Preparation of synthetic micro- and nano plastics for method validation studies.

Microplastic (MP) pollution is a persisting global problem. Accurate analysis is essential in quantifying the effects of microplastic pollution and develop novel technologies that reliably and reproducibly measure microplastic content in various samples. The most common methods for this are FTIR and Raman spectroscopy. Coloured, standardized beads are often used for method validation tests, which limits the conclusions to a very specific case rarely observed in the natural environment. This study focuses on the preparation of reference micro- and nanoplastics via cryogenic milling and shows their use for FTIR and Raman method validation studies. MPs can now be reproducibly milled from various plastics, offering the advantages of a better representation of MPs in real environment. Moreover, this study highlights issues with the current detection methods, up to now considered as the most reliable ones for MP detection and identification. Such issues, e.g. misidentification, will need to be addressed in the future. Additionally, milled MPs were used in experiments with commercial high-resolution imaging device, enabling a possible in-situ optical detection of microplastics. These experiments represent a step forward in understanding MPs in a water sample and provide a basis for a more accurate detection and identification directly from water, which would considerably reduce the time of analysis.

Historical and current occurrence of microplastics in water and sediment of a Finnish lake affected by WWTP effluents.

Only scarce information is available about the abundance of microplastics (MPs) in Nordic lakes. In this study, the occurrence, types, and distribution of MPs were assessed based on the lake water and sediment samples collected from a sub-basin of Lake Saimaa, Finland. The main goal was to estimate the possible effect of the local wastewater treatment plant (WWTP) on the abundance of MPs in different compartments of the recipient lake area. Collected bottom sediment samples were Cs-137 dated and the chronological structure was utilized to relate the concentrations of MPs to their sedimentation years. Raman microspectroscopy was used for the MPs' identification from both sample matrices. In addition, MPs consisting of polyethylene (PE), polypropylene (PP) and polystyrene (PS) were quantified from lake water samples by pyrolysis-gas chromatography-mass spectrometry to provide a complementary assessment of MPs based on two different analysis methods, which provide different metrics of the abundance of microplastics. MPs concentrations were highest in sediment samples closest to the discharge site of WWTP effluents (4400 ± 620 n/kg dw) compared to other sites. However, such a trend was not found in lake water samples (0.7 ± 0.1 n/L). Overall, microplastic fibers were relatively more abundant in sediment (70%) than in water (40%), and the majority of detected microplastic fibers were identified as polyester. This indicates that a part of textile fibers passing the WWTP processes accumulate in the sediment close to the discharge site. In addition, the abundance of MPs was revealed to have increased slightly during the last 30 years.

Variation of microplastics in the shore sediment of high-altitude lakes of the Indian Himalaya using different pretreatment methods.

Microplastics pollution is a growing environmental concern. However, microplastics studies in high altitude remote lakes are scarce. In this study, microplastics pollution was assessed in the shore sediment of three high altitude lakes in Ladakh of the Indian Himalaya, namely Pangong Lake, Tsomoriri Lake and Tsokar Lake. Sampling of lakes shore sediment was performed in August 2019. Two different pretreatment methods were implemented with sediment samples from same sites, resulting two sets of samples. One set of samples was pretreated utilizing enzymatic degradation together with Fenton reactions. Another set of samples from the same sites were pretreated with 30 % hydrogen peroxide (H2O2) and Fenton reaction. Enzymatically pretreated samples resulted in higher microplastics concentrations than the set of H2O2 pretreated samples, which indicated that microplastics concentrations in sediment samples varies even among samples from the same site and that the pretreatment procedure may impact on the reported microplastics concentrations. Considering both sets of samples, microplastic concentration was 160-1000 MP/kg dw in Pangong Lake, 960-3800 MP/kg dw in Tsomoriri Lake, and 160-1000 MP/kg dw in Tsokar Lake. Blank correction based on the limit of detection and the limit of quantification indicated that microplastics concentrations at some sites of the studied lakes are higher than the limit of detection and the limit of quantification. The findings of this study indicated that the studied lakes in the Indian Himalaya are contaminated with microplastics. In addition, the comparison of microplastics using different pretreatment methods illustrated the importance of harmonization of microplastics studies to enable a reliable comparison among microplastics data. Therefore, this study contributes towards an assessment of microplastics in the high-altitude lakes in Indian Himalaya. The findings attributed towards clearer understanding regarding the need of harmonization of pretreatment methods and demonstrated the importance of reporting complete information in microplastics research.

The assessment of particle selection and blank correction to enhance the analysis of microplastics with Raman microspectroscopy.

Although microplastics research has received enormous attention in the last decade, both the research practices and the quality of produced data should still be improved. In this study, the identification process of microplastics with Raman imaging microscope was improved by decreasing the time needed for the analysis. To do that, new features, including terrain mosaic and automatic particle selection, were utilized and various ways of handling the produced microplastics data were implemented and discussed. Furthermore, blank correction of microplastic concentrations was demonstrated and its effects on the recovery of spiked microplastics was assessed with aqueous and solid samples. Six types of microplastics, including fragments and fibers, were spiked in triplicates of ultra-pure water and reference sediment samples. The spiked samples were pretreated by a modified method of the universal enzymatic purification protocol. Microplastics were analyzed with Raman imaging microscope, using terrain mosaic combined with automatic particle selection. The microplastics data were subjected to different identification steps to estimate the potential overestimation and underestimation of microplastics counts. With the complete correction of Raman-based data, the average recovery rates of fragments (77-80%) were higher than fibers (20-33%). The decrease in recovery rates of spiked microplastics (49-57%) were observed when blank correction was applied (28-47%). The impact of the blank correction depended on the polymer, causing exclusion of PE, PET, and PP from sediment samples. For the completely corrected Raman-based data, the average recovery rates of microplastics were higher for water than sediment samples both with and without blank correction. The results demonstrated the impact of blank correction on the microplastics recovery rates. To our knowledge, this is the first study to explore the use of automatic particle selection of Raman imaging microscope for microplastics analysis. Hence, potential drawbacks and advantages of the new features of Raman imaging microscope were explicitly discussed.

Microplastics pollution in the Brahmaputra River and the Indus River of the Indian Himalaya.

Rivers act as temporary sinks of microplastics and a key medium allowing microplastics to enter the ocean. In this study, microplastics pollution in river shore sediment of the Indian Himalaya, including the Brahmaputra River and the Indus River was discussed. Sampling campaigns were performed in years 2018 and 2019. Sample pretreatment was performed using Na2WO4·2H2O for density separation and H2O2 for oxidation of organic material. Microplastics analysis was performed by using FTIR microscope. The smaller size of microplastics 20-150 µm were more abundant (531-3485 MP/kg in the Brahmaputra River and 525-1752 MP/kg in the Indus River) than microplastics in size range between 150 µm and 5 mm (20-240 MP/kg in the Brahmaputra River and 60-340 MP/kg in the Indus River). Microplastics were found in sediments of all sampling sites. Fragmented, secondary microplastics were dominant in the river shore sediment of the Indian Himalaya. This study contributes towards filling research gap of microplastics in India's freshwater source and highlights the importance of in-depth complete studies of microplastics in the rivers that act as pathways and sinks for microplastics.