gemindert werden. Als besonders wirkungsvoll hat sich Schwertmannit (Eisen-Oxyhydroxysulfat) erwiesen. Es entsteht durch Oxidation von pyrithaltigem Material durch Mikroorganismen und wird deshalb in Gebieten gefunden, in denen Braunkohle abgebaut wurde, z.B. in der Lausitz. Weitere untersuchte Eisenoxidverbindungen waren Hämatit und Schlämme aus der Abtrennung von Eisen und Mangan in Wasserwerken.
The classification of incineration bottom ash (IBA) as hazardous or non-hazardous according to ecotoxic hazard property HP14 is still under debate. In this context, only the compounds of Zn and Cu with the hazard statement code H410 are of relevance. With an approach based on the grouping of substances, it was shown that such substances are either readily water-soluble or slightly and sparingly soluble. The concentrations of readily soluble Cu and Zn compounds in IBA are far below the cut-off value of 0.1%. Slightly and sparingly soluble Zn and Cu compounds could be quantified in the first fraction of a four-step sequential extraction procedure. With the results from the complete sequence, the dimensionless synthesis toxicity index (STI) was calculated and was in the range of 494 to 1218 for the four investigated IBA samples. It was concluded that IBA can usually be classified as non-hazardous.
Half of the global material consumption is mineral material. The circularity is still low so that 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 laid 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, soil-like material and IBA were characterized with respect to their material composition. The environmental compatibility in particular was 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 2. 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 regulation. Higher quality levels of utilization might be achievable with better treatment technologies.
Die Thermische Abfallbehandlung in Abfallverbrennungsanlagen sorgt für eine Inertisierung des Restmülls bei gleichzeitiger Minimierung von abgas- und abwasserseitigen Emissionen. Da der Großteil der Rückstände in verwertbare Sekundärprodukte überführt wird, fördert die thermische Abfallbehandlung die Verwirklichung einer Circular Economy in Europa.
Clay is increasingly coming back into people's consciousness with the demand for ecological, healthy and sustainable building materials.
Earthen building materials, including clay from the historical building stock, offer a high potential for their reusability and thus for saving natural resources. Unfired clay can be reused at any time and indefinitely. Dry clay only needs to be crushed and moistened with water and it can be processed again. However, there exist only a few studies on the contamination with pollutants and on the accumulation of salts in existing historic buildings regarding the evaluation of reuse potential. Within the framework of a project, preliminary tests are being carried out taking into account the previous usage of the buildings. In order to evaluate the suitability for indoor use, the potential transfer of volatile organic compounds into the air is investigated.
Fine fractions of C&D waste (particle size less than 2 mm) are currently mostly landfilled. However, such materials can be suitable for substituting primary resources of earthen building materials provided they are adequately processed. Therefore, in another research project it is investigated whether and to what extent fine and ultra-fine fractions of construction and demolition waste processed by washing can be employed for that purpose. The recycled fines are investigated considering organic and inorganic contaminants in solid matter and leaching tests are carried out to assess the potential to mobilize harmful substances. Additionally, the recycled fines are investigated in emission test chambers regarding indoor air requirements to construction products. The results will be transferred to standardization work as in Germany in standards for earthen building materials only aggregates and binders from natural sources are permitted currently.
Direct and indirect effects (DIERec) of the recovery of secondary resources are in the range of 500 million tons per year in Germany; energy savings are 1.4 million TJ. These savings are between 10 and 20% of the total. The effects of materials recovery exceed those of energy recovery by far except for secondary plastic material, where DIERec from energy recovery is higher by factor of 2.7. Untapped potential for the recovery of secondary resources exists in the fine fraction of bottom ash from municipal solid waste incineration, mainly Cu and precious metals, and in urban mining.
Waste-to-energy (WtE) is one of the leading technologies for municipal solid waste (MSW) treatment in Europe. According to Eurostat data, in 2015, 27 % of MSW was utilized in WtE plants, which represents more than 80 million tons per year. Therefore, the European annual production of incineration bottom ash (IBA) is about 20 million tons, as it is about 25 wt% of input MSW. In the European List of Waste, IBA is listed as mirror entry (i.e. waste materials which should be classified as either non-hazardous or hazardous, depending on its hazardous properties and/or content of hazardous substances) under codes 19 01 11 and 19 01 12.
Recent trends indicate that WtE allows, apart from utilization of the energy content of waste, also the recovery of various valuable components. Hence, WtE can be included in the key technologies that can put the circular economy concept into practice. Secondary raw materials in the case of WtE are solid residues, especially IBA, as it is a secondary source, particularly of ferrous metals (Fe) and non-ferrous metals (NF) and glass. Moreover, the residual mineral fraction can be used for various applications in the construction industry, i.e. as aggregates substitute for bound or unbound applications, in cement manufacturing or, as indicated by recent research, also in more sophisticated applications, e.g. for ceramics production. Recovery of these metals can also cause huge greenhouse gas savings. Alone in Europe, metal recovery from IBA reduces greenhouse gas emissions by approximately 3.2 million tonnes of CO2 equivalent.
Release of substances from joint grouts based on various binder types and their ecotoxic effects
(2022)
Background: The leaching of substances and the ecotoxic effects of eluates were studied for joint grouts that are based on various types of binders. Eight products, two of them containing either epoxy resin, polybutadiene or polyurethane binders, or modifed cement, were investigated using harmonized leaching tests for construction products in combination with ecotoxicity tests on algae, daphnia, luminescent bacteria, fish eggs and mutagenicity in accordance with CEN/TR 17105. In addition to basic parameters, such as pH, TOC, and inorganic components, organic substances in the eluates were analysed by gas and liquid chromatography in combination with mass spectrometry. Quantitative analyses in combination with ecotoxicity data on selected substances were used to deduce which substances cause the observed ecotoxic effects.
