Preparation of Block Copolymer-Stabilized Microspheres from Commercial Plastics and Their Use as Microplastic Proxies in Degradation Studies.

This study presents a novel one-pot procedure for preparing sub-10 µm poly(ethylene glycol) (MPEG)-stabilized glycol-modified poly(ethylene terephthalate), poly(ethylene terephthalate) (PET), poly(lactic acid) (PLA), polycarbonate, and polycaprolactone (PCL) particles from commercial plastics. The prepared particles can be dried and directly resuspended in water, making them easy to handle and relevant mimics of microplastics. In addition, the method was extended to the preparation of unstabilized PET particles and somewhat larger polyethylene (PE)-based particles. Selected stabilized microparticles were subjected to aerobic biodegradation studies and compared with nonstabilized PET particles. All of the particles exhibited some degradation. For PLA and PET particles, the degradation corresponded well to the amount of surface-stabilizing MPEG groups or known impurities, confirming that these polymers do not degrade under the applied conditions but that the stabilizing groups do. PCL particles degraded relatively rapidly, which is consistent with the literature data and their relatively small size. PE-based particles degraded more than expected if only degradation of the stabilizing groups was taken into account, indicating that the surface chemistry of these particles plays a role in bulk degradation.

Finding the tiny plastic needle in the haystack: how field flow fractionation can help to analyze nanoplastics in food.

While the exact health risks associated with nanoplastics are currently the focus of intense research, there is no doubt that humans are exposed to nanoplastics and that food could be a major source of exposure. Nanoplastics are released from plastic materials and articles used during food production, processing, storage, preparation, and serving. They are also likely to enter the food chain via contaminated water, air, and soil. However, very limited exposure data for risk assessment exists so far due to the lack of suitable analytical methods. Nanoplastic detection in food poses a great analytical challenge due to the complexity of plastics and food matrices as well as the small size and expectedly low concentration of the plastic particles. Multidetector field flow fractionation has emerged as a valuable analytical technique for nanoparticle separation over the last decades, and the first studies using the technique for analyzing nanoplastics in complex matrices are emerging. In combination with online detectors and offline analysis, multidetector field flow fractionation is a powerful platform for advanced characterization of nanoplastics in food by reducing sample complexity, which otherwise hampers the full potential of most analytical techniques. The focus of this article is to present the current state of the art of multidetector field flow fractionation for nanoplastic analysis and to discuss future trends and needs aiming at the analysis of nanoplastics in food.

Are We Speaking the Same Language? Recommendations for a Definition and Categorization Framework for Plastic Debris.

The accumulation of plastic litter in natural environments is a global issue. Concerns over potential negative impacts on the economy, wildlife, and human health provide strong incentives for improving the sustainable use of plastics. Despite the many voices raised on the issue, we lack a consensus on how to define and categorize plastic debris. This is evident for microplastics, where inconsistent size classes are used and where the materials to be included are under debate. While this is inherent in an emerging research field, an ambiguous terminology results in confusion and miscommunication that may compromise progress in research and mitigation measures. Therefore, we need to be explicit on what exactly we consider plastic debris. Thus, we critically discuss the advantages and disadvantages of a unified terminology, propose a definition and categorization framework, and highlight areas of uncertainty. Going beyond size classes, our framework includes physicochemical properties (polymer composition, solid state, solubility) as defining criteria and size, shape, color, and origin as classifiers for categorization. Acknowledging the rapid evolution of our knowledge on plastic pollution, our framework will promote consensus building within the scientific and regulatory community based on a solid scientific foundation.

A call for action: Improve reporting of research studies to increase the scientific basis for regulatory decision-making.

This is a call for action to scientific journals to introduce reporting requirements for toxicity and ecotoxicity studies. Such reporting requirements will support the use of peer-reviewed research studies in regulatory decision-making. Moreover, this could improve the reliability and reproducibility of published studies in general and make better use of the resources spent in research.

Influence of pH and media composition on suspension stability of silver, zinc oxide, and titanium dioxide nanoparticles and immobilization of Daphnia magna under guideline testing conditions.

