Quantification and Characterization of Ti-, Ce-, and Ag-Nanoparticles in Global Surface Waters and Precipitation.

Nanoparticle (NP) emissions to the environment are increasing as a result of anthropogenic activities, prompting concerns for ecosystems and human health. In order to evaluate the risk of NPs, it is necessary to know their concentrations in various environmental compartments on regional and global scales; however, these data have remained largely elusive due to the analytical difficulties of measuring NPs in complex natural matrices. Here, we measure NP concentrations and sizes for Ti-, Ce-, and Ag-containing NPs in numerous global surface waters and precipitation samples, and we provide insights into their compositions and origins (natural or anthropogenic). The results link NP occurrences and distributions to particle type, origin, and sampling location. Based on measurements from 46 sites across 13 countries, total Ti- and Ce-NP concentrations (regardless of origin) were often found to be within 104 to 107 NP mL-1, whereas Ag NPs exhibited sporadic occurrences with low concentrations generally up to 105 NP mL-1. This generally corresponded to mass concentrations of <1 ng L-1 for Ag-NPs, <100 ng L-1 for Ce-NPs, and <10 µg L-1 for Ti-NPs, given that measured sizes were often below 15 nm for Ce- and Ag-NPs and above 30 nm for Ti-NPs. In view of current toxicological data, the observed NP levels do not yet appear to exceed toxicity thresholds for the environment or human health; however, NPs of likely anthropogenic origins appear to be already substantial in certain areas, such as urban centers. This work lays the foundation for broader experimental NP surveys, which will be critical for reliable NP risk assessments and the regulation of nano-enabled products.

Exposure of nanoplastics to freeze-thaw leads to aggregation and reduced transport in model groundwater environments.

Despite plastic pollution being a significant environmental concern, the impact of environmental conditions such as temperature cycling on the fate of nanoplastics in cold climates remains unknown. To better understand nanoplastic mobility in subsurface environments following freezing and thawing cycles, the transport of 28 nm polystyrene nanoplastics exposed to either constant (10°C) temperature or freeze-thaw (FT) cycles (-10°C to 10°C) was investigated in saturated quartz sand. The stability and transport of nanoplastic suspensions were examined both in the presence and absence of natural organic matter (NOM) over a range of ionic strengths (3-100 mM NaCl). Exposure to 10 FT cycles consistently led to significant aggregation and reduced mobility compared to nanoplastics held at 10°C, especially at low ionic strengths in the absence of NOM. While NOM increased nanoplastic mobility, it did not prevent the aggregation of nanoplastics exposed to FT. We compare our findings with existing literature and show that nanoplastics will largely aggregate and associate with soils rather than undergo long range transport in groundwater in colder climates following freezing temperatures. In fact, FT exposure leads to the formation of stable aggregates that are not prone to disaggregation. As one of the first studies to examine the coupled effect of cold temperature and NOM, this work highlights the need to account for climate and temperature changes when assessing the risks associated with nanoplastic release in aquatic systems.

Understanding and Improving Microplastic Removal during Water Treatment: Impact of Coagulation and Flocculation.

The efficacy of plastic particle removal by municipal water treatment plants is currently uncertain, and the mechanisms involved in microplastic (MP) coagulation and flocculation have only been superficially investigated. The removal of pristine versus weathered plastic debris and the impact of plastic particle size on removal remain largely unexplored. In this study, coagulation, flocculation, and settling performances were investigated using pristine and weathered MPs (polyethylene (PE) and polystyrene (PS) microspheres, and polyester (PEST) fibers). Weathering processes that changed the surface chemistry and roughness of MPs impacted MP affinity for coagulants and flocculants. A quartz crystal microbalance with dissipation monitoring was used to identify the mechanisms involved during MP coagulation and flocculation. Measured deposition rates confirmed the relatively low affinity between plastic surfaces and aluminum-based coagulants compared to cationic polyacrylamide (PAM). In every case examined, coagulant efficiency increased when the plastic surface was weathered. Removals of 97 and 99% were measured for PEST and weathered PE, respectively. Larger pristine PE MPs were the most resistant to coagulation and flocculation, with 82% removal observed even under enhanced coagulation conditions. By understanding the interaction mechanisms, the removal of weathered MPs was optimized. Finally, this study explored the use of settled water turbidity as a possible indicator of MP removal.