Results: Different patterns of ecotoxic effects were observed in joint grouts with different binder types. The most ecotoxic effects were observed in epoxy resin-based products, followed by polybutadiene-based products. Fewer ecotoxic effects were observed in polyurethane-based products and modifed cements. Some of these showed no ecotoxicity. Some of the substances in the eluates were identified and related to ecotoxic effects. 4-Tert-butylphenol and amines probably contributed to the ecotoxic effects of at least one of the epoxy resin-based renders, whereas cobalt is assumed to contribute to the toxic effect on algae of one of the polybutadiene-based products. However, only some of the leached substances could be identifed, and only some of the ecotoxic effects can be explained by the available information on the composition of eluates and known ecotoxic profiles of the identified substances.
Conclusions: Ecotoxicity tests on eluates from leaching tests indicate whether environmentally hazardous substances can be leached from construction products. Combined ecotoxicity tests and chemical analysis of eluates from EU-wide harmonized leaching tests for construction products can provide information on substances that cause these effects. This supports the identifcation and development of environmentally friendly construction products.
This study confirmed that ecotoxicity tests in accordance with CEN/TR 17105 are a tool well-suited to support the implementation of the European Commission’s zero pollution vision for 2050 and to reduce pollution to levels no longer considered harmful to health and natural ecosystems.
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.
The production of secondary materials from waste materials requires, in most cases, significantly lower energy amounts than the primary material production of raw materials. Along with lower energy demand, the greenhouse gas emissions produced are also lower. The duty of a modern waste management system should therefore be to collect and sort the waste materials in a way that the highest amounts of single material fractions with the highest qualities can be generated. In this contribution, the greenhouse gas balances of the theoretical treatment of the household waste, if collected as mixed waste in sanitary landfills, in waste incineration plants, or in mechanical-biological treatment plants, are compared to the existing separate waste collection and treatment in Germany in 2014.
Weltweit werden etwa 80–85 % aller abgebauten Rohphosphate für die Produktion von Düngemitteln verwendet. Bei noch steigendem Bedarf an Phosphor (P) geht man derzeit davon aus, dass die weltweiten P-Reserven noch über 200 Jahre ausreichen. Um den P-Vorrat langfristig abzusichern, sollte der in Reststoffen enthaltene Phosphor möglichst umfänglich genutzt werden. Dieser Forderung trägt das von der Bundesregierung 2012 erstmals beschlossene Deutsche Ressourceneffizienzprogramm ProgRess Rechnung. Rohphosphat wird auch seitens der Europäischen Kommission aufgrundseiner ökonomischen Bedeutung und des unsicheren Angebots als „kritischer Rohstoff“ eingestuft. Vor diesem Hintergrund hat die Bundesregierung in der Verordnung zur Neuordnung der Klärschlammverwertung vom 27. September 2017 in Deutschland eine verpflichtende technische Rückgewinnung von Phosphor für Abwasserbehandlungsanlagen ab einer Ausbaugröße von 100.000 Einwohnerwerten (12 Jahre nach Inkrafttreten der Verordnung) bzw. ab einer Ausbaugröße von über 50.000 Einwohnerwerten (15 Jahre nach Inkrafttreten der Verordnung) vorgeschrieben. Die Verordnung enthält keine Vorgaben hinsichtlich der anzuwendenden Technologie bei der Phosphorrückgewinnung. Ausgenommen von der Rückgewinnungspflicht sind Klärschlämme mit niedrigen Phosphorgehalten (weniger als 20 Gramm Phosphor je Kilogramm Klärschlamm-Trockenmasse). Auch die im Jahre 2017 verabschiedeten neuen Rechtsvorschriften für die Düngung verlangen zukünftig einen nachhaltigen und ressourceneffizienten Umgang mit Nährstoffen bei der landwirtschaftlichen Erzeugung und schränken die P-Zufuhr insbesondere auf hoch versorgten Böden ein (Düngeverordnung vom 26. Mai 2017). Dies wird zu einem mehr am Pflanzenbedarf orientierten und ggf. vermehrt überbetrieblichen Einsatz von wirtschaftseigenen Düngern führen. Um den politischen und gesetzlichen Anforderungen gerecht zu werden, müssen einerseits wirksame und kosteneffiziente technische Verfahren zum P-Recycling (weiter)entwickelt werden. Andererseits müssen die Recyclingprodukte die Anforderungen für eine direkte Verwendung in der Landwirtschaft oder als Rohstoff für die Herstellung von Düngemitteln erfüllen. In dem vorliegenden Standpunkt wird zunächst der potenzielle Beitrag von Reststoffen zur Deckung des P-Bedarfs in der deutschen Pflanzenproduktion geschätzt. Für die wichtigsten Reststoffe werden technische Verfahren zur P-Rückgewinnung bzw. Aufarbeitung skizziert. Auf Basis der Anforderungen der Landwirtschaft bzw. der Düngemittelindustrie
an die P-Recyclingprodukte werden deren Herstellungsverfahren bewertet. Schließlich wird der Regelungs- und Forschungsbedarf formuliert.
Small grain size fractions of municipal solid waste incineration (MSWI) bottom ash (BA) contain elemental and chemically bonded metals in appreciable amounts, especially copper. Investigations with a centrifugal concentrator were carried out using samples, which had been treated with different impact devices. Partly the impacts of single devices were visible in outlines, but mostly the surfaces of the metals were still covered with mineral residues. To generate copper rich fractions, parameters of the separation process should ensure mass yields <2%, best between 0.5 and 1%. The density of the concentrates is then generally >3.2 g/cm3. Best results were achieved with material from a special treatment train which is adapted to grain sizes <2 mm. Reliable copper contents between 20 and 40% (single runs >50%) could be realised.
However, considering the required mass yields, referred to this subset only 150–170 g copper would be recovered from 1 Mg MSWI BA. Furthermore, this copper is only in parts present in elemental form. A
dependable added value of such treatment step seems to be given only, if that enables a recycling of the mineral aggregates (tailings) in parallel to avoid landfill costs.
