Riverbed depth-specific microplastics distribution and potential use as process marker.

Riverbed sediments have been identified as temporary and long-term accumulation sites for microplastic particles (MPs), but the relocation and retention mechanisms in riverbeds still need to be better understood. In this study, we investigated the depth-specific occurrence and distribution (abundance, type, and size) of MPs in river sediments down to a depth of 100 cm, which had not been previously investigated in riverbeds. In four sediment freeze cores taken for the Main River (Germany), MPs (≥ 100 µm) were detected using two complementary analytical approaches (spectroscopy and thermoanalytical) over the entire depth with an average of 21.7 ± 21.4 MP/kg or 31.5 ± 28.0 mg/kg. Three vertical trends for MP abundance could be derived, fairly constant in top layers (0-|30 cm), a decrease in middle layers (30-60 cm), and a strong increase in deep layers (60-100 cm). The dominant polymer types were polyethylene (PE), polypropylene (PP), and polystyrene (PS). Polyethylene terephthalate (PET) and PP were also found in deep layers, albeit with the youngest age of earliest possible occurrence (EPO age of 1973 and 1954). The fraction of smaller-sized MPs (100-500 µm) increased with depth in shallow layers, but the largest MPs (> 1 mm) were detected in deep layers. Based on these findings, we elucidate the relationship between the depth-specific MP distribution and the prevailing processes of MP retention and sediment dynamics in the riverbed. We propose some implications and offer an initial conceptual approach, suggesting the use of microplastics as a potential environmental process tracer for driving riverbed sediment dynamics.

Microplastic analysis in drinking water based on fractionated filtration sampling and Raman microspectroscopy.

Microplastics (MP) as emerging persistent pollutants were found in raw and drinking water worldwide. Since different methods were used, there is an urgent need for harmonized protocols for sampling, sample preparation, and analysis. In this study, a holistic and validated analytical workflow for MP analysis in aqueous matrices down to 5 µm is presented. For sampling of several cubic meters of water, an easily portable filter cascade unit with different pore sizes (100-20-5 µm) was developed and successfully applied for the sampling of three processed drinking waters, two tap waters and one groundwater. The size distribution and polymer types of MP were determined using a two-step semi-automated Raman microspectroscopy analysis. For quality control, comprehensive process blanks were considered at all times and a recovery test yielded an overall recovery of 81%. The average concentration of identified MP was 66 ± 76 MP/m3 ranging from 1 MP/m3 to 197 MP/m3. All found concentrations were below the limit of quantitation (LOQ) of 1880 MP/m3. The majority consisted of PE (86% ± 111%) while comparatively low numbers of PET (10% ± 25%), PP (3% ± 6%), and PA (1% ± 4%) were found. 79% of all particles were smaller than 20 µm. In summary, this study presents the application of a workflow for sampling and analysis of MP down to 5 µm with first results of no significant contamination in drinking water and groundwater.

When Good Intentions Go Bad-False Positive Microplastic Detection Caused by Disposable Gloves.

Apart from being considered a potential threat to ecosystems and human health, the ubiquity of microplastics presents analytical challenges. There is a high risk of sample contamination during sampling, sample preparation, and analysis. In this study, the potential of sample contamination or misinterpretation due to substances associated with disposable laboratory gloves or reagents used during sample preparation was investigated. Leachates of 10 different types of disposable gloves were analyzed using Raman microspectroscopy (µ-Raman), Fourier-transform infrared microspectroscopy (µ-FTIR), and pyrolysis-gas chromatography/mass spectrometry (pyr-GC/MS). There appeared to be polyethylene (PE) in almost all investigated glove leachates and with all applied methods. Closer investigations revealed that the leachates contained long-chain compounds such as stearates or fatty acids, which were falsely identified as PE by the applied analytical methods. Sodium dodecyl sulfate, which is commonly applied in microplastic research during sample preparation, may also be mistaken for PE. Therefore, µ-Raman, µ-FTIR, and pyr-GC/MS were further tested for their capability to distinguish among PE, sodium dodecyl sulfate, and stearates. It became clear that stearates and sodium dodecyl sulfates can cause substantial overestimation of PE.

Critical Review of Processing and Classification Techniques for Images and Spectra in Microplastic Research.

Microplastic research is a rapidly developing field, with urgent needs for high throughput and automated analysis techniques. We conducted a review covering image analysis from optical microscopy, scanning electron microscopy, fluorescence microscopy, and spectral analysis from Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, pyrolysis gas-chromatography mass-spectrometry, and energy dispersive X-ray spectroscopy. These techniques were commonly used to collect, process, and interpret data from microplastic samples. This review outlined and critiques current approaches for analysis steps in image processing (color, thresholding, particle quantification), spectral processing (background and baseline subtraction, smoothing and noise reduction, data transformation), image classification (reference libraries, morphology, color, and fluorescence intensity), and spectral classification (reference libraries, matching procedures, and best practices for developing in-house reference tools). We highlighted opportunities to advance microplastic data analysis and interpretation by (i) quantifying colors, shapes, sizes, and surface topologies with image analysis software, (ii) identifying threshold values of particle characteristics in images that distinguish plastic particles from other particles, (iii) advancing spectral processing and classification routines, (iv) creating and sharing robust spectral libraries, (v) conducting double blind and negative controls, (vi) sharing raw data and analysis code, and (vii) leveraging readily available data to develop machine learning classification models. We identified analytical needs that we could fill and developed supplementary information for a reference library of plastic images and spectra, a tutorial for basic image analysis, and a code to download images from peer reviewed literature. Our major findings were that research on microplastics was progressing toward the use of multiple analytical methods and increasingly incorporating chemical classification. We suggest that new and repurposed methods need to be developed for high throughput screening using a diversity of approaches and highlight machine learning as one potential avenue toward this capability.

