Impacts of polystyrene nanoplastics on microgel formation from effluent organic matter.

Municipal effluents discharged from wastewater treatment plants (WWTPs) are considered major contributors of nanoplastics (NPs) and dissolved effluent organic matter (dEfOM) to environments. Due to their small sizes, NPs can travel easily in waterways and evade wastewater treatment processes, and may directly interact with dEfOM, altering their environmental fates. However, although much research has examined the impact of natural organic matter on NPs, the interactions between NPs and dEfOM remain unexplored. This study investigated the influences of NPs on the behavior and capacity of dEfOM aggregation and surface granularity, and identified the possible aggregation mechanism. We also adjusted the salinity of water samples to simulate scenarios based on WWTP-sea continuums. Our data suggest that dEfOM can self-assemble with 55 nm polystyrene NPs to form microgels, particularly under high salinity conditions. NPs accelerates the formation speed and number of dEfOM aggregates, but the sizes of the aggregates remain largely unchanged. The relative particle counts at a salinity of 34 psu increased by 300 % compared to the control group. The potential mechanism behind NPs-microgels aggregation is likely driven by the synergistic effect of the divalent ion crosslinking and hydrophobic interactions between EfOM and NPs. Notably, NPs incorporation into microgels decreases the surface granularity, thereby possibly affecting settling velocity and colonization of aggregates, as well as microbial attachment and community diversity. Overall, our findings demonstrate the potential influence of NPs on dEfOM assembly and surface properties following effluent discharge, and can inspire further relevant studies on microorganism interactions, removal technologies, and the environmental transport of NPs.

Temperature Effects on Effluent Microgel Formation.

Wastewater treatment plant effluent is considered an important hotspot of dissolved organic matter. The behavior and transformation of dissolved effluent organic matter (dEfOM) regulate particle sedimentation, pollutant fate, microbial attachment, and biofilm formation. However, studies have so far focused on the transformation of marine and riverine organic matter, and the current knowledge of dEfOM behavior is still limited. Fluctuations in water conditions, especially temperature, may directly alter the size, assembly speed, and structure of microgels, thereby potentially disturbing fate and the transportation of organic matter. In this study, we firstly investigated the effects of temperature on the behavior and capacity of dEfOM assembly into microgels and the possible mechanism. The microgel size and granularity of dEfOM were monitored by flow cytometry. Our results suggest that, with regard to microgels, a higher temperature leads to a higher assembly capacity but also a decrease in the size distribution. By contrast, assembly at 4 °C reduces the relative assembly capacity but increases the microgel size and granularity. The size distribution of the formed microgels at the various temperatures was ordered as follows: 4 °C > 20 °C > 35 °C. The size reduction in dEfOM assembly may be closely tied to the enhancement of hydrophobic interactions. The reduction in microgel granularity in warm conditions (35 °C) in terms of the effluent water may be caused by thermally induced condensation. Overall, the findings demonstrate the effects of temperature on dEfOM assembly and can facilitate further relevant studies on aquatic organic particle formation during current global warming scenarios.

Stickiness of extracellular polymeric substances on different surfaces via magnetic tweezers.

Organic particle dynamics in the surface ocean plays a critical part in the marine carbon cycle. Aggregation of marine organic particles drives their downward transport to support various marine organisms on their transit to the sediments. Extracellular polymeric substances (EPS) from various microbes are a major contributor to the oceanic organic particle pool. The stickiness of EPS is expected to play a determining role in the aggregation process of particles; however, stickiness parameters are usually indirectly estimated through data fitting without direct assessment. Here a magnetic tweezer method was developed to quantitatively assess the stickiness of three model EPS produced by: Amphora sp., (diatom), Emiliania huxleyi (coccolithophore), and Sagittula stellata (bacteria), under different in vitro environmental conditions (salinity or EDTA complexed cations) and surface matrices (EPS-EPS and bare glass). Our results showed the stickiness of three microbial EPS decreasing for S. stellata > E. huxleyi > Amphora sp., in line with their decreasing protein-to-carbohydrate (P/C) ratios (related to their relative hydrophobicity). The data not only emphasize the importance of hydrophobicity on EPS stickiness, but also demonstrates that salinity and the nature of the substrate surface can influence the stickiness. Furthermore, we investigated stickiness between various types of EPS, and the observed selective stickiness of EPS between species may shed light on the interactions among heterogeneous marine microorganisms. Overall, this newly developed system provides a platform to assess the EPS stickiness to advance our understanding of the aggregation and sedimentation process of organic particles that are critical for the fate of organic carbon as well as for biofilm formation and microbial colonization of surfaces in the ocean.

