6 Materialchemie
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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.
Im Vortrag wird die Problematik Mikroplastik eingeführt und ein Probenset aus dem Mittelmeer mit ersten Ergebnissen besprochen. Die Alterung von Polymeren im Umweltkontext sowie Möglichkeiten der Analyse von Polymeralterungsfortschritten werden diskutiert. Die thermoanalytische Methode mit Zersetzungsgasanalytik (TED-GC-MS) wird eingeführt und deren Einsatzmöglichkeiten in der Thematik umrissen.
µ-FTIR spectroscopy is a widely used technique in microplastics research. It allows to simultaneously characterize the material of the small particles, fibers or fragments, and to specify their size distribution and shape. Modern detectors offer the possibility to perform two-dimensional imaging of the sample providing detailed information. However, datasets are often too large for manual evaluation calling for automated microplastic identification. Library search based on the comparison with known reference spectra has been proposed to solve this problem.
To supplement this ‘targeted analysis’, an exploratory approach was tested. Principal component analysis (PCA) was used to drastically reduce the size of the data set while maintaining the significant information. Groups of similar spectra in the prepared data set were identified with cluster analysis. Members of different clusters could be assigned to different polymer types whereas the variation observed within a cluster gives a hint on the chemical variability of microplastics of the same type. Spectra labeled according to the respective cluster can be used for supervised learning. The obtained classification was tested on an independent data set and results were compared to the spectral library search approach.
Plastics and rubber are used in many applications, such as packaging, building, construction and mobility. Due to their favourable properties like light weight, flexible processing and low costs their production and consequently their input into the environment has increased significantly over the last decades. In the environment, oxidation processes and mechanical abrasion lead to the decomposition of these plastics into small fragments, called microplastic (< 5 mm). By definition, microplastics only involve thermoplastics and duroplastics but elastomers made out of synthetic polymers (e. g. styrene butadiene rubber), modified natural polymers (e. g. natural rubber) and products of synthetic polymers (e. g. tires) are also part of the current microplastic discussion. The main entry pathway of rubber into the environment is the wear of used tire treads in road traffic. Lassen et al. showed that 60 % of the microplastic emissions in Denmark into the environment come from secondary microplastics generated by tires. Rain events can cause microplastic and rubber to get from the street into the street inlets. Depending on the sewage system, these waters are sometimes not cleaned in the sewage treatment plants and reach the surface waters untreated.
To analyse microplastic particles in samples, mainly FTIR or Raman spectroscopic methods are applied at present. Rubber or tire particles in environmental samples cannot be analysed by these methods, because the added carbon black leads to annoying absorption and fluorescent effects.
We developed a thermoanalytical method, the so-called TED-GC-MS (thermal extraction desorption gas chromatography mass spectrometry), which allows the simultaneous detection of microplastic and tire wear with almost no sample preparation in about 2.5 h. The TED-GC-MS is a two-step analytical method which consists of a thermobalance and a GC-MS system. Up to 50 mg of an environmental sample is heated up to 600 °C in a nitrogen atmosphere. During pyrolysis, between 300 and 600 °C polymer-specific decomposition products are produced and collected on a solid phase. Afterwards the substances are desorbed, separated and analysed using the GC-MS.
The aim of the present work is to present the TED-GC-MS as a time efficient screening method to quantify the industrial most relevant polymers in street run-off samples. Analytical challenges in the determination of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET) and polyamide (PA), polymethyl methacrylate (PMMA) and styrene-butadiene-rubber (SBR) as a component of tire wear are honestly discussed.
The study area is a 200 m long section of the Clayallee in Berlin, a representative typical urban catchment area. The road run-off in this section flows through the gullies directly into a sample chamber, which directs the runoff in an open channel to the rainwater sewer of this area. The sample chamber allows a sample to be taken directly from the road run-off without mixing with the run-off from other areas. The sample chamber is equipped with an automatic sampler. The automatic sampler is controlled by a conductivity sensor to detect the storm event at an early stage. The sensor gives the sampler a signal to start the sampling program when it gets in contact with water and reaches a certain conductivity threshold. The capacity of the sample container is 100 l and the maximum delivery of the automatic sampler is 2.8 l/min.
Afterwards, the water was pumped through various stainless-steel sieves with a diameter of approximately 20 cm and mesh widths of 500, 100, 50 μm. The obtained solids were steam sterilized, freeze-dried and measured with the TED-GC-MS.
The results of the TED-GC-MS-measurements are summarized in Figure 1. It shows the polymers which were detected in 1 mg of the dry masses of various street run off samples obtained during a period of 1.5 years. We detected PMMA, PS, PP, PE and SBR, as a component of tire wear in the samples. The quantification of the polymers leads to amounts of PS, PP, PE and SBR between 0 µg and 10 µg. PMMA was only detected in traces.
The TED-GC-MS analysis is a two-step method. A sample is first decomposed in a thermogravimetric analyzer (TGA) and the gaseous decomposition products are then trapped on a solid-phase adsorber. Subsequently, the solid-phase adsorber is analyzed with thermal desorption gas chromatography mass spectrometry (TDU-GC-MS). This method is ideally suited for the analysis of polymers and their degradation processes. Here, a new entirely automated System is introduced which enables high sample throughput and reproducible automated fractioned collection of decomposition products. Strengths and limitations of the system configuration are elaborated via three examples focused on practical challenges in materials analysis and identification: i) separate analysis of the components of a wood-plastic-composite material, ii) quantitative determination of weight concentration of the constituents of a polymer blend and iii) quantitative analysis of model samples of microplastics in suspended particulate matter.
The occurrence of microplastic particles (MP) in nearly each environmental compartment but especially in water is well documented in an increasing amount of publication within the last few years. However, a comprehensive understanding of MP occurrence, sources and pathways in the environment as well as effects of MP on the environment is still unclear. Many of the studies are not compatible, because they used different sampling, sample preparation and detection techniques, resulting in a very broad variation and very different dimension of archived results. Hence a useful avoiding strategy for reduction the MP entry in the environment is not possible. Furthermore, the existing methods are often very time consuming, need user knowledge and labour force, which is often not acceptable for the routine monitoring of an action or sanction.
The call for harmonised methods become loud and louder and promising efforts are done in this area. However, the scientific discussion is often focus on advantages and disadvantages of detection tools and sample preparation, less initiative is given to the sampling strategy. That is a pity, because every environmental scientist knows, a good analytical result depend on a good sampling strategy.
The sampling of water seems on the first view easy because the sampling process include already an up concentration of the MP by means of sieves and filters. However, this filtering of water is often limited by filter cake on the sieves, consisting of high amount of natural particular matter. Hence often a small water volume is filtered, which will not own a representative amount of trait carriers or complex sieves cascades are used, which need a high technical equipment.
Recently we presented a fast thermoanalytical method for the detection of polymers fractions in water samples. This method, thermo-extraction desorption gas chromatography mass spectrometry (TED-GC-MS) can analyse MP in water filtrates without sample preparations within 2-3 hours. Advantageous is the additional analysis of rubber particles from tires beside the MP. In order to come even faster we now start to develop new sampling strategies, which should be use for different water systems. It is intended to reduce the effort in the field and to elongate times for sampling to obtain a representatives result without random effects.
In the present presentation we will show first result using a sedimentation box for sampling of MP from surface water. Advantages and disadvantages will be discussed and comparison to data from conventional fractionated filtration will be given.