In aquatic toxicity testing of engineered nanoparticles (ENPs) the process of agglomeration is very important as it may alter bioavailability and toxicity. In the present study, we aimed to identify test conditions that are favorable for maintaining stable ENP suspensions. We evaluated the influence of key environmental parameters: pH (2-12) and ionic strength using M7, Soft EPA (S EPA) medium, and Very Soft EPA (VS EPA) medium; and observed the influence of these parameters on zeta potential, zeta average, and acute immobilization of Daphnia magna for three different ENPs. Despite being sterically stabilized, test suspensions of silver (Ag) ENPs formed large agglomerates in both VS EPA and M7 media; and toxicity was found to be higher in VS EPA medium due to increased dissolution. Low-agglomerate suspensions for zinc oxide (ZnO) could be obtained at pH 7 in VS EPA medium, but the increase in dissolution caused higher toxicity than in M7 medium. Titanium dioxide (TiO2) ENPs had a point of zero charge in the range of pH 7-8. At pH 7 in VS EPA, agglomerates with smaller hydrodynamic diameters (~200nm) were present compared to the high ionic strength M7 medium where hydrodynamic diameters reached micrometer range. The stable suspensions of TiO2 ENPs caused immobilization of D. magna, 48-h EC50 value of 13.7mgL(-1) (95% CI, 2.4mg-79.1mgL(-1)); whereas no toxicity was seen in the unstable, highly agglomerated M7 medium suspensions, 48-h EC50 >100mgL(-1). The current study provides a preliminary approach for methodology in testing and assessing stability and toxicity of ENPs in aquatic toxicity tests of regulatory relevance.

Techniques and Protocols for Dispersing Nanoparticle Powders in Aqueous Media-Is there a Rationale for Harmonization?

Selecting appropriate ways of bringing engineered nanoparticles (ENP) into aqueous dispersion is a main obstacle for testing, and thus for understanding and evaluating, their potential adverse effects to the environment and human health. Using different methods to prepare (stock) dispersions of the same ENP may be a source of variation in the toxicity measured. Harmonization and standardization of dispersion methods applied in mammalian and ecotoxicity testing are needed to ensure a comparable data quality and to minimize test artifacts produced by modifications of ENP during the dispersion preparation process. Such harmonization and standardization will also enhance comparability among tests, labs, and studies on different types of ENP. The scope of this review was to critically discuss the essential parameters in dispersion protocols for ENP. The parameters are identified from individual scientific studies and from consensus reached in larger scale research projects and international organizations. A step-wise approach is proposed to develop tailored dispersion protocols for ecotoxicological and mammalian toxicological testing of ENP. The recommendations of this analysis may serve as a guide to researchers, companies, and regulators when selecting, developing, and evaluating the appropriateness of dispersion methods applied in mammalian and ecotoxicity testing. However, additional experimentation is needed to further document the protocol parameters and investigate to what extent different stock dispersion methods affect ecotoxicological and mammalian toxicological responses of ENP.

Adapting OECD Aquatic Toxicity Tests for Use with Manufactured Nanomaterials: Key Issues and Consensus Recommendations.

The unique or enhanced properties of manufactured nanomaterials (MNs) suggest that their use in nanoenabled products will continue to increase. This will result in increased potential for human and environmental exposure to MNs during manufacturing, use, and disposal of nanoenabled products. Scientifically based risk assessment for MNs necessitates the development of reproducible, standardized hazard testing methods such as those provided by the Organisation of Economic Cooperation and Development (OECD). Currently, there is no comprehensive guidance on how best to address testing issues specific to MN particulate, fibrous, or colloidal properties. This paper summarizes the findings from an expert workshop convened to develop a guidance document that addresses the difficulties encountered when testing MNs using OECD aquatic and sediment test guidelines. Critical components were identified by workshop participants that require specific guidance for MN testing: preparation of dispersions, dose metrics, the importance and challenges associated with maintaining and monitoring exposure levels, and the need for reliable methods to quantify MNs in complex media. To facilitate a scientific advance in the consistency of nanoecotoxicology test results, we identify and discuss critical considerations where expert consensus recommendations were and were not achieved and provide specific research recommendations to resolve issues for which consensus was not reached. This process will enable the development of prescriptive testing guidance for MNs. Critically, we highlight the need to quantify and properly interpret and express exposure during the bioassays used to determine hazard values.

Assessing the Biodegradability of Tire Tread Particles and Influencing Factors.