Ultrashort PFAS (≤ 3 carbon atoms) were overlooked for a long time in analytical monitoring. Beside through the use of these substances, they contribute to the PFAS background in the environment through (environmental/ bio-) degradation and incomplete destruction3 of PFAS with longer carbon chains or other fluorinated compounds. As part of the German-Israeli Cooperation in Water Technology Research project „Detection, quantification, and treatment of per- and polyfluoroalkyl substances in groundwater“ (DEFEAT-PFAS), we are developing an as simple as possible direct headspace (HS-)GC-MS method to detect trifluoroacetic acid (TFA) and perfluoropropanioc acid (PFPrA), as well as trifluoroethanol (TFEtOH), pentafluoropropanol(PFPrOH) and hexafluoroiospropanol (HFIP) in water samples. Here we present the results of the PFAS mentioned in spiked ultrapure water solutions.
Per- and polyfluoroalkyl substances (PFAS) were classified as a group of highly concerning chemicals over the last decades. Because of the high persistence of PFAS, their previous use led to contamination of the environment and human population. Due to ongoing use and incomplete remediation or destruction methods, the PFAS background in the environment is growing continuously.
The presence of ultrashort PFAS (with ≤3 carbon atoms) in the environment is often overlooked despite their contributions to PFAS levels. These compounds may directly contaminate the environment and arise from degradation of polyfluorinated compounds as well as incomplete PFAS destruction in certain industrial processes. Nonetheless, few approaches for targeted analysis of ultrashort PFASs have been developed, except for trifluoroacetic acid (TFA). Beside liquid (LC-MS/MS), supercritical fluid (SFC-MS/MS), and ion chromatography (IC-MS)-based systems, gas chromatography coupled with mass spectrometry (GC-MS) is a promising method for detection and quantification of ultrashort PFAS.
The goal of this study was to develop a simple headspace GC-MS method for the quantification of ultrashort perfluorocarboxylic acids (PFCAs) and polyfluorinated alcohols (PFOHs) in water samples. In contrast to PFOHs, functionalization of PFCAs was required for quantification. This was done by esterification with methanol at 80 °C, which can be carried out directly in the headspace GC-MS system.
Moreover, several parameters were optimized to achieve a low limit of quantification (LOQ) for the analytes used: i) The ratio of the aqueous solution, methanol, and available gas phase within the analysis vessel, ii) the concentration of additional acid in esterification mixtures of PFCAs, iii) shaking frequency and iv) shaking time before analysis. After optimizing the procedure, we were able to quantify ultrashort PFCAs and PFOHs. Thus, our developed headspace GC-MS method has the potential to be used as an alternative target analysis for ultrashort-chain PFCAs and PFOHs in various water samples (groundwater, wastewater).
Geosynthetic materials are applied in measures for coastal protection. Weathering or any damage of constructions, as shown by a field study in Kaliningrad Oblast (Russia), could lead to the littering of the beach or the sea (marine littering) and the discharge of possibly harmful additives into the marine environment. The ageing behavior of a widely used geotextile made of polypropylene was studied by artificial accelerated ageing in water-filled autoclaves at temperatures of 30 to 80° C
and pressures of 10 to 50 bar. Tensile strength tests were used to evaluate the progress of ageing, concluding that temperature rather than pressure was the main factor influencing the ageing of geotextiles. Using a modified Arrhenius equation, it was possible to calculate the half-life for the loss of 50% of the strain, which corresponds to approximately 330 years.
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.
Potential use of incineration bottom ash in construction – Evaluation of environmental impact
(2018)
Around 5 million tonnes of MSWI bottom ash (BA) are generated per year in Germany. The incineration itself serves for metals as a concentrating and cleaning process. However, due to the almost exclusive wet extraction out of the furnace chamber the various metals are integrated in a heterogeneous and instable matrix. The metal recovery is therefore still a challenge relating the recovery rate and the purity, respectively. With state of the art treatment trains in Germany around 7.7% of ferrous metals and 1.3% of non-ferrous metals can be recovered out of MSWI BA. Large quantities of the mineral fraction are reused for sub-base material in road construction. A three month ageing period has been established as the common practice of further treatment of bottom ash before reuse applications. In the course of this aging the pH value of bottom ash decreases and contaminants are immobilized by processes like carbonation, hydration and oxidation. In particular leaching of heavy metals may be reduced to environmentally acceptable levels. However, the aging results in fixing of other valuable resources such as metals. Two laboratory scale lysimeters (30 cm in diameter) are being operated for more than three years aiming at the investigation of the long-term leaching behavior of a 0.25/45 mm mineral material obtained by treatment of MSWI bottom ash directly after incineration by a wet processing technology. Artificial rainwater is used as leachant (pH ≈ 6, ingredients NO32-, Cl-, SO42-, Na+, K+, Ca2+, Mg2+). The lysimeters are irrigated related to an average annual precipitation rate of 600 mm/a leading to a liquid to solid ratio (L/S) of about 0.7 per year of operation. Lysimeter tests are more adequate to simulate field scenarios and long-term leaching behavior in contrast to laboratory column tests particularly due to the unsaturated conditions and realistic contact time with the leachant.
In comparison to the leaching of bottom ash (aged for 3 month and non-treated) in column tests the chloride and sulfate leaching in the lysimeters was reduced as a consequence of the previous wet processing. The sulfate release kept almost constant limited by CaSO4 solubility up to an L/S of about 0.7 l/kg. The chloride concentrations dropped quickly, starting from 7300 mg/l, and are now at an almost constant level of 50 mg/l which is significantly above the chloride concentration in the leachant. After an initial decrease of the pH from about 10.4 to 8 at L/S of 0.2 l/kg, the pH increased again and leveled out around 9.8 up to L/S 2.2 l/kg. At an L/S of about 2.5 l/kg now, Cr, Cu are still released. The Cu and Cr concentrations in the leachates were about 760 µg/l and 90 µg/l respectively at the beginning. For both metals the concentration decreased to about 35 µg/l now. The Mo concentrations dropped steadily from 1300 to 250 µg/l, whereas V and Sb concentrations increased in the course of the tests. Fe and Mn are not detectable anymore. More results of this experimental study will be presented and discussed with a special focus on elements forming oxyanions.
