Innovative reference materials for method validation in microplastic analysis including interlaboratory comparison exercises.

Reference materials (RMs) are vital tools in the validation of methods used to detect environmental pollutants. Microplastics, a relatively new environmental pollutant, require a variety of complex approaches to address their presence in environmental samples. Both interlaboratory comparison (ILC) studies and RMs are essential to support the validation of methods used in microplastic analysis. Presented here are results of quality assurance and quality control (QA/QC) performed on two types of candidate microplastic RMs: dissolvable gelatin capsules and soda tablets. These RMs have been used to support numerous international ILC studies in recent years (2019-2022). Dissolvable capsules containing polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), and polystyrene (PS), in different size fractions from 50 to 1000 µm, were produced for one ILC study, obtaining relative standard deviation (RSD) from 0 to 24%. The larger size fraction allowed for manual addition of particles to the capsules, yielding 0% error and 100% recovery during QA/QC. Dissolvable capsules were replaced by soda tablets in subsequent ILC studies and recovery test exercises because they were found to be a more reliable carrier for microplastic RMs. Batches of soda tablets were produced containing different single and multiple polymer mixtures, i.e., PE, PET, PS, PVC, polypropylene (PP), and polycarbonate (PC), with RSD ranging from 8 to 21%. Lastly, soda tablets consisting of a mixture of PE, PVC, and PS (125-355 µm) were produced and used for recovery testing during pretreatment of environmental samples. These had an RSD of 9%. Results showed that soda tablets and capsules containing microplastics >50 µm could be produced with sufficient precision for internal recovery tests and external ILC studies. Further work is required to optimize this method for smaller microplastics (< 50 µm) because variation was found to be too large during QA/QC. Nevertheless, this approach represents a valuable solution addressing many of the challenges associated with validating microplastic analytical methods.

Fate of microplastics in agricultural soils amended with sewage sludge: Is surface water runoff a relevant environmental pathway?

Sewage sludge used as agricultural fertilizer has been identified as an important source of microplastics (MPs) to the environment. However, the fate of MPs added to agricultural soils is largely unknown. This study investigated the fate of MPs in agricultural soils amended with sewage sludge and the role of surface water runoff as a mechanism driving their transfer to aquatic ecosystems. This was assessed using three experimental plots located in a semi-arid area of Central Spain, which were planted with barley. The experimental plots received the following treatments: (1) control or no sludge application; (2) historical sludge application, five years prior to the experiment; and (3) sludge application at the beginning of the experiment. MPs were analyzed in surface water runoff and in different soil layers to investigate transport and infiltration for one year. The sewage sludge used in our experiment contained 5972-7771 MPs/kg dw. Based on this, we estimated that about 16,000 MPs were added to the agricultural plot amended with sludge. As expected, the sludge application significantly increased the MP concentration in soils. The control plot contained low MP concentrations (31-120 MPs kg-1 dw), potentially originating from atmospheric deposition. The plot treated five years prior to the experiment contained 226-412 and 177-235 MPs kg-1 dw at the start and end of the experiment, respectively; while the recently treated plot contained 182-231 and 138-288 MPs kg-1 dw. Our study shows that MP concentrations remain relatively constant in agricultural soils and that the MP infiltration capacity is very low. Surface water runoff had a negligible influence on the export of MPs from agricultural soils, mobilizing only 0.2-0.4% of the MPs added with sludge. We conclude that, in semi-arid regions, agricultural soils can be considered as long-term accumulators of MPs.

Bypass of Booming Inputs of Urban and Sludge-Derived Microplastics in a Large Nordic Lake.

Microplastic research, initially focusing on marine environments, left freshwater ecosystems largely unexplored. Freshwaters are also vulnerable to microplastics and are likely the largest microplastic supplier to the ocean. However, microplastic sources, transport pathways, and fluxes at the catchment level remain to be quantified, compromising efficient actions toward mitigation and remediation. Here we show that 70-90% of microplastics reaching Norway's largest lake, originating primarily from urban waste mismanagement and sludge application on crops, continue their journey toward the ocean without being buried. Indeed, our microplastic budget for the catchment shows that out of the 35.9 tons (7.4-119.4 t) of microplastics annually released into the lake, only 3.5 tons (1.3-8.8 t) are settling to the lake bottom. The spatial and vertical microplastic distribution and diversity in lake sediments, the socio-economic modeling of plastic fluxes and spatial information on land use and potential plastic sources all point toward urban and agricultural areas as emission hotspots of increasing importance. We conclude that the degree to which lake sediments represent a net microplastic sink is likely influenced by the nature of microplastics the lake receives, and ultimately on their origin.

An interlaboratory comparison exercise for the determination of microplastics in standard sample bottles.

An interlaboratory comparison exercise was conducted to assess the consistency of microplastic quantification across several laboratories. The test samples were prepared by mixing one liter seawater free of plastics, microplastics made from polypropylene, high- and low-density polyethylene, and artificial particles in two plastic bottles, and analyzed concurrently in 12 experienced laboratories around the world. The minimum requirements to quantify microplastics were examined by comparing actual numbers of microplastics in these sample bottles with numbers measured in each laboratory. The uncertainty was due to pervasive errors derived from inaccuracies in measuring sizes and/or misidentification of microplastics, including both false recognition and overlooking. The size distribution of microplastics should be smoothed using a running mean with a length of >0.5 mm to reduce uncertainty to less than ±20%. The number of microplastics <1 mm was underestimated by 20% even when using the best practice for measuring microplastics in laboratories.