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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.
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.
Investigation on the Durability of a Polypropylene Geotextile under Artificial Aging Scenarios
(2024)
Geosynthetics are widely used in various civil engineering applications, such as geotextiles in coastal protection, and display a sustainable alternative to natural mineral materials. However, the full benefits of using geosynthetics can only be gained with a long service lifetime of the products. With the use of added stabilizers to the polymers, service lifetimes can be achieved in the range of 100 years. Therefore, accelerated aging methods are needed for the assessment of the long-term performance of geotextiles. In the present study, the behavior of geosynthetic materials made of polypropylene was investigated under artificial aging conditions involving elevated temperatures ranging from 30 to 80 °C, increased oxygen pressures ranging from 10 to 50 bar in water-filled autoclaves, and UV irradiation under atmospheric conditions. ATR-IR spectroscopy was employed to detect the increase in the carbonyl index over various aging durations, indicating the oxidative degradation of the geotextile. The most pronounced increase was observed in the case of aging through UV irradiation, followed by thermal aging. Elevated pressure, on the other hand, had a lower impact on oxidation. High-temperature size exclusion chromatography was utilized to follow the reduction in molar mass under different degradation conditions, and the results were consistent with those obtained from ATR-IR spectroscopy. In polyolefins such as polypropylene, Hindered Amine Stabilizers (HAS) are used to suppress oxidation caused by UV radiation. The quantitative analysis of HAS was carried out using a UV/Vis method and HPLC. The degradation of UV stabilizers during the aging of geotextiles is responsible for the oxidation and the reduction in the molar mass of polypropylene. From the results, it can be concluded that applications of PP geotextile without soil or sand cover might cause the risk of the formation of microplastic particles. Material selection, design, and maintenance of the construction must follow best practices, including the system’s removal or replacement at end-of-life. Otherwise, a sustainable use of geotextiles in civil engineering is not possible.
Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (<LOD to 58.1 μg/g). Moreover, the methods were contrasted with the "total hydrolyzable precursor" (THP) assay analyzed using gas-chromatography coupled mass spectrometry (GC-MS), which yielded concentrations of 6:2–10:2 fluorotelomer alcohols (<LOD-568 μg/g) for textile and paper samples. Furthermore, targeted analytical investigation of 25 compounds via liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) was conducted and accounted for significantly lower sum amounts (<LOD-0.98 μg PFAS/g). To estimate the fluorine mass balance of all methods, the fluorine levels of target analytical data were calculated and compared to the sum parameter values and evaluated. Finally, the efficiency of the extraction method was approximated by the recovery analysis of four selected SFP model compounds compared to their TF values, yielding 36.7–74.0% after extraction and 3.8–36.3% after processing the extract for the HOF sum parameter.
The long-term leaching behavior of incineration bottom ash (IBA) was studied with large-scale samples from two German waste incinerators with grate technology. The observation period was up to 281 days. The aging processes proceeded faster in the outdoor storage of the samples. The dominant factor in the leaching behavior is the pH, which starts at values above 12 and decreases to values below 10 (outdoors, <11 indoors). Most heavy metals exhibit minimum solubility in this pH range. The solubility of Sb depends on the prevailing Ca concentration, due to the formation of low-soluble Ca antimonate. The very low sulfate concentrations observed in the leaching tests with fresh IBA could be explained by the presence of ettringite. In the course of the aging reaction, ettringite is transformed into gypsum. The results from batch tests were compared with those from column tests, showing reasonable agreement. Leaching dynamics can be better followed with column tests. All results confirm that the use of IBA is possible under German law.
Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.
Das Recycling von gemischten Baustoffen führt neben der Herstellung von Gesteinskörnungen parallel zu einem stärker schadstoffbelasteten Stoffstrom, der circa ein Drittel der ursprünglichen Masse ausmacht. Dieser sogenannte Brechsand endet derzeit in der Deponierung und wird somit der Kreislaufwirtschaft entzogen. Der vorliegende Beitrag untersucht nun die Aufbereitung dieses Materials unter Verwendung einer Setzmaschine im Pilotmaßstab. Hierbei wird die Eignung dieser Technik evaluiert und das Aufbereitungsprodukt als möglicher Ersatzbaustoff untersucht.
Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted
and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but
consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values
of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations.
Half of global material consumption involves mineral material. The circularity is still low so that the enhanced use of secondary building material is required to close loops. Three different secondary building materials are discussed based on exemplary research results: construction and demolition waste (C&D waste), soil-like material, and incineration bottom ash (IBA). Focus was placed on the environmental compatibility of the materials examined mainly by standardized leaching tests. C&D waste was investigated after a wet treatment using a jigging machine, and soil-like material and IBA were characterized with respect to their material composition. Their environmental compatibilities in particular were studied using standard leaching tests (batch tests and column tests).
It was concluded that soil-like material can mostly be utilized even when the precautionary limit values set are exceeded by a factor of less than two. For C&D waste, the fine fraction below 2 mm and the content of brick material is problematic. IBA fulfills quality level “HMVA-2” following German regulations. Improved levels of utilization might be achievable with better treatment technologies.
For the first time, µ-X-ray fluorescence (µ-XRF) mapping combined with fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substances (PFAS) contamination and inorganic fluoride in samples concentrations down to 100 µg/kg fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheet) were investigated. µ-XRF mapping allows for a unique element-specific visualisation at the sample surface and enables localisation of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analysed via fluorine K-edge µ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded µ-XANES spectra. Complementarily, solvent extracts of all samples were target-analysed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg/kg dry weight (dw). All environmentally exposed samples revealed higher concentration of PFAS with a chain length >C8 (e.g. 580 µg/kg dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent from quantified PFAS amounts via target analysis, µ-XRF mapping combined with µ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples.
The release of hazardous compounds from construction products can harm human health and the environment. To improve the sustainability of construction materials, the leaching of substances from construction products and their potential environmental impact should be assessed. Twenty-seven construction products from different product groups were examined with a combination of standardized leaching tests (dynamic surface leaching test and percolation test) and biotests (algae, daphnia, fish egg, luminescent bacteria, umu and Ames fluctuation tests). To identify the released substances, extensive qualitative and quantitative chemical analyses were performed, including gas chromatographic and liquid chromatographic screening techniques.
Results: Many of the tested eluates caused signifcant ecotoxic efects. Particularly high ecotoxicities were observed for grouts (lowest ineffective dilution (LID) up to 16384) and cork granules (LID up to 24578). The results of ecotoxicity tests allow the prioritization of the eluates that should be subjected to detailed chemical analyses. Organic screening by different methods and ranking the identifed substances based on recorded hazard classification is a suitable approach to identify the relevant toxic substances.
Conclusions: Determining the ecotoxicity of eluates from construction products records the summary effect of all leachable substances. This instrument is especially useful for construction products of complex and largely unknown composition. The ecotoxicological and the chemical–analytical approach complement each other in an ideal way to characterize the potential hazard of eluates from construction products and to identify the environmentally hazardous components in these eluates. Our results confirm that the proposed harmonized methods for testing eluate toxicity are an adequate and applicable procedure to move toward a more sustainable way of building and to reduce toxic effects of construction products in their use phase in the environment.
The most massive design on the Baltic shore used geosynthetic materials, the landslide protection construction in Svetlogorsk (1300 m long, 90,000 m2 area, South-Eastern Baltic, Kaliningrad Oblast, Russian Federation) comprises the geotextile and the erosion control geomat coating the open-air cliff slopes. Due to changes in elastic properties during long-term use in the open air, as well as due to its huge size, this structure can become a non-negligible source of microplastic pollution in the Baltic Sea. Weather conditions affected the functioning of the structure, so it was assessed that geosynthetic materials used in this outdoor (open-air) operation in coastal protection structures degraded over time. Samples taken at points with different ambient conditions (groundwater outlet; arid places; exposure to the direct sun; grass cover; under landslide) were tested on crystallinity and strain at break. Tests showed a 39–85% loss of elasticity of the polymer filaments after 3 years of use under natural conditions. Specimens exposed to sunlight are less elastic and more prone to fail, but not as much as samples taken from shaded areas in the grass and under the landslide, which were the most brittle.