Die Autoren zeigen dazu die gesetzlichen und energiepolitischen Rahmenbedingungen und Perspektiven auf, widmen sich in aktuellen Beiträgen zur Verfahrenstechnik der thermischen Abfallbehandlung sowohl den thermischen Hauptverfahren als auch der Abgasreinigung und gehen auf das Thema Wertstoffrückgewinnung ein. Ihr Fazit: Durch Anstrengungen, das stoffliche Recycling weiter zu optimieren, können künftig weitere Kreisläufe von Produkten und Materialien hochwertig geschlossen werden. Für manche Abfallströme wird dies aber aus verschiedenen Gründen nicht möglich sein – hier bleibt die thermische Abfallbehandlung unverzichtbar.
Per- and polyfluoroalkyl substances (PFAS) are anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms (see Figure 1) and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, because of the continuous contamination through PFAS containing commercial products, effluents and sewage sludge from WWTPs have been shown to be an important source of PFAS discharge into the aquatic environment. In the last few years, legacy PFAS (≥C4) have been found in various environments, including soil, water and wastewater, and their environmental pathways have been partly described. To get a better
overview of the amount of “total PFAS,” sum parameter methods like total oxidizable precursor (TOP) assay and methods based on combustion ion chromatography (CIC) are in development. CIC results in data regarding the sum of absorbable organic fluorine (AOF) or extractable
organic fluorine (EOF), which can also quantify other organically bound fluorine compounds such as fluorinated pesticides and pharmaceutical. Additionally, for research purpose several spectroscopical methods like X-ray photoelectron spectroscopy (XPS), fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy, particular induced gamma-ray emission (PIGE) spectroscopy and 19F nuclear magnetic resonance (NMR) spectroscopy are available. Therefore, an overview is given on various analytical techniques for PFAS in environmental samples and their application possibilities discussed for different kind of PFAS compounds
Per- and polyfluoroalkyl substances (PFAS) are a large group of more than 10,000 anionic, cationic, zwitterionic or neutral organofluorine surfactants. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. While liquid chromatography tandem mass spectrometry (LC-MS/MS) is commonly used technique to characterize targeted PFAS in environmental samples, there are more than 10,000 different PFAS known, which have various headgroups and properties. Therefore, several analytical techniques are available to analyse various groups or pools of PFAS or “all” PFAS as a sum parameter. Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Previously, mechanochemical treatment of polychlorinated organic compounds in soils showed an efficient dechlorination. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well es the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
Per- und polyfluorierte Alkylsubstanzen (PFAS) im Klärschlamm - Analytische Methoden und Grenzwerte
(2022)
Per- und Polyfluoralkylsubstanzen (PFAS) sind eine Gruppe von mehr als 4700 anionischen und kationischen anthrophonen Stoffen, die aufgrund ihrer inerten chemischen Stabilität und ihrer Widerstandsfähigkeit gegen den Abbau durch Hitze oder Säuren in einer Vielzahl von Produkten verwendet werden. Infolge der ständigen Verwendung, vor allem in Feuerlöschschäumen für die Luftfahrt, wurden in Tausenden von Industrie- und Militäranlagen kontaminierte Böden und Grundwasservorkommen gefunden. Aufgrund der ständigen Verwendung von fluorierten Konsumgütern haben sich jedoch auch Abwässer und Klärschlamm aus Kläranlagen als Quelle für die Kontamination der aquatischen Umwelt mit PFAS erwiesen. Infolge der strengeren Vorschriften und Beschränkungen, die in den letzten Jahren für die Verwendung langkettiger (≥C8) PFAS erlassen wurden, findet in der chemischen Industrie eine deutliche Verlagerung hin zur Herstellung kurz- (C4-C7) und ultrakurzkettiger (C1-C3) Alternativen statt. Mit der Novellierung der Klärschlammverordnung im Jahr 2017 hat der deutsche Gesetzgeber die Ausbringung von Klärschlamm auf landwirtschaftlichen Flächen verboten, und bis 2029/2032 wird die Ausbringung von Klärschlamm in der Landwirtschaft vollständig verboten sein. Während die Belastung der Umwelt mit organischen Schadstoffen wie PFAS, Pestiziden und Arzneimitteln nicht mehr erwünscht ist, muss Phosphor (P) aus Klärschlamm weiterhin zur Herstellung hochwertiger P-Dünger für eine Kreislaufwirtschaft genutzt werden. Derzeit können pflanzenverfügbare P-Düngemittel aus Klärschlamm/Abwasser mit verschiedenen Behandlungsmethoden hergestellt werden, darunter Fällung, Auslaugung und thermische Behandlung. Der Verbleib von PFAS bei der Auslaugung, Ausfällung und Behandlung von Klärschlamm und Abwasser ist jedoch noch weitgehend unbekannt.
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.
Per- and polyfluoroalkyl substances (PFAS) are a group of anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. As a result of the perpetual use of PFAS containing products, effluents and sewage sludge from wastewater treatment plants (WWTPs) have been observed to be an important pathway for PFAS into the environment. In Germany, phosphorus and other nutrients from sewage sludge and wastewater should be recycled in WWTPs of cities with a large population. However, it is not clear if PFAS contamination from wastewater and sewage sludge end up in novel wastewater-based fertilizers. Normally, PFAS are analyzed using PFAS protocols typically with liquid chromatography tandem mass spectrometry (LC-MS/MS) quantification. To get a better overview of the amount of “total PFAS,” we applied sum parameter methods based on combustion ion chromatography (CIC) to screen the PFAS contaminations in various sewage sludge and wastewater-based fertilizers. Furthermore, current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem.