Abrasion of tire tread, caused by friction between vehicle tires and road surfaces, causes release of tire wear particles (TWPs) into various environmental compartments. These TWPs contribute to chemical, microplastic, and particulate matter pollution. Their fate remains largely unknown, especially regarding the extent and form in which they persist in the environment. The present study investigated (1) the biodegradability of tread particles (TPs) in the form of ground tire tread, (2) how accelerated ultraviolet (UV) weathering affects their biodegradability, and (3) which TP constituents are likely contributors to TP biodegradability based on their individual biodegradability. A series of closed-bottle tests, with aerobic aqueous medium inoculated with activated sludge, were carried out for pristine TPs, UV-weathered TPs, and selected TP constituents; natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), and treated distillate aromatic extracts (TDAE). Biodegradation was monitored by manometric respirometry, quantifying biological oxygen consumption over 28 days. Pristine TP biodegradability was found to be 4.5%; UV-weathered TPs showed higher biodegradability of 6.7% and 8.0% with similar and increased inoculum concentrations, respectively. The observed TP biodegradation was mainly attributed to biodegradation of NR and TDAE, with individual biodegradability of 35.4% and 8.0%, respectively; IR and BR showed negligible biodegradability. These findings indicate that biodegradability of individual constituents is decreased by a factor of 2 to 5 when compounded into TPs. Through scanning electron microscopy analysis, biodegradation was found to cause surface erosion. Processes of TP biodegradation are expected to change throughout their lifetime as new constituents are incorporated from the road and others degrade and/or leach out. Tire emissions likely persist as particles with an increased fraction of synthetic rubbers and carbon black. Environ Toxicol Chem 2024;43:31-41. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

The time for ambitious action is now: Science-based recommendations for plastic chemicals to inform an effective global plastic treaty.

The ubiquitous and global ecological footprint arising from the rapidly increasing rates of plastic production, use, and release into the environment is an important modern environmental issue. Of increasing concern are the risks associated with at least 16,000 chemicals present in plastics, some of which are known to be toxic, and which may leach out both during use and once exposed to environmental conditions, leading to environmental and human exposure. In response, the United Nations member states agreed to establish an international legally binding instrument on plastic pollution, the global plastics treaty. The resolution acknowledges that the treaty should prevent plastic pollution and its related impacts, that effective prevention requires consideration of the transboundary nature of plastic production, use and pollution, and that the full life cycle of plastics must be addressed. As a group of scientific experts and members of the Scientists' Coalition for an Effective Plastics Treaty, we concur that there are six essential "pillars" necessary to truly reduce plastic pollution and allow for chemical detoxification across the full life cycle of plastics. These include a plastic chemical reduction and simplification, safe and sustainable design of plastic chemicals, incentives for change, holistic approaches for alternatives, just transition and equitable interventions, and centering human rights. There is a critical need for scientifically informed and globally harmonized information, transparency, and traceability criteria to protect the environment and public health. The right to a clean, healthy, and sustainable environment must be upheld, and thus it is crucial that scientists, industry, and policy makers work in concert to create a future free from hazardous plastic contamination.

Time to integrate "One Health Approach" into nanoplastic research.

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Exposure protocol for ecotoxicity testing of microplastics and nanoplastics.

Despite the increasing concern about the harmful effects of micro- and nanoplastics (MNPs), there are no harmonized guidelines or protocols yet available for MNP ecotoxicity testing. Current ecotoxicity studies often use commercial spherical particles as models for MNPs, but in nature, MNPs occur in variable shapes, sizes and chemical compositions. Moreover, protocols developed for chemicals that dissolve or form stable dispersions are currently used for assessing the ecotoxicity of MNPs. Plastic particles, however, do not dissolve and also show dynamic behavior in the exposure medium, depending on, for example, MNP physicochemical properties and the medium's conditions such as pH and ionic strength. Here we describe an exposure protocol that considers the particle-specific properties of MNPs and their dynamic behavior in exposure systems. Procedure 1 describes the top-down production of more realistic MNPs as representative of MNPs in nature and particle characterization (e.g., using thermal extraction desorption-gas chromatography/mass spectrometry). Then, we describe exposure system development for short- and long-term toxicity tests for soil (Procedure 2) and aquatic (Procedure 3) organisms. Procedures 2 and 3 explain how to modify existing ecotoxicity guidelines for chemicals to target testing MNPs in selected exposure systems. We show some examples that were used to develop the protocol to test, for example, MNP toxicity in marine rotifers, freshwater mussels, daphnids and earthworms. The present protocol takes between 24 h and 2 months, depending on the test of interest and can be applied by students, academics, environmental risk assessors and industries.

Reuse of Water in Laundry Applications with Micro- and Ultrafiltration Ceramic Membrane.