Nano-plastics induce aquatic particulate organic matter (microgels) formation.

The pervasive presence of plastic waste in the aquatic environment is widely viewed as one of the most serious environmental challenges for current and future generations. Microplastics ultimately degrade into nano and smaller-sizes. In turn, their biological and ecological impacts become more complicated and ambiguous. Nano-plastic particles travel from freshwater systems to estuarine and oceanic regions, during which they can interact with dissolved organic matter (DOM) to form microgels. Microgel formation is ubiquitous in aquatic systems, serving as a shunt between DOM and particulate organic matter (POM), as well as playing key roles in particle aggregation/sedimentation and pollutant transport. Currently the influences and mechanisms of the aggregation behavior and environmental fate of nano-plastics in different aquatic environments is poorly understood. Here, we report that 25 nm polystyrene nano-particles in lake and river water can promote POM (microgel) formation and accelerate the DOM-POM transition. We also adjusted various salinities of water samples to simulate scenarios based on plastic transport in waters flowing from rivers to seas. The results indicate polystyrene nanoparticles can interact with organic matter to form large organic particles, which may undergo further settling in response to specific salinity levels. Polystyrene-induced microgel formation appears to involve the hydrophobic interactions between plastics and DOM. Our data provides much needed information for modeling and understanding the retention and sedimentation of nano-plastics. We show that nano-plastics alter the DOM-POM shunt to cause unanticipated perturbations in the functionality of aquatic ecosystems.

Nano- and microplastics trigger secretion of protein-rich extracellular polymeric substances from phytoplankton.

The substantial increase in plastic pollution in marine ecosystems raises concerns about its adverse impacts on the microbial community. Microorganisms (bacteria, phytoplankton) are important producers of exopolymeric substances (EPS), which govern the processes of marine organic aggregate formation, microbial colonization, and pollutant mobility. Until now, the effects of nano- and micro-plastics on characteristics of EPS composition have received little attention. This study investigated EPS secretion by four phytoplankton species following exposure to various concentrations of polystyrene nano- and microplastics (55 nm nanoparticles; 1 and 6 µm microparticles). The 55 nm nanoparticles induced less growth/survival (determined on a DNA basis) and produced EPS with higher protein-to-carbohydrate (P/C) ratios than the exposure to microplastic particles. The amount of DNA from the four marine phytoplankton showed a higher negative linear correlation with increasing P/C ratios, especially in response to nanoplastic exposure. These results provide evidence that marine phytoplankton are quite sensitive to smaller-sized plastics and actively modify their EPS chemical composition to cope with the stress from pollution. Furthermore, the release of protein-rich EPS was found to facilitate aggregate formation and surface modification of plastic particles, thereby affecting their fate and colonization. Overall, this work offers new insights into the potential harm of different-sized plastic particles and a better understanding of the responding mechanism of marine phytoplankton for plastic pollution. The data also provide needed information about the fate of marine plastics and biogenic aggregation and scavenging processes.

Impact of exposure of crude oil and dispersant (Corexit) on aggregation of extracellular polymeric substances.

Spilled oil treated with Corexit dispersant can cause unintended impacts on marine environment systems including altering marine organic matter dynamics; however, impacts on microgels and marine oil snow (MOS) formation are still debated and remain to be fully understood. Extracellular polymeric substances (EPS) are a major source of marine organic carbon for MOS and microgel formation. EPS initial aggregation plays key roles in the oil degrading process and various biogeochemical reactions. Here we used four types of EPS with water accommodated fraction (WAF), chemically-enhanced WAF (CEWAF) and Corexit, to represent potential situations during oil spills and post-application of Corexit. We found that Corexit alone can inhibit EPS aggregation and disperse pre-existing microgels. CEWAF can enhance EPS aggregation with efficiency by up to 80%-100% and more aggregates accumulated within the air-water interface. Additionally, more hydrophobic EPS aggregates showed high resistance to Corexit dispersion while hydrophilic EPS were more sensitive. Effects of oil spills on marine gel particle formation are primarily determined by chemical characteristics (hydrophobicity and protein content) of the constituent EPS. This study offers unique insights for organic particle dynamics and identifies controlling factors for MOS or gel particles associated with oil spills and Corexit dispersant used.