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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. Furthermore, current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. 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. In this presentation the advantages of fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy for various environment samples are shown.
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
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.
The substance class of per- and polyfluorinated alkyl substances (PFAS) comprises more than 5300 organic compounds. PFAS are completely fluorinated on at least one carbon atom. They are associated with negative impacts on human and animal health, are extremely persistent in the environment, and bioaccumulate along food chains. Therefore, PFAS are classified as emerging pollutants. At the same time, their physicochemical properties make them attractive for use in diverse technical applications. They are both hydrophobic and lipophobic and show high thermal as well as chemical resistance due to the strong C-F bond.
First regulations of some PFAS in combination with the technically excellent properties generated an innovation pressure and led to an enormous increase in the number of fluorinated substitution compounds. Due to the increasing complexity of this substance class, target analysis is not able to cover such a variety and multitude of analytes.
Therefore, a suitable PFAS sum parameter method is necessary for an accurate detection of PFAS pollution in the environment, the identification of PFAS hotspots and an evaluation of appropriate remediation measures.
Here we provide insights into the current state of PFAS sum parameter development and present our latest results on method development for the quantitative analysis of PFAS as extractable organically bound fluorine (EOF) in environmental samples using high-resolution molecular absorption spectrometry (HR-CS-GFMAS). For this purpose, we optimized the extraction of PFAS from different solid matrices with simultaneous separation of inorganic fluoride. For quantification resulting extracts were measured using a fluorine specific HR-CS-GFMAS method. By adding gallium salt solutions as modifiers in HR-CS-GFMAS, fluorine can be indirectly quantified very selectively by the in situ formation of GaF with low limits of quantification (instrumental LOQ c(F) < 3 µg/L). Here we will show results from real soil samples from sites with and without known contamination.
Per- and polyfluoroalkyl substances (PFAS) have been used extensively in the past because of their inert chemical character and resistance to degradation by environmental influences. Since the beginning of their commercial use, PFAS have been widely exposed to the environment by application of PFAS in consumer products or as foaming agent in firefighting foams, thus several cases of contaminated soils sites have been reported. Since the number of known PFAS already exceeds 4700, their characterization and direct analysis is challenging given the current available techniques. Here, we introduce the novel fluorine (F) K-edge X-ray absorption near-edge structure (XANES) spectroscopy as a tool to analyze PFAS and inorganic fluorine compounds in contaminated soils and sewage sludges. While F K-edge bulk-XANES spectroscopy provide us information on the overall fluorine bonding in a sample micro X-ray fluorescence (XRF) in combination with F K-edge micro-XANES spectroscopy can also detect minor fluorine compounds and PFAS hotspots in investigated soils and sludges. Additionally, we used the combustion ion chromatography (CIC) to analyze the total amount of all PFAS as a sum parameter (extractable organic fluoride: EOF) in soils and sewage sludges. During combustion in the CIC, the PFAS in the sample get destroyed at temperatures of approx. 1000 °C and converted in inorganic fluorides that subsequently gets quantified by ion chromatography. Thus, for the first time we successfully combined F K-edge XANES spectroscopy and CIC as analytical tools to detect and quantify PFAS contaminants in soils and sewage sludges.
Tire wear particles (TW) are generated by the abrasions of tires on the road surface through traffic. These particles can be transported by air and surface runoff and might also infiltrate the soil and consequently affect terrestrial ecosystems. The estimated tire wear (TW) emissions are immense, with 1.33 106 t a-1 in Europe. Despite this, only little is known about the environmental contents or the fate of TW.
One reason for this knowledge gap is the challenging analysis of TW in environmental samples. Detection of TW with spectroscopic methods is problematic due to high fluorescence interferences caused by contained black carbon. One analytical approach is to use zinc (Zn), a typical additive in tires, as a specific marker for the quantification of tire wear. However, any Zn originating from the sample matrix must be separated beforehand and requires elaborate sample preparation.