This study compares the performance of a microfiltration membrane, made by silicon carbide (SiC) and an ultrafiltration membrane, made by zirconia (ZrO2), in the treatment of wastewater from a washing machine designed to clean industrial tents. The filtration of deionized water, containing model microplastics (i.e., nylon fiber), was performed. This was followed by the filtration of real wastewater from a single washing cycle of industrial tents, made from polyvinyl chloride (PVC) textile. The filtration parameters of the membranes and physical-chemical parameters of the wastewater, including the concentration of microplastics in the shape of tent fibers (PVC), were calculated before and after filtration. The microfiltration membrane manifested a greater decrease in permeability (95%) compared to the ultrafiltration membrane (37%). The resulting water quality in terms of Total Solids, turbidity, and microplastics concentration was better for the ultrafiltration. This is evident from 99.2% versus 98.55% removal efficiency of microplastics from the laundering wastewater, respectively.

Separating toxicity and shading in algal growth inhibition tests of nanomaterials and colored substances.

Nanoparticles and colored substances can inhibit algal growth by light shading and chemical toxicity. This study presents two complementary approaches to account for shading in algal growth inhibition tests of engineered nanomaterials (ENMs) and colored substances. The first approach distinguishes between shading effects and toxicity by varying the light path in parallel algal growth inhibition tests. This Multiple Path-Length (MPL) test was applied to TiO2 ENMs and the colored substances sodium picramate and Rhodamine B. A left shifting of concentration-response curves, with increasing light path lengths, indicated shading for Rhodamine B, sodium picramate and TiO2 ENMs. EC50-values obtained at the shortest light path length were generally found best suited to quantify the toxicity of ENMs and colored substances. The second approach addresses shading at the cellular level, where particles can attach to the cell surface and affect photo-pigment content and composition. Pigments associated with photosystem I and II were determined at varying light intensities and concentrations of TiO2 ENMs. The photo-pigments that increased in response to physical shading, decreased after TiO2 ENMs exposure. This indicates that toxicity rather than cellular shading dominated the response of algae exposed to TiO2 ENMs. Additional tests were conducted with the nanomaterials CeO2 and goethite to evaluate the applicability of this approach to other ENMs. On this basis, we recommend MPL testing for determining EC50-values that are not confounded by shading in the test solution, and the pigment-based approach for investigating shading on the cellular level.

Accelerated Weathering Increases the Release of Toxic Leachates from Microplastic Particles as Demonstrated through Altered Toxicity to the Green Algae Raphidocelis subcapitata.

Studies that evaluate the impact of microplastic particles (MPs) often apply particles of pristine material. However, MPs are affected by various abiotic and biotic processes in the environment that possibly modify their physical and chemical characteristics, which might then result in their altered toxic effect. This study evaluated the consequence of weathering on the release of toxic leachates from microplastics. MPs derived from six marine antifouling paints, end-of-life tires, and unplasticised PVC were exposed to UV-C radiation to simulate weathering. Non-weathered and weathered MPs were leached in algae growth medium for 72 h to demonstrate additive release under freshwater conditions. The model organism, green algae Raphidocelis subcapitata, was exposed to the resulting leachates of both non-weathered and weathered MPs. The results of the growth inhibition tests showed that the leachates of weathered microparticles were more toxic than of the non-weathered material, which was reflected in their lower median effect concentration (EC50) values. Chemical analysis of the leachates revealed that the concentration of heavy metals was several times higher in the leachates of the weathered MPs compared to the non-weathered ones, which likely contributed to the increased toxicity. Our findings suggest including weathered microplastic particles in exposure studies due to their probably differing impact on biota from MPs of pristine materials.

How fast, how far: Diversification and adoption of novel methods in aquatic microplastic monitoring.

Since 2004, there has been a marked diversification in the methods used to determine aquatic microplastic (MP) concentrations. Despite calls for a unified approach to MP sampling, the proliferation of new methods has accelerated in recent years. Both minor method adaptations and entirely novel approaches have been introduced to overcome barriers to reliable MP sampling, extraction and quantification, resulting in a variety of complimentary but also competing approaches. However, there is little clarity regarding the extent to which new methods are acknowledged and adopted, or of the apparent drivers of, as well as barriers to, said adoption. To explore these issues, the rate of method diversification was examined in a systematic review. The rate and degree of diversification were determined by scoring each method by its "degree of novelty": highly novel methods, secondary adaptations of existing methods and smaller, tertiary adaptations of existing methods. This analysis revealed that the rate of method diversification has been greatest since 2011. Our results indicate limited use of these novel methods and adaptations in the subsequent literature, with many researchers falling back on methods that are well established in the existing literature. Importantly, there is little consistency in the units used when reporting MP concentrations. However, these differences are seldom driven by method selection and are rather the result of discrepancies between researchers. Thus, in understanding the requirements of comparability and consistent reporting for monitoring purposes, we can apply a diverse approach to sampling whilst maintaining the applicability and usefulness of the resulting data.

