6.6 Physik und chemische Analytik der Polymere
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Material Selection Strategy
(2023)
Microplastic and nanoplastic particles (MNP) are spread all over the world in various types, shapes and sizes making it very challenging to accurately analyse them. Each sampling procedure, sample preparation method and detection technique needs suitable reference materials to validate the method for accurate results. Furthermore, the effects of these MNPs should be evaluated by risk and hazard assessment with test particles close to reality. To better understand MNP behavior and aid in clarification of their interactions with organisms, we produced several MNP materials by top-down procedure and characterized their properties. Since surface properties mostly determine particles’ toxicity, the aim of the present study was to determine which functional groups are present on MNPs and how the surface can be affected by the production process and particle’s environment.
Monitoring of microplastics in food matrices is crucial to determinate the human exposure. By direct ingestion microplastics could be released in the food during the production, through packaging and by consumer’s use. The absence of standard methods to quantify and detect different size range and type of microplastics has led to difficult and time consuming procedural steps, poor accuracy and lack of comparability. In this work, matrix characterization and laboratory experiments were used to investigate the efficiency of sample preparation in milk powder. This information is crucial to compile a standard procedure for sample preparation and digestion of common milk powder to detect different particle sizes and types of polymers. Charaterisation is done by TGA and TOC measurements.
Due to the favorable properties of polymers, their production and thus their input into the environment has increased significantly in recent decades. Currently, FTIR or Raman spectroscopy are mainly applied for the analysis of microplastic particles (MP) in environmental samples. However, these methods have great difficulties in determining metrologically traceable MP values, especially with regard to the limiting values, as preferred in regulation. Therefore, we developed a systematic and fast thermoanalytical method called TED-GC-MS (thermal extraction desorption gas chromatography mass spectrometry), which determines mass contents. Now the current goal is the determination of its process parameters.
This poster illustrates the theoretical requirements for MP analysis (left side) and contrast them with the current state of research (right side).Unexpected practical problems are presented and the relatively new method is discussed concerning the quality requirements of well-established methods such as LC-or GC-MS.
The ubiquitous presence of unwanted plastics in the environment, especially microscale particles, has been an issue in scientific studies and public debate in the last years. It is well known that oxidative degradation and subsequent fragmentation, caused by UV-radiation, oxidative aging and abrasion lead to the decomposition of larger plastic products into microplastics (MP). Possible effects of these MP on ecosystems are still unclear. Recent studies on MP findings are focused mainly on aquatic systems, while little is known about MP in terrestrial ecosystems.
A possible source of MP input into the soil is compost from domestic bio-waste. Inappropriate waste separation causes plastic fragments in the bio-waste, some of which end up in the compost. In Germany compost is used as fertilizer in agriculture, hence MP could enter the soil by this pathway. So far, there have been only a few studies on this object. For this reason, analysis of compost as a sink and source of MP in ecosystems is of high interest.
To estimate and monitor the MP content in compost and soil, fast and harmonised analytical methods are essential, which not only measure the polymer type and number of particles, but also the mass content. The most common spectroscopic methods are very time-consuming, often require complex sample preparation steps and cannot determine mass contents. Therefore, we used ThermoExtractionDesorption-GasChromatography-MassSpectrometry (TED-GC-MS) as a fast, integral analytical technique. The sample is pyrolyzed to 600°C in a nitrogen atmosphere and an excerpt of the pyrolysis gases is collected on a solid phase adsorber. Afterwards, the decomposition gases are desorbed and measured in a GC-MS system. Characteristic pyrolysis products can be used to identify the polymer type and determine the mass contents. This method is well established for the analysis of MP in water filtrate samples.
In the present work we optimized the TED-GC-MS method for compost and compost/soil matrix and very common polymers, such as polyethylene, polypropylene, polyethylene-terephthalate and polystyrene (sample mass, detection limits, interfering signals, etc.). Additionally, specific pyrolysis products of polymers used for bio-waste bags, such as polylactide (PLA) and polybutylenadipat-terephthalat (PBAT) had to be identified and evaluated.
First measurements were carried out on model and real samples from prepared mixtures and composting plant. The samples were sterilized, fractionated, filtered and dried. In addition, half of the sample material was treated with hydrogen peroxide to investigate a possible effect on detection.