Biofilm formation by marine bacteria is impacted by concentration and surface functionalization of polystyrene nanoparticles in a species-specific manner.

The world's oceans are becoming increasingly polluted by plastic waste. In the marine environment, larger plastic pieces may degrade into nanoscale (<100 nm in at least one dimension) plastic particles due to natural weathering effects. We observe that the presence of 20 nm plastic nanoparticles at concentrations below 200 ppm had no impact on planktonic growth of a panel of heterotrophic marine bacteria. However, the presence of plastic nanoparticles significantly impacted the formation of biofilms in a species-specific manner. While carboxylated nanoparticles increased the amount of biofilm formed by several species, amidine-functionalized nanoparticles decreased the amount of biofilm of many but not all bacteria. Further experiments suggested that the aggregation dynamics of bacteria and nanoparticles were strongly impacted by the surface properties of the nanoparticles. The community structure of an artificially constructed community of marine bacteria was significantly altered by exposure to plastic nanoparticles, with differently functionalized nanoparticles selecting for unique and reproducible community abundance patterns. These results suggest that surface properties and concentration of plastic nanoparticles, as well as species interactions, are important factors determining how plastic nanoparticles impact biofilm formation by marine bacteria.

Separation and Analysis of Microplastics and Nanoplastics in Complex Environmental Samples.

The vast amount of plastic waste emitted into the environment and the increasing concern of potential harm to wildlife has made microplastic and nanoplastic pollution a growing environmental concern. Plastic pollution has the potential to cause both physical and chemical harm to wildlife directly or via sorption, concentration, and transfer of other environmental contaminants to the wildlife that ingest plastic. Small particles of plastic pollution, termed microplastics (>100 nm and <5 mm) or nanoplastics (<100 nm), can form through fragmentation of larger pieces of plastic. These small particles are especially concerning because of their high specific surface area for sorption of contaminants as well as their potential to translocate in the bodies of organisms. These same small particles are challenging to separate and identify in environmental samples because their size makes handling and observation difficult. As a result, our understanding of the environmental prevalence of nanoplastics and microplastics is limited. Generally, the smaller the size of the plastic particle, the more difficult it is to separate from environmental samples. Currently employed passive density and size separation techniques to isolate plastics from environmental samples are not well suited to separate microplastics and nanoplastics. Passive flotation is hindered by the low buoyancy of small particles as well as the difficulty of handling small particles on the surface of flotation media. Here we suggest exploring alternative techniques borrowed from other fields of research to improve separation of the smallest plastic particles. These techniques include adapting active density separation (centrifugation) from cell biology and taking advantage of surface-interaction-based separations from analytical chemistry. Furthermore, plastic pollution is often challenging to quantify in complex matrices such as biological tissues and wastewater. Biological and wastewater samples are important matrices that represent key points in the fate and sources of plastic pollution, respectively. In both kinds of samples, protocols need to be optimized to increase throughput, reduce contamination potential, and avoid destruction of plastics during sample processing. To this end, we recommend adapting digestion protocols to match the expected composition of the nonplastic material as well as taking measures to reduce and account for contamination. Once separated, plastics in an environmental sample should ideally be characterized both visually and chemically. With existing techniques, microplastics and nanoplastics are difficult to characterize or even detect. Their low mass and small size provide limited signal for visual, vibrational spectroscopic, and mass spectrometric analyses. Each of these techniques involves trade-offs in throughput, spatial resolution, and sensitivity. To accurately identify and completely quantify microplastics and nanoplastics in environmental samples, multiple analytical techniques applied in tandem are likely to be required.