Car tires consist partly of synthetic rubbers, such as styrene-butadiene-rubber (SBR). This SBR could be identified and quantified via Thermal-Extraction-Desorption-Gas Chromatography-Mass Spectrometry (TED-GC-MS). This newly developed and fast screening method allows the simultaneous detection of microplastics and TW mass contents and requires minimal to no sample preparation. Firstly the sample is thermally extracted in a thermobalance under a nitrogen atmosphere. The resulting specific decomposition products are sorbed on a solid phase adsorber, which is then transferred to a GC-MS via an autosampler, where the products are desorbed, separated and identified. Cyclohexenylbenzene is used as a specific marker for SBR.
Here we investigated top layer soil samples, collected at the roadside of highly frequented German highways. Samples were analyzed without sample preparation, and SBR was detected in all investigated samples in mass contents ranging from 67.2 to 2230 mg kg-1. A correlation between SBR and Zn content in the soil was confirmed, while the correlation between SBR and Corg was hardly pronounced. We successfully demonstrated the application of TED-GC-MS as a screening method for tire wear in soil samples.
The present study will discuss these analytical results in detail as well as sampling parameters like sampling depth and distance to the roadside, and the effect of the particle size on the particle transport by water runoff and air.
Das Verhalten von Erdböden gegenüber metallenen Konstruktionswerkstoffen ähnelt in vielen Fällen der von neutralen Wässern. Der in natürlichen Erdböden vorhandene Wasseranteil bildet mit den löslichen Inhaltsstoffen eine Elektrolytlösung. Eine merkbare Korrosionsgeschwindigkeit tritt erst dann auf, wenn der Boden einen bestimmten Wassergehalt aufweist, der eine Sauerstoffdiffusion im Boden zur Oberfläche des Metalls gewährleistet. Von maßgebendem Einfluss auf die korrosionsverursachende Wirkung der Böden ist neben dem Feuchtegehalt, der die Leitfähigkeit des Bodens bestimmt, der pH-Wert. Verschiedene Bodenarten besitzen unterschiedliche Wasser- und Sauerstoffdurchlässigkeiten, sowie Unterschiede der gelösten Inhaltsstoffe wie Chloride oder Sulfate, wodurch sich das Korrosionsverhalten von Metallen in verschiedenen Böden stark unterscheidet. In der DIN 50929-3 werden Böden in vier verschiedene Bodenklassen mit Korrosionsbelastungen von sehr niedrig bis hoch unterteilt. Durch verschiedene Bodenanalysen und örtliche Gegebenheiten kann nach DIN 50929-3 zwar die Korrosivität eines Bodens bestimmt werden, jedoch ist die Reproduzierbarkeit eines Bodens (Prüfmediums) praktisch nicht möglich.
Es gibt jedoch Überlegungen, wie die Einstellung einer Bodenklasse durch Verwendung von Normsand und der Zugabe von Stoffen erzielt werden kann, wodurch die Reproduzierbarkeit eines Bodens ermöglicht wird.
While plastics have become indispensable in our daily lives over the last decades, the input into the environment has been increasing concurrently. Plastics often end up in the environment because of intensive use and poor waste management practice. They are subjected to aging and fragmentation and finally be deposited as microplastic particles or in short microplastics (MP). MP are defined as particles originating from synthetic polymers between 1 µm and 5 mm.
Although the pervasive abundance of MP in aquatic environments has been demonstrated comprehensively, less is known about the occurrence and fate of MP in terrestrial ecosystems. It is still unclear if soil functions as a MP source or a sink for aquatic environments. MP can either be transported into water bodies by soil erosion or be retained in soils. The few studies published are not comparable because of non-existent harmonized and standardized methods for sampling, sample preparation, and analysis.