Microplastics are widely distributed in aquatic and terrestrial environments, up to now less is known on toxicological impacts under realistic conditions. Research so far has focused mainly on the impacts on organisms by fresh plastic fragments or beats. However, plastic materials found in the environment are mainly a mixture of different polymers and particularly degraded during aging processes. Although especially oxidized degradation products might escape from plastic materials during aging, there is a lack of information on potentially adverse effects on aquatic biota. The latter is of particular interest as oxidized chemicals become more water soluble due to higher polarity and are more bio-available, therefore.
The present study focussed on plastic leachates of polystyrene (PS) and polylactic acid (PLA), which were derived from alternating stress by hydrolysis and UV radiation. Test specimen of PS, PLA or PS/PLA blends (each 50 %) were alternatingly maintained in water at 45 °C for five days and UV radiated at 45 °C for two days, for in total six weeks. Ecotoxicological effects of potentially generated degradation products of plastic materials in the storage water (mineral water, pH: 7.2) were detected by algae growth inhibition tests with Desmodesmus suspicatus and photosystem II inhibition tests with Raphidocelis subcapitata.
Results clearly indicate inhibitory effects on algae growth by contaminants in the storage water of stressed plastic materials with increasing growth inhibition of proceeding hydrolysis and UV stress times. Here, different plastics cause variable responses of algal growth. First chemical analyses indicate dissolved monomers and their oxidation products of plastic materials as possible driver of detected ecotoxicological effects, since detected microplastic particles do not seem to harm algae.
The existing data highlight the relevance of plastic aging as a framework for microplastic ecotoxicity evaluation and allow a proof of concept.
Despite abundant evidence of the occurrence of microplastics (MP) – these are particles smaller 5 mm – in aquatic environments, little is known about the accumulation of plastic in terrestrial environments, especially in soils.
Possible major input pathways could be the use of plastic mulching, the use of compost, sewage sludge or residues from biogas facilities as fertilizers, as well as littering in urban areas. To estimate the MP pollution, the development of reliable, fast methods for sampling, sample preparation, and detection is needed. The obtained data must be representative of the sampled environmental compartment and measurements from different environmental compartments must be comparable. A first breakthrough is an application of ThermoExtractionDesorption-Gas Chromatography-MassSpectrometry (TED-GC-MS) for the detection of MP, including tire abrasives. This method allows the determination of mass content within a few hours and only a minimum of sample preparation for samples from aquatic environments is needed.
However, in contrast to filtrate samples from aquatic environments, sediment or soil samples need an enrichment of MP. Whereas MP concentration from marine sediments can be obtained by floatation and density Separation techniques using NaCl solutions, the extraction or separation from soils proves to be more difficult, as plastic particles are often part of organo-mineral aggregates within the soil matrix.
The aim of this study is the development of a practicable processing guideline for representatively taken soil samples in order to concentrate microplastics, without complex and time-consuming treatment steps. Dispersants or detergents can be applied to decompose the soil matrix, but each preparation step carries the risk of crosscontamination of the sample and prolongs the preparation procedure.
For this reason, we choose ZnCl2-solution with a density of 1.7 g/cm3, which include the densities of relevant MP types (0.9-1.7 g/cm3). It was tested to achieve both, disaggregation and separation as it decomposes organic material and dissolves carbonates. Also, ZnCl2 is inert to the precipitation of undesirable salts and Carbonates during the process of density separation, as polytungstate solution does. ZnCl2 can be reused after stepwise filtering (7 µm, 1.5 µm, 0.7 µm). Thus, disposal costs can be reduced. Efficiency and reproducibility of the sample preparation as well as the degradation behavior of MP under the present conditions were demonstrated with model samples.
Real sampling campaigns were conducted at several agricultural sites and floodplains in south-west Germany. The sampling was performed according to practice for soil sampling, using adequate sampling strategies (pattern of sampling, number of field samples, homogenization, etc). The lab sample was fractioned into three size classes (5-100 µm, 100-1000 µm, and 1-5 mm). The identification and determination of mass fraction were done using TED-GC-MS.