Quality of nanoplastics and microplastics ecotoxicity studies: Refining quality criteria for nanomaterial studies.

It is becoming increasingly important to develop assessment criteria for the quality of nanoplastics studies. This study is an attempt to establish such criteria based on those developed for engineered nanomaterials, the GUIDEnano and DaNa criteria being two representatives. These criteria were applied to studies on polystyrene nanoparticles (PS NPs), which currently represent the majority of studies on nanoplastics. We compiled a list of existing nanomaterial-related criteria that are not fully relevant to PS NPs and propose additional nanoplastic-specific criteria targeting polymer chemical composition, source, production and field collection, impurities/chemical additives, density, hydrophobicity, colour, and chemical leaching. For each criterion, scientific justification is provided. We conclude that the existing study quality assessments originally developed for nano(eco)toxicity studies can, through refinements, be applied to those dealing with nanoplastics studies, with a further outlook on microplastics. The final quality criteria catalogue presented here is intended as a starting point for further elaborations considering different purposes of an assessment.

A nationwide assessment of plastic pollution in the Danish realm using citizen science.

Plastic pollution is considered one of today's major environmental problems. Current land-based monitoring programs typically rely on beach litter data and seldom include plastic pollution further inland. We initiated a citizen science project known as the Mass Experiment inviting schools throughout The Danish Realm (Denmark, Greenland and the Faeroe Islands) to collect litter samples of and document plastic pollution in 8 different nature types. In total approximately 57,000 students (6-19 years) collected 374,082 plastic items in 94 out of 98 Danish municipalities over three weeks during fall 2019. The Mass Experiment was the first scientific survey of plastic litter to cover an entire country. Here we show how citizen science, conducted by students, can be used to fill important knowledge gaps in plastic pollution research, increase public awareness, establish large scale clean-up activities and subsequently provide information to political decision-makers aiming for a more sustainable future.

Setting the limits for engineered nanoparticles in European surface waters - are current approaches appropriate?

The current widespread and diverse use of engineered nanoparticles (ENPs) in consumer products is expected to result in direct and indirect emissions to the aquatic environment. In Europe, the Water Framework Directive (WFD) is responsible for maintaining a good chemical and ecological status of surface waters. This review provides an insight to the likely scenarios if an engineered nanoparticle should be considered a "priority substance" in the WFD. Through a brief literature review of the aquatic toxicity of carbon- and metal-containing ENPs and in light of principles to establish environmental quality standards, we conclude that it is impossible to set limit values for ENPs in surface waters now and in the foreseeable future. This is due to the extensive lack of knowledge not only in relation to unknown toxic effects, degradability, and bioaccumulation of ENPs in the aquatic environment, but also due to the questionable validity of test systems and methods to establish environmental quality standards (EQS). From this, we also suggest some paths to follow to compensate for these knowledge gaps which include environmental monitoring and a closer look at the use of ENPs in consumer products.

Ingestion and effects of micro- and nanoplastics in blue mussel (Mytilus edulis) larvae.

It is well known that mussels are exposed to microplastics but ingestion and potential effects on mussel larvae are not well understood. We quantified ingestion and egestion of 100 nm and 2 µm polystyrene beads in blue mussel larvae after 4 h exposure and 16 h depuration using different plastic-to-microalgae ratios. Effects on growth and development of mussel larvae were investigated at 0.42, 28.2 and 282 µgL-1 within 15 days of exposure. We found that, on a mass basis, larvae ingested a higher amount of 2 µm than 100 nm beads, while egestion was independent of particle size and the plastics-to-algae ratio. Although particle egestion occurred readily, microplastics remained inside the larvae. Larval growth was not affected but abnormally developed larvae increased after exposure to polystyrene beads. Malformations were more pronounced for 100 nm beads, at higher concentration and after longer exposure time.