Per- and polyfluoroalkyl substances (PFAS) are chemicals which were developed to improve humanity’s quality of life. Due to their high chemical stability and resistance to degradation by heat or acids, PFAS were used in a variety of consumer products. The continuous use of PFAS in household products and the discharge of PFAS from industrial plants into the sewer system resulted in the contamination of effluents and sewage sludge from wastewater treatment plants (WWTPs) (Roesch et al. 2022). Since sewage sludge is often used as fertilizer, its application on agricultural soils has been observed as a significant entry path for PFAS into the environment, specifically in our food chain. In Germany the sewage sludge/biosolid application on agricultural land was banned with the amendment of the German Sewage Sludge Ordinance and by 2029 sewage sludge application will be totally prohibited. However, phosphorus (P) from sewage sludge should still be recycled in WWTPs of cities with a population larger than 50,000 residents. To produce high-quality P-fertilizers for a circular economy, PFAS and other pollutants (e.g. pesticides and pharmaceuticals) must be separated from sewage sludge. Due to the strong diversity of industrial PFAS usage it is not clear if a safe application of novel recycled P-fertilizers from WWTPs can be guaranteed. Therefore, we analyzed various sewage sludges and wastewater-based fertilizers. Sewage sludge (SL) samples from various WWTPs in Germany and Switzerland, six sewage sludge ashes (SSA) from Germany, six thermally treated SL and SSA samples with different additives (temperatures: 700-1050 °C), two pyrolyzed SL samples (temperature: 400 °C) and two struvite samples from Germany and Canada were analyzed. The goal was to quantify PFAS in sewage sludges and wastewater-based P-fertilizers with the sum parameter extractable organic fluorine (EOF) by combustion ion chromatography (CIC). The results were compared with data from classical LC-MS/MS target analysis as well as selected samples by HR-MS suspect screening. The EOF values of the SLs mainly range between 154 and 538 µg/kg except for one SL which showed an elevated EOF value of 7209 µg/kg due to high organofluorine contamination. For the SSA samples the EOF values were lower and values between LOQ (approx. 60 µg/kg) and 121 µg/kg could be detected. For the pyrolyzed SLs no EOF values above the LOQ were detected. Moreover, the two wastewater-based struvite fertilizers contain 96 and 112 µg/kg EOF, respectively. In contrast to the EOF values, the sum of PFAS target values were relatively low for all SLs. Additional applied PFAS HR-MS suspect screening aimed to tentatively identify PFAS that could contribute to the hitherto unknown part of the EOF value. The majority of the detected fluorinated compounds are legacy PFAS such as short- and long-chain perfluorocarboxylic acids (PFCA), perfluorosulfonic acids (PFSA), polyfluoroalkyl phosphate esters (PAPs) and perfluorophosphonic acids (PFPA). Moreover, fluorinated pesticides, pharmaceutical as well as aromatic compounds were also identified, which are all included in the EOF parameter. Our research revealed that the current PFAS limit of 100 µg/kg for the sum of PFOS + PFOA in the German Fertilizer Ordinance is no longer up to date. Since the number of known PFAS already exceeds 10,000, the ordinance limit should be updated accordingly. Recent regulations and restrictions on using long-chain PFAS (≥C8) have resulted in a significant shift in the industry towards (ultra-)short-chain alternatives, and other, partly unknown, emerging PFAS. Ultimately, also fluorinated pesticides and pharmaceuticals, which end up as ultrashort PFAS in the WWTPs, have to be considered as possible pollutants in fertilizers from wastewater, too.
Abstract: Since it is unknown for many applications, which PFASs are used and how they enter the environment, target analysis-based methods reach their limits. The two most frequently used sum parameters are the adsorbable organically bound fluorine (AOF) and the extractable organically bound fluorine (EOF). Both can be quantified using either combustion ion chromatography (CIC) or high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Here we provide an insight on the advantageous and disadvantageous of both sum parameters and both detection methods. Our study is based on the analysis of surface water samples. Next to total fluorine (TF) analysis, AOF and EOF were determined as well as CIC and HR-CS-GFMAS are compared and results are comparatively discussed. Fluorine mass balancing revealed that, the AOF/TF proportion was higher than the EOF/TF proportion. The AOF made up 0.14–0.81% of TF and the EOF 0.04–0.28% of TF. Although, organically bound fluorine represents only a small portion of TF, PFASs are of worldwide concern, because of their extreme persistence and their bioaccumulation potential. The EOF-HR-CS-GFMAS method turned out to be more precise and sensitive than the AOF-CIC method and is a promising tool for future monitoring studies/routine analysis of PFASs in the environment.
Der Verwertung von Bodenmaterialien wird auf Grund des Volumens dieses Stoffstromes eine hohe umweltpolitische Bedeutung beigemessen. Dabei ist unter Gewährleistung des Vorsorge- und Nachhaltigkeitsprinzips eine möglichst hochwertige Verwertung anzustreben, um natürliche Ressourcen zu schonen und die Beseitigung von Abfällen weitestgehend zu vermeiden.
Die vorgesehene Novelle der BBodSchV enthält in den Paragraphen 6 bis 8 neue Vorgaben hinsichtlich des Auf- und Einbringens von Bodenmaterialien unterhalb oder außerhalb einer durchwurzelbaren Bodenschicht. So soll die Möglichkeit eingeräumt werden, Bodenmaterialien mit Feststoffgehalten von regulierten Stoffen zwischen dem einfachen und doppelten Vorsorgewert einer weiteren Verwertung zuzuführen unter der Voraussetzung, dass die Eluatwerte eingehalten werden.
Im Rahmen eines Forschungsvorhabens des Umweltbundesamtes (FKZ: 3716 74 203 0) wurden unterschiedliche Bodenmaterialien (Baggergut, Bankettschälgut, Stadt- und Auenböden, Bergematerial), die unter diese Kriterien fallen, mit besonderem Fokus auf PAK hinsichtlich ihres Verwertungspotentials untersucht.