Industrial-scale mechanical recycling of plastics has been established for years, but has technical and economic limits. Chemical recycling processes lead back to monomers or to the raw materials, so that in the end new goods can be produced for all areas of application of plastics. The variety of chemical recycling processes is large. The capacities of the plants are still low today. The profitability of the plants is strongly influenced by the price of oil; the profitability limit is currently between 50 and 60 US $ per barrel.
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.
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.
The diffusive gradients in thin-films (DGT) technique shows in many publications a superior correlation to the amount of plant-available phosphorus (P) in soil. However, this technique cannot give information on the plant-available P species in soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time.
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.
Buildings exposed to water can release undesirable substances which, once transported to environmental compartments, may cause unwanted effects. These exposure pathways need to be investigated and included in risk assessments to safeguard water quality and promote the sustainability of construction materials. The applied materials, exposure conditions, distribution routes and resilience of receiving compartments vary considerably. This demonstrates the need for a consistent concept that integrates knowledge of emission sources, leaching processes, transport pathways, and effects on targets. Such a consistent concept can serve as the basis for environmental risk assessment for several scenarios using experimentally determined emissions. Typically, a source–path–target concept integrates data from standardized leaching tests and models to describe leaching processes, the distribution of substances in the environment and the occurrence of substances at different points of compliance. This article presents an integrated concept for assessing the environmental impact of construction products on aquatic systems and unravels currently existing gaps and necessary actions. This manuscript outlines a source–path–target concept applicable to a large variety of construction products. It is intended to highlight key elements of a holistic evaluation concept that could assist authorities in developing procedures for environmental risk assessments and mitigation measures and identifying knowledge gaps.
The database gives information on the contamination of the shore of the South-Eastern Baltic with the debris of geosynthetic materials for the period 2018–2020. This new type of coastal pollution enters the natural environment due to the destruction of coastal protection structures and construction activities. The database contains sections:
(1) a list of types of geosynthetic material residues, their photographic images and photographs illustrating examples of finds in natural conditions
[1 List_geosynthetic_debris_SEB],
(2) monitoring data on the contamination of the beach strip with the debris of geotextiles, braids from gabions, geocontainers (big bags), geocells and geogrids for the beaches of the South-Eastern Baltic for the period 2018–2020
[2 Monitoring_geosynthetic_debris_SEB];
(3) statistical distributions of the found geosynthetic debris by size
[3 Scales_geosynthetic_debris_SEB] and (4) results of test surveys on the shores of Lithuania and Poland adjacent to Kaliningrad Oblast.
All data refer to the beaches of the Kaliningrad Oblast (Russia), including the Russian parts of the Vistula and Curonian Spits, but also contains information on a one-time assessment of the pollution of the beaches of the adjacent territories: the Polish shore from the Poland-Russia border on the Vistula Spit to the mouth of the Vistula River, the Lithuanian shore from the border Lithuania-Russia on the Curonian Spit to the border of Latvia-Lithuania. Materials were collected during field surveys within the ERANET-RUS_Plus joint project EI-GEO, ID 212 (RFBR 18-55-76002 ERA_a, BMBF 01DJ18005).
For the first time, fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to detect per- and polyfluoroalkyl substances (PFAS) in various soil and sewage sludge samples. The method can be used to determine the speciation of inorganic and organic fluorides, without pre-treatment of solid samples. Therefore, XANES spectra of several inorganic fluorides as well as selected fluorinated organic compounds were recorded. While inorganic fluorides partially exhibit a variety of sharp spectral features in the XANES spectrum, almost all inspected organofluorine compounds show two distinct broad features at 688.5 and 692.0 eV. Moreover, the peak intensity ratio 688.5 eV/692.0 eV in the PFAS XANES spectrum can be inversely correlated to the chain length of the perfluoro sulfonic acid group. The detection of targeted PFAS by bulk-XANES spectroscopy in combination with linear combination fitting in soils and sewage sludges was not applicable due to the low organic fluorine to total fluorine ratio of the samples (0.01–1.84%). Nonetheless, direct analysis of pure PFAS revealed that analysis of organofluorine species might be achieved in higher concentrated samples. Furthermore, quantitative measurements by combustion ion chromatography (CIC) evaluated as sum parameters extractable organically bound fluorine (EOF) and total fluorine (TF) emphasize that besides soils, sewage sludges are a significant source of organic fluorine in agriculture (154–7209 μg/kg).