For an assessment of a potential exposure situation of MP, the determination of a mass content in the soil is crucial. Consequently, spectroscopic methods like Raman or FTIR are not suitable, as they deliver information about the shape and size of individual particles. Therefore, we show the application of ThermoExtractionDesorption-GasChromatography-MassSpectrometry (TED-GC-MS) for MP analysis in the soil. In this method, the soil sample is heated up to 600 °C in a nitrogen atmosphere. The decomposition gases are sorbed on a solid phase, then transferred to a GS-MS system where they are desorbed, separated and identified. The method allows the rapid identification of individual polymers through the detection of specific decomposition products, but also the quantitative determination of the MP mass. Besides thermoplastics, elastomers originated from tire abrasion, can be detected.
In the present study, several terrestrial ecosystems in south-west Germany were systematically sampled. Subsequent sample preparation included sieving in fractions of 5-100 µm, 100-1000 µm, and 1-5 mm. MP were extracted by density separation using ZnCl2 solutions. The detection was done by TED-GC-MS measurements. Data of agricultural areas and floodplains are presented exemplarily. A quantitative assessment of highly occurring MP from littering as well as tire abrasion is conducted.
Leaching tests are fundamental tools for the assessment of groundwater impact by contaminated soils concerning the soil-groundwater pathway. Such procedures are supposed to serve as the basis for a reliable leachate prognosis. They can be applied to determine the short and long term leaching behaviour as well as the source term of contaminated soils. For this purpose two types of leaching procedures have been validated in Germany for the examination of the leaching behaviour of frequently occurring organic substances (DIN 19528 - column test and DIN 19529 - batch test). A liquid-to-solid ratio (L/S) of 2 L/kg and 10 L/kg) is the basis for the risk assessment which is implemented in different German regulations. The equivalence of test results for both tests for the same material under investigation has been investigated for a variety of pollutants in order to assess their reliability in compliance testing. However, for emerging pollutants there is hardly data available on this issue.
Leaching tests on soils contaminated with emerging pollutants such as PFC (Perfluorinated Surfactants) are currently coming more into consideration due to the increasing detection of contaminated sites.
Therefore, two soils were investigated in this study from different contamination source (paper sludge containing compost and fire distinguishing foam) using both leaching tests and both liquid-to-solid ratios. The leachability of the various perfluorinated compounds in relation to their content in solid matter was considered. Furthermore the eluate pre-treatment prior analysis (in particular liquid/solid separation step needed for batch tests) has been taken into account.
The comparability of the results from batch and column is dependent on the solubility of the various compounds, on the L/S and on the turbidity in the eluates.
The preservation and the improvement of the fertility of soils by agricultural management measures requires carefully planned decisions which are based on a detailed capture of the soil qualities and a detailed understanding of soil processes. Profit losses can be caused on the one hand by conventional, surface-uniform managements (e.g., fertilization) by too low management intensity on one part of the surface, while other parts of the field receive too high doses and it thereby comes to environmental impacts or to waste of resources.
X-ray fluorescence analysis (XRF) and the Laser-induced Breakdown Spectroscopy (LIBS) are possible technologies which permit online analyses of the chemical composition.
Reliable analysis of chemical indicators in water, sediment and soil samples for the purpose of environmental pollution assessment poses one of the greatest analytical challenges, having in mind the complexity of sample matrix and low concentrations of pollutants. Organics (pesticides, PAHs, PCBs, etc.) and heavy metals (Hg, Cd, Ni, Pb and As) represent target parameters. Laboratories performing sampling and tests in this field regulated by respective EU directives [1], need strong support in terms of providing them with appropriate matrix CRMs enabling the process of quality control. NMIs and DIs with proven metrological capabilities for the production and certification of such materials are necessary for the provision of quality data. This project is aiming to develop capacity to produce CRMs for environmental analysis by transferring the theoretical and practical know-how between the partners and combining their skills to focus on environmental CRM production in accordance with ISO Guide 34 [2]. Production process includes good manufacturing practices for processing materials, method development and validation for homogeneity, stability and characterisation tests, characterisation of selected analytes together with additional information about matrix constituents, the calculation of individual uncertainties (between units inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of the matrix reference materials. Inter laboratory comparison registered as EURAMET project is set as the ultimate project outcome, confirming the partners’ capabilities in applying newly acquired skills.