Dabei wurden auch die Auswirkungen der Umstellung des Elutionsverfahrens von einem Wasser-Feststoffverhältnis (W/F) von 10 l/kg auf ein W/F von 2 l/kg auf die Einstufung von Bodenmaterialien betrachtet.
Insbesondere für die Stoffgruppe der PAK konnte gezeigt werden, dass sich mit Verabschiedung der neuen Regelungen zusätzliche Verwertungsmöglichkeiten von Bodenmaterialien außerhalb der durchwurzelbaren Bodenschicht eröffnen und deren Deponierung teilweise vermieden werden kann.
Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from <LOQ to over ~1000 mg F/kg after oxidation/hydrolysis and <LOQ to over 2000 mg F/kg for TF, while EOF and target PFAS in extracts were detected at much lower concentrations (up to ~ 60 mg F/kg) (amount of fluorine in the order: extraction << EOF << oxidation/hydrolysis ≤ TF). Perfluoroalkyl carboxylic acids (PFCAs) and fluorotelomer alcohols (FTOHs) from THP and PhotoTOP both represented the chain-length distribution in the textiles showing that long-chain SFPs are still used in current textiles. Further advantages and disadvantages of the applied methods are discussed.
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.
Wood treated with nano metal fluorides is found to resist fungal decay. Sol−gel synthesis was used to synthesize MgF2 and CaF2 nanoparticles. Electron microscopy images confirmed the localization of MgF2 and CaF2 nanoparticles in wood. Efficacy of nano metal fluoride-treated wood was tested against brown-rot fungi Coniophora puteana and Rhodonia placenta. Untreated wood specimens had higher
mass losses (∼30%) compared to treated specimens, which had average mass loss of 2% against C. puteana and 14% against R. placenta, respectively. Nano metal fluorides provide a viable alternative to current wood preservatives.
Dem Fachbeirat Bodenuntersuchungen des BMBF/UBA wurden die abschließenden Ergebnisse zum UFOPLAN-Forschungsvorhaben „Monitoring zur Verwertung von Bodenmaterial“ vorgestellt. Die potentielle Auswirkung der neuen Regularien in der geplanten Novelle der BBodSchV (4. Referentenentwurf der Mantelverordnung) auf die Erweiterung der Verwertungsmöglichkeiten von Bodenmaterialien wurden aufgezeigt.
Mit der Novellierung der Bundes-Bodenschutz- und Altlastenverordnung (BBodSchV) (am 6.11.2020 im Bundesratsverfahren beschlossen) werden Regelungen zum Auf- und Einbringen von Bodenmaterial außerhalb der durchwurzelbaren Bodenschicht aufgenommen (sogenannte Verfüllungen). Ziel des Vorhabens war es, durch die Auswertung vorhandener und durchzuführender Untersuchungen eine Einstufung von Bodenmaterialien (jährlich fallen weit über 100 Mio. Tonnen davon an) für bestimmte Verwertungswege vornehmen zu können. Es sollte herausgefunden werden, ob Veränderungen hinsichtlich des Verwertungspotentials nachgewiesen werden können.
Basis für die Durchführung und Bewertung waren die neuen Regelungen (hier insbesondere die Untersuchung mit einem Wasser/Feststoffverhältnis von 2:1, neue nationale und europäische Elutions- und Untersuchungsverfahren) der novellierten BBodSchV. Der Fokus lag dabei auf den polyzyklischen aromatischen Kohlenwasserstoffen (PAK) sowie ausgewählte anorganische Stoffe (Schwermetalle und Anionen) unter der Berücksichtigung unterschiedlicher Bodenmaterialien zur Verwertung.
Dabei handelte es sich um:
- Böden aus urban geprägten Gebieten,
- Oberböden aus dem Straßenrandbereich in Form von Bankettschälgut,
- Baggergut aus Gewässern mit Verdacht auf eine Kontamination,
- Bergematerial (Mischung von Abraum- und Bodenmaterial),
- Auenböden mit vermuteten Verunreinigungen aus Industrie und Gewerbe.
Anhand der vorgelegten Ergebnisse kann nun eine Versachlichung der Diskussion um Ressorcenschutz vs. Schadlosigkeit der Verwertung erfolgen. Sie zeigen für die untersuchten Stoffe, dass bei einer Einführung der §§ 6-8 Novelle BBodSchV mit einer Erhöhung der Verwertungsquote für Bodenmaterial gerechnet werden kann. Eine Erhöhung des Deponievolumens ist somit nicht zu befürchten. Neben den ermittelten Daten konnten Grundlagen für die Überarbeitung verschiedener DIN-Normen für Bodenuntersuchungen erarbeitet werden.
Paragraphs 6 to 8 of the proposed amendment to the German Federal Soil Protection and Contaminated Sites Ordinance contain new requirements regarding the application of soil-like material outside of a rootable soil layer. For example, it is intended to enable reusing of soil-like materials containing regulated substances in concentrations between the single and double precautionary values (PV), provided that the limit values for the eluate are complied with. The aim of a running project (funding code UFOPLAN 3716 74 203 0, German Federal Environmental Agency) is to fill data deficits for soil-like materials which meet the above-mentioned criteria to promote circular economy and conservation of natural resources. Different soil-like materials of various origin (for example dredged material, banquet peeling material, urban and meadow soils) are considered with a special focus on PAHs. A major challenge in sample acquisition is the relatively narrow target range of the PAH content between 3 and 6 mg/kg dm considering a high measurement uncertainty at this concentration level.
The contents of PAHs, heavy metals and other inorganic elements in solid matter are determined following established standards. In addition, the soil-like materials are characterized concerning particle size, pH, conductivity, SOM, TOC and carbonate content. To determine the eluate concentration, column tests according to DIN 19528 and batch tests according to DIN 19529 at a liquid/solid ratio (L/S) of 2 l/kg and 10 l/kg are performed comparatively.