Critical Assessment of Analytical Methods for the Harmonized and Cost-Efficient Analysis of Microplastics.

Microplastics are of major concerns for society and is currently in the focus of legislators and administrations. A small number of measures to reduce or remove primary sources of microplastics to the environment are currently coming into effect. At the moment, they have not yet tackled important topics such as food safety. However, recent developments such as the 2018 bill in California are requesting the analysis of microplastics in drinking water by standardized operational protocols. Administrations and analytical labs are facing an emerging field of methods for sampling, extraction, and analysis of microplastics, which complicate the establishment of standardized operational protocols. In this review, the state of the currently applied identification and quantification tools for microplastics are evaluated providing a harmonized guideline for future standardized operational protocols to cover these types of bills. The main focus is on the naked eye detection, general optical microscopy, the application of dye staining, flow cytometry, Fourier transform infrared spectroscopy (FT-Ir) and microscopy, Raman spectroscopy and microscopy, thermal degradation by pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) as well as thermo-extraction and desorption gas chromatography-mass spectrometry (TED-GC-MS). Additional techniques are highlighted as well as the combined application of the analytical techniques suggested. An outlook is given on the emerging aspect of nanoplastic analysis. In all cases, the methods were screened for limitations, field work abilities and, if possible, estimated costs and summarized into a recommendation for a workflow covering the demands of society, legislation, and administration in cost efficient but still detailed manner.

Microplastic analysis-are we measuring the same? Results on the first global comparative study for microplastic analysis in a water sample.

This paper presents the results of the first international comparative study of commonly applied analytical methods for microplastic analysis. Although it was shown that the comparability between previously published studies is highly limited, there are ambitious efforts regarding the standardization of microplastic analysis. This comparative study serves as a first step to assess the suitability of frequently used methods in microplastic research. Furthermore, it highlights obstacles when conducting a comparative study for microplastics. Results from 17 laboratories from eight different countries are compared. Samples comprised of five different types of microplastic reference particles with diameters ranging from 8 µm to 140 µm suspended in ultrapure water. Microscopy, Fourier-transform infrared microspectroscopy (µ-FTIR), Raman microspectroscopy (µ-Raman), thermo-extraction-and-desorption- or pyrolysis- combined with gas chromatography coupled to mass spectrometry (Σ-GC/MS), scanning electron microscopy and particle counter were compared regarding results on total particle number, polymer type, number of particles and/or particle mass for each polymer type. In the scope of this comparative study, for the identification of polymer type µ-Raman and Σ-GC/MS performed best. The quantification of polymer mass for identified polymer types was questionable for Σ-GC/MS, whereas other methods failed to determine the correct polymer mass. Quantification of particle number per identified polymer type was evaluated successful for µ-FTIR and the quantification of total particle numbers was best for microscopy and to a lesser extent for µ-FTIR. Remarkable was the large variance of results between the methods but also within the methods. The latter is likely due to individual interpretations of methods and preparation protocols, in particular in regard to the handling of blank values. Results strongly emphasize the need for standardization and validation of analytical methods in microplastic research both on a global scale as well as in the context of individual laboratories.

Repeated detection of polystyrene microbeads in the Lower Rhine River.

Microplastics are emerging pollutants in water bodies worldwide. The environmental entry areas must be studied to localise their sources and develop preventative and remedial solutions. Rivers are major contributors to the marine microplastics load. Here, we focus on a specific type of plastic microbead (diameter 286-954 µm, predominantly opaque, white-beige) that was repeatedly identified in substantial numbers between kilometres 677 and 944 of the Rhine River, one of Europe's main waterways. Specifically, we aimed (i) to confirm the reported abrupt increase in microbead concentrations between the cities of Leverkusen and Duisburg and (ii) to assess the concentration gradient of these particles along this stretch at higher resolution. Furthermore, we set out (iii) to narrow down the putative entry stretch from 81.3 km, as reported in an earlier study, to less than 20 km according to our research design, and (iv) to identify the chemical composition of the particles and possibly reveal their original purpose. Surface water filtration (mesh: 300 µm, n = 9) at regular intervals along the focal river stretch indicated the concentration of these spherules increased from 0.05 to 8.3 particles m-3 over 20 km. This spot sampling approach was supported by nine suspended solid samples taken between 2014 and 2017, encompassing the river stretch between Leverkusen and Duisburg. Ninety-five percent of microbeads analysed (202/212) were chemically identified as crosslinked polystyrene-divinylbenzene (PS-DVB, 146/212) or polystyrene (PS, 56/212) via Raman or Fourier-transform infrared spectroscopy. Based on interpretation of polymer composition, surface structure, shape, size and colour, the PS(-DVB) microbeads are likely to be used ion-exchange resins, which are commonly applied in water softening and various industrial purification processes. The reported beads contribute considerably to the surface microplastic load of the Rhine River and their potential riverine entry area was geographically narrowed down.