Investigation of pH-dependent extraction methods for PFAS in (fluoropolymer-based) consumer products: A comparative study between targeted and sum parameter analysis.

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 (

Taking a look at the surface: µ-XRF mapping and fluorine K-edge µ-XANES spectroscopy of organofluorinated compounds in environmental samples and consumer products.

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 substance (PFAS) contamination and inorganic fluoride in sample concentrations down to 100 µg kg-1 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 sheets) were investigated. µ-XRF mapping allows for a unique element-specific visualization at the sample surface and enables localization of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analyzed 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-analyzed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg kg-1 dry weight (dw). All environmentally exposed samples revealed a higher concentration of PFAS with a chain length > C8 (e.g. 580 µg kg-1 dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent of 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.

Measurement of the Environmental Impact of Materials.

Global material use has increased by a factor of eight in the 20th century, and has reached more than 10 tons per capita per year [...].

Dataset on geosynthetic material debris contamination of the South-East Baltic shore.

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).

Investigation of per- and polyfluoroalkyl substances (PFAS) in soils and sewage sludges by fluorine K-edge XANES spectroscopy and combustion ion chromatography.

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).

Mini-review of waste-to-energy related air pollution and their limit value regulations in an international comparison.

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.

A Novel Dry Treatment for Municipal Solid Waste Incineration Bottom Ash for the Reduction of Salts and Potential Toxic Elements.

The main obstacle to bottom ash (BA) being used as a recycling aggregate is the content of salts and potential toxic elements (PTEs), concentrated in a layer that coats BA particles. This work presents a dry treatment for the removal of salts and PTEs from BA particles. Two pilot-scale abrasion units (with/without the removal of the fine particles) were fed with different BA samples. The performance of the abrasion tests was assessed through the analyses of particle size and moisture, and that of the column leaching tests at solid-to-liquid ratios between 0.3 and 4. The results were: the particle-size distribution of the treated materials was homogeneous (25 wt % had dimensions <6.3 mm) and their moisture halved, as well as the electrical conductivity of the leachates. A significant decrease was observed in the leachates of the treated BA for sulphates (44%), chlorides (26%), and PTEs (53% Cr, 60% Cu and 8% Mo). The statistical analysis revealed good correlations between chloride and sulphate concentrations in the leachates with Ba, Cu, Mo, and Sr, illustrating the consistent behavior of the major and minor components of the layer surrounding BA particles. In conclusion, the tested process could be considered as promising for the improvement of BA valorization.

Environmental Impact of Geosynthetics in Coastal Protection.

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. Dynamic surface leaching and ecotoxicological tests were performed to determine the possible release of contaminants. No harmful effects on the test organisms were observed.

Determination of organically bound fluorine sum parameters in river water samples-comparison of combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS).

In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples from river Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 µg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14-0.81% of TF (determined using CIC) and EOF 0.04-0.28% of TF (determined using HR-CS-GFMAS). The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct. Graphical abstract.

Reductive Defluorination and Mechanochemical Decomposition of Per- and Polyfluoroalkyl Substances (PFASs): From Present Knowledge to Future Remediation Concepts.

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.

Using Environmental Simulations to Test the Release of Hazardous Substances from Polymer-Based Products: Are Realism and Pragmatism Mutually Exclusive Objectives?

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.

Metal recovery from incineration bottom ash: State-of-the-art and recent developments.

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.

Legal situation and current practice of waste incineration bottom ash utilisation in Europe.

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.

The effect of polymer aging on the uptake of fuel aromatics and ethers by microplastics.

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 µg L-1 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.

Innovative treatment trains of bottom ash (BA) from municipal solid waste incineration (MSWI) in Germany.

The industrial sector of bottom ash (BA) treatment from municipal solid waste incineration (MSWI) in Germany is currently changing. In order to increase the recovery rates of metals or to achieve a higher quality of mineral aggregates derived from BA, new procedures have been either implemented to existing plants or completely new treatment plants have been built recently. Three treatment trains, which are designated as entire sequences of selected processing techniques of BA, are introduced and compared. One treatment train is mainly characterized by usage of a high speed rotation accelerator whereas another is operating completely without crushing. In the third treatment train the BA is processed wet directly after incineration. The consequences for recovered metal fractions and the constitution of remaining mineral aggregates are discussed in the context of legislative and economical frameworks. Today the recycling or disposal options of mineral residues still have a high influence on the configuration and the operation mode of the treatment trains of BA despite of the high value of recovered metals.

Significance of cadmium from artists' paints to agricultural soil and the food chain.

BACKGROUND: An Annex XV restriction dossier for cadmium in artists' paints was submitted by an EU member state to the European Chemicals Agency ECHA. By cleaning, used brushes under the tap cadmium can enter the food chain via waste water treatment and subsequent agricultural application of the sewage sludge. It was estimated that 110 kg Cd per year is spread on agricultural land via this exposure route. Other sources of Cd amount to almost 120 tons per year. RESULTS: The mobility of Cd from pigments was studied in a field-like scenario by leaching experiments using soil samples amended with sewage sludge and spiked with Cd pigments in percolation columns. The redox conditions were confirmed to be the decisive factor for the release of Cd. The release of Cd from artists' paints was in most cases 1 % or lower in the experiments performed. CONCLUSIONS: Application of sewage sludge containing Cd from artist paints does not increase the amount of Cd leached from this soils. Furthermore, the quantity of Cd from artists' paints calculated in the restriction dossier is negligible compared to other sources of Cd to agricultural soil. Therefore, ECHA did not consider the proposed restriction to be the most appropriate EU wide measure to address the negligible level of risk.

Effect of contact time on the release of contaminants from granular waste materials during column leaching experiments.

When reusing or disposing of contaminated granular waste materials there is a need to evaluate how the contaminants will interact on the pathway soil-groundwater and the effect this interaction will have on the surrounding environment. While column testing can provide a closer approximation to field percolation conditions than batch testing, there is still a need to develop column testing procedures that consider the requirements of practical testing time frames. This study evaluates the effect of different column contact times (2.5, 5, and 16h) on the release of inorganic constituents from bottom ash and demolition waste, two commonly reused granular materials. Leaching data for representative constituents of concern, such as copper, chromium, sulfate and chloride, as well as pH and electrical conductivity was compared for all different contact times studied. Results for the materials investigated in this study showed that variations in contact time have no significant effect on the release of the selected constituents and leaching parameters at low liquid to solid ratios. However, after a liquid to solid ratio of 1L/kg, the effect is more noticeable, and higher contact times show lower pH values as well as a reduction in the release of constituents of concern from bottom ash. In the case of demolition waste, the variation of contact time did not have a strong effect on the leaching behavior.

Evaluation of leaching and extraction procedures for soil and waste.

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.

Results of interlaboratory comparisons of column percolation tests.

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathway (leachate forecast) on contaminated sites in Germany. Interlaboratory comparisons on the evaluation of the reproducibility of column percolation tests were conducted within the framework of an integrated R+D program using three waste reference materials. The interlaboratory comparisons of column percolation tests showed good reproducibility of the results for inorganic and organic parameters as well as for the accompanying parameters. This is due to the stipulations concerning the time of contact between leachant and sample material as well as the sample placement in the columns. Different column dimensions used by the participants of the interlaboratory comparisons did not have any substantial influence on the column test results.