The results show that the new requirements of the planned amendment to the Federal Soil Protection and Contaminated Sites Ordinance certainly opens additional possibilities for reuse of soil-like materials. Even most soil-like materials within 2-3 x PV comply with the eluate value for PAH (0.2 μg/l) both in the batch test and in the column test at L/S 2 l/kg. Selected inorganic substances lead to similar evaluations. Therefore, the application of such soil-like materials outside of rootable soil layers would be possible. Previously, those materials were often used for landfill construction. In the future, a utilization in the adjacent environment by backfilling, recultivation, renaturation, composting or landscaping would be conceivable.
The concept of circular economy supports mitigation of climate change and other environmental pressures to the planet. Circulating materials in anthropogenic processes come with the risk of accumulating hazardous substances and compounds. In this concept, waste incineration or waste-to-energy (WtE) is a necessary technology to remove these compounds from the life cycle. In this mini-review, contaminants of major importance in the flue gas from waste incineration plants and their environmental impact are discussed. Air pollution of WtE is often seen as the most relevant environmental impact of this treatment option. The emission values parameter set for different countries is presented and compared. The most stringent legally set of emission values could be found in parts of Europe and South Korea. Japan also permits similar strict values when authorising individual incineration plants. In North America, the values are partially less strict as the best available technologies in Europe suggest being possible. Emerging economies, such as India and China, have shown efforts to improve their environmental protection standards but still have room to improve. This could be set in relation to other industrial emitting processes and therefore could be used to assess the relevance of this industry sector to the national emission inventories.
Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure)
and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to colocation with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils
through atmospheric deposition.
Microspectroscopy reveals dust-derived apatite grains in acidic, highly-weathered Hawaiian soils
(2021)
Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic Gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure) and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to co-location with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils through atmospheric deposition.
Die Umweltverträglichkeit von Bauprodukten, die in Kontakt mit Regen- oder Sickerwasser kommen, wurde durch Kombination normierter Elutions- (DSLT, Perkolationstest) und Ökotoxizitätstests (Algen, Daphnien, Fischeier, Leuchtbakterien) sowie Gentoxizitätstests (Ames, umu) untersucht. Ziel des Projektes war es einerseits, einen Beitrag zur Harmonisierung der Prüfmethoden unter CEN/TC 351 zu leisten und andererseits potentielle Produktgruppen, die sich für die Umweltzeichenvergabe des Blauen Engels eignen würden, zu erkennen. Durch umfangreiche qualitative und quantitative chemische Analysen (u. a. GC-MS- sowie LC-MS-Screening) wurden einige der freigesetzten Stoffe identifiziert und anhand von Literaturdaten ökotoxikologisch charakterisiert. Insgesamt wurden 34 Bauprodukte (Dachbahnen, Lacke, Wood-Plastic-Composites, Pflasterfugenmörtel, Korkgranulate, Schaumglasschotter, Wegedecken, Dichtmassen) untersucht. Hierbei wurden insbesondere bei den Fugenmörteln und Korkgranulaten sehr hohe
Ökotoxizitäten (bis LID = 16384 bei den Fugenmörteln und LID = 24578 bei den Korkgranulaten) beobachtet. Algen- und Leuchtbakterientests waren in der Regel deutlich empfindlicher als der Daphnien- und Fischeitest. Die untersuchten Dachbahnen, Lacke, Wood-Plastic-Composites und Schaumglasschotter zeigten hingegen keine oder nur sehr geringe Ökotoxizitäten. Zur Qualitätssicherung und Validierung wurde ein Europäischer Ringversuch gemäß den Vorgaben der DIN ISO 5725 organisiert, durchgeführt und ausgewertet. Hierzu wurde ein Fugenmörtel als flächiges Produkt im DSLT und als gebrochenes körniges Produkt im Perkolationstests eluiert und die Eluate nachfolgend in den 29 teilnehmenden Laboren hinsichtlich ihrer Ökotoxizität untersucht. Hierbei wurden insgesamt plausible Ergebnisse und gute (<50 %) bis sehr gute (<20 %) Reproduzierbarkeiten erzielt. Es wird empfohlen, für die Produktgruppen Dachbahnen, Kunstrasen und Sportböden sowie Fugenmörtel Vergabekriterien für den Blauen Engel zu entwickeln
Angesichts stetig steigender Rohstoffnachfrage und sich verknappenden Ressourcen rücken Sekundärrohstoffe zur Deckung des Bedarfes immer stärker in den Fokus.
Besonders Hausmüllverbrennungsaschen (HMVA) verfügen über hohe Anteile an Metallen wie Aluminium, Kupfer, oder Eisen, aber auch Spuren von Silber und Gold.
Aus diesem Grund wurde bereits in einer Vielzahl von Arbeiten und Projekte die Behandlung von Rostaschen diskutiert. Hauptaugenmerk der Betrachtungen ist die Rückgewinnung von Wertstoffen, insbesondere der Metallfraktion, sowie die Aufbereitung der Rostasche als Ersatzbaustoff. Die bisherigen Betrachtungen konzentrierten sich auf die Fraktionen der Partikel größer 2 mm. Die Feinfraktion kleiner 2 mm wurde bislang meist deponiert. Da die Feinfraktion etwa 25 M% der
HMVA ausmacht, wurde für weitere Untersuchungen zum Zweck einer besseren Verwertung das Projekt „BASH-TREAT“ im Programm ERA-MIN 2 initiiert.
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.
Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. These approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well as the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
Per- and polyfluoroalkyl substances (PFAS) are a large group of anionic, cationic, or zwitterionic organofluorine surfactants used in the formulations of thousands of products and consumer goods, including aqueous film-forming foams (AFFF) used to suppress aviation fires in training scenarios, non-stick cookware, fast-food wrappers, water-repellent fabrics, medical equipment. Because PFAS have been extensively used in a variety of AFFF products they can be found in soils from industrial and military installations. Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Previously, mechanochemical treatment of polychlorinated organic compounds in soils showed an efficient dechlorination. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GCMS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well es the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
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.
Throughout their life cycles—from production, usage, through to disposal—materials and products interact with the environment (water, soil, and air). At the same time, they are exposed to environmental influences and, through their emissions, have an impact on the environment, people, and health. Accelerated experimental testing processes can be used to predict the long-term environmental consequences of innovative products before these actually enter the environment.
We are living in a material world. Building materials, geosynthetics, wooden toys, soil, nanomaterials, composites, wastes and more are research subjects examined by the authors of this book. The interactions of materials with the environment are manifold. Therefore, it is important to assess the environmental impact of these interactions. Some answers to how this task can be achieved are given in this Special Issue.
In 2018 municipal solid waste (MSW) incineration in Europe produced nearly 19 Mt of bottom ash (BA); only 46 %-wt. was treated, often in poorly performing plants, leaving behind 10 Mt of untreated and unrecovered BA, destined to landfill. This work was based on the inventory of BA across Europe, and on the hypothesis to achieve complete BA valorisation through two assumptions: treating 100% BA and minimizing the loss of valuable fractions due to technical limitations of state-of-the-art processes in comparison to advanced innovative processes. The research involved three phases: characterization of potential secondary raw materials (metals and mineral fraction) currently lost from untreated (the surplus compared to treatment capacity) and unrecovered BA (the fine fraction) through material flow analysis; environmental assessment (energy balance and net GHG emissions) of complete BA valorisation; investigation of the economic feasibility of complete BA Valorisation through state-of-the-art technologies. 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. The energy balance and GHGs emissions required by the treatment of the currently untreated and unrecovered fractions of BA resulted in energy and GHGs emissions savings. Economic profitability was driven by iron and copper recycling and avoided landfill fees. Profitability was achieved by two thirds of considered countries (average values: NPV 83 M€, ROI 20%, payback time 11 years) with BA mass flow exceeding 0.02 Mt.
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.
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.
Brominated flame retardants have widely been used for more than 50 years and have been frequently detected in environmental samples as surface water and fish. Leaching from construction products was identified as one possible source. The use of substances as e.g. hexabromocyclododecane (HBCCD) was restricted recently due to increasing concern about negative impacts on the environment and human health caused by the persistent, bio accumulative and toxic properties. New polymeric brominated flame retardants have been developed to replace HBCCD in expanded polystyrene (XPS), which is used for insulation of buildings. It is assumed that the release from the polymer is much smaller in comparison to release of small molecules as HBCCD. The release from the polymer may include monomers or small fragments of different size. Thus, a sum parameter is needed. According to Schlummer et al. it is possible to detect brominated molecules using X-ray fluorescence spectroscopy by determination of brome content in XPS extracts. As only small brominated compounds can be extracted it also allows for the differentiation between the two classes of compounds. This method was applied to verify the presence of different kinds of flame retardants in XPS samples and to evaluate the leaching behavior.
Bottom ash (BA) from municipal solid waste incineration (MSWI) contains harmful substances such as heavy metals, chloride and sulfate which are mobilized in contact with water. Standardized leaching tests are used to measure the extent of mobilization. It is known that fresh bottom ash displays elevated concentrations of various heavy metals such as lead or zinc due to the formation of hydroxo complexes as a result of high pH values of 12 and above. Storage of BA is accompanied by ageing processes, mainly the reaction of CaO and Ca(OH)2 with CO2 leading to lower pH values in contact with water around 11. Usually heavy metals concentrations are minimum at these conditions. 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 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 was 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 as secondary building material.
Stormwater from urban areas can transport biocidally active substances and related transformation products from buildings into the environment. The occurrence of these substances in urban runoff depends on the availability of water, and on ultraviolet radiation exposure that causes photolytic reactions. In a systematic laboratory study, painted test specimens were exposed to either ultraviolet radiation, water contact, or a combination of both. Leaching of the biocidally active substances carbendazim, diuron, octylisothiazolinone, terbutryn, and selected transformation products of terbutryn and diuron were observed under various exposure conditions. Remaining concentrations of these substances in the paint were quantified. It was demonstrated that the distribution of active substances and transformation products in eluates and in the coatings themselves differs with exposure conditions. Strategies for environmental monitoring of biocide emissions need to consider the most relevant transformation products. However, environmental concentrations of biocidally active substances and transformation products depend on earlier exposure conditions. As a consequence, monitoring data cannot describe emission processes and predict expected leaching of biocidally active substances from buildings if the data are collected only occasionally.
Leachiing tests - a useful tool for the environmental impact assessment of construction products?
(2018)
Construction products and waste materials used for construction can be in contact with the environment and may release potential harmful compounds. Information on the total content of these substances in the product is not sufficient to assess its envrionmental impact since it does not consider realistic exposure conditions.The impact of these compounds is often assessed by using the total content in the product. This estimation lacks realistic exposure conditions.
Concerning the pathway to soil and groundwater by contact with rain or seepage water leaching tests, which were developed and standardized by the European Committee for Standardization, are available. While for secondary construction products and waste this investigation of the leaching behaviour is standard procedure and is already part of regulation in Germany (draft ordinance on reuse of mineral waste) and within Europe (landfill directive) the release from primary construction products got in the focus more recently. Several monitoring studies found unexpected high concentrations of substances used as herbicides and fungicides in surface water and stormwater originating from urban areas. As some of these compounds are even banned for the use in agricultural applications in Europe alternative sources as roof materials and façade coatings exposed to rain were suggested. Further field and laboratory tests confirmed construction products as sources of these substances in water.
The aim of this presentation is to show exemplary results of existing leaching methods and underline the strength and weaknesses of the test system with selected examples from our work. We especially draw the attention to the research which is still needed to close the gap between the results of leaching experiments and the subsequent risk assessment of the products.