Aggregation Of Nanoplastics Research Articles

Mechanisms underlying the detrimental impact of micro(nano)plastics on the stability of aerobic granular sludge: Interactions between micro(nano)plastics and extracellular polymeric substances

Microplastics (MPs) and nanoplastics (NPs) present in wastewater can pose a negative impact to aerobic granular sludge (AGS). Herein, this study found that MPs and NPs (20 mg/L) deteriorated the sludge settleability and granule integrity, resulting in a 15.7 % and 21.9 % decrease in the total nitrogen removal efficiency of the AGS system, respectively. This was possibly due to the reduction of the extracellular polymeric substances (EPS) content. The subsequent analysis revealed that tyrosine, tryptophan, and humic acid-like substances in EPS exhibited a higher propensity for chemisorption and inhomogeneous multilayer adsorption onto NPs compared to MPs. The binding of EPS onto the surface of plastic particles increased the electronegativity of the MPs, but facilitated the aggregation of NPs through reducing the electrostatic repulsion, thereby mitigating the adverse effects of MPs/NPs on the AGS stability. Additionally, comprehensive analysis of the extended Derjaguin-Landau-Verwey-Overbeek theory indicated that the suppressed aggregation of microorganisms was the internal mechanisms contributing to the inadequate stability of AGS induced by MPs/NPs. This study provides novel insights into the detrimental mechanisms of MPs/NPs on the AGS stability, highlighting the key role of EPS in maintaining the structural stability of AGS when exposed to MPs/NPs.

New Insights into the Formation of Aggregates of Bidisperse Nano- and Microplastics in Water Based on the Analysis of In Situ Microscopy and Molecular Simulation.

Microplastics (MPs) and nanoplastics (NPs) in water pose a global threat to human health and the environment. To develop efficient removal strategies, it is crucial to understand how these particles behave as they aggregate. However, our knowledge of the process of aggregate formation from primary particles of different sizes is limited. In this study, we analyzed the growth kinetics and structures of aggregates formed by polystyrene MPs in mono- and bidisperse systems using in situ microscopy and image analysis. Our findings show that the scaling behavior of aggregate growth remains unaffected by the primary particle size distribution, but it does delay the onset of rapid aggregation. We also performed a structural analysis that reveals the power law dependence of aggregate fractal dimension (df) in both mono- and bidisperse systems, with mean df consistent with diffusion-limited cluster aggregation (DLCA) aggregates. Our results also suggest that the df of aggregates is insensitive to the shape anisotropy. We simulated molecular forces driving aggregation of polystyrene NPs of different sizes under high ionic strength conditions. These conditions represent salt concentration in ocean water and wastewater, where the DLVO theory does not apply. Our simulation results show that the aggregation tendency of the NPs increases with the ionic strength. The increase in the aggregation is caused by the depletion of clusters of ions from the NPs surface.

Algae polysaccharide-induced transport transformation of nanoplastics in seawater-saturated porous media

This study examined the distinct effects of algae polysaccharides (AP), namely sodium alginate (SA), fucoidan (FU), and laminarin (LA), on the aggregation of nanoplastics (NP) in seawater, as well as their subsequent transport in seawater-saturated sea sand. The pristine 50 nm NP tended to form large aggregates, with an average size of approximately 934.5 ± 11 nm. Recovery of NP from the effluent (Meff) was low, at only 18.2 %, and a ripening effect was observed in the breakthrough curve (BTC). Upon the addition of SA, which contains carboxyl groups, the zeta (ζ)-potential of the NP increased by 2.8 mV. This modest enhancement of electrostatic interaction with NP colloids led to a reduction in the aggregation size of NP to 598.0 ± 27 nm and effectively mitigated the ripening effect observed in the BTC. Furthermore, SA's adherence to the sand surface and the resulting increase in electrostatic repulsion, caused a rise in Meff to 27.5 %. In contrast, the introduction of FU, which contains sulfate ester groups, resulted in a surge in ζ-potential of the NP to -27.7 ± 0.76 mV. The intensified electrostatic repulsion between NP and between NP and sand greatly increased Meff to 45.6 %. Unlike the effects of SA and FU, the addition of LA, a neutral compound, caused a near disappearance of ζ-potential of NP (-3.25 ± 0.68 mV). This change enhanced the steric hindrance effect, resulting in complete stabilization of particles and a blocking effect in the BTC of NP. Quantum chemical simulations supported the significant changes in the electrostatic potential of NP colloids induced by SA, FU and LA. In summary, the presence of AP can induce variability in the mobility of NP in seawater-saturated porous media, depending on the nature of the weak, strong, or non-electrostatic interactions between colloids, which are influenced by the structure and functionalization of the polysaccharides themselves. These findings provide valuable insights into the complex and variable behavior of NP transport in the marine environment.

The suspension stability of nanoplastics in aquatic environments revealed using meta-analysis and machine learning

Nanoplastics (NPs) aggregation determines their bioavailability and risks in natural aquatic environments, which is driven by multiple environmental and polymer factors. The back propagation artificial neural network (BP-ANN) model in machine learning (R2 = 0.814) can fit the complex NPs aggregation, and the feature importance was in the order of surface charge of NPs > dissolved organic matter (DOM) > functional group of NPs > ionic strength and pH > concentration of NPs. Meta-analysis results specified low surface charge (0 ≤ |ζ| < 10 mV) of NPs, low concentration (< 1 mg/L) and low molecular weight (< 10 kg/mol) of DOM, NPs with amino groups, high ionic strength (IS > 700 mM) and acidic solution, and high concentration (≥ 20 mg/L) of NPs with smaller size (< 100 nm) contribute to NPs aggregation, which is consistent with the prediction in machine learning. Feature interaction synergistically (e.g., DOM and pH) or antagonistically (e.g., DOM and cation potential) changed NPs aggregation. Therefore, NPs were predicted to aggregate in the dry period and estuary of Poyang Lake. Research on aggregation of NPs with different particle size,shapes, and functional groups, heteroaggregation of NPs with coexisting particles and aging effects should be strengthened in the future. This study supports better assessments of the NPs fate and risks in environments.

A green approach to nanoplastic detection: SERS with untreated filter paper for polystyrene nanoplastics.

Plastic pollution at the nanoscale continues to pose adverse effects on environmental sustainability and human health. However, the detection of nanoplastics (NPLs) remains challenging due to limitations in methodology and instrumentation. Herein, a "green approach" for surface-enhanced Raman spectroscopy (SERS) was exploited to detect polystyrene nanospheres (PSNSs) in water, employing untreated filter paper and a simple syringe-filtration set-up. This SERS protocol not only enabled the filtration of nano-sized PSNSs, which are smaller than the pore size of the ordinary filter paper, but also offered SERS enhancement by utilizing quasi-spherical-shaped silver nanoparticles (AgNPs) as the SERS-active substrate. The filtering of NPLs was accomplished by adding an aggregating agent to the nanoparticle mixture, which caused the aggregation of NPLs and AgNPs, resulting in a larger cluster and more hot spots for SERS detection. The optimal aggregating agent and its concentration, as well as the volume ratio between the AgNPs and NPLs, were also optimized. This SERS method successfully detected and quantified PSNSs of various sizes (i.e., 100, 300, 460, 600, and 800 nm) down to a limit of detection (LOD) of about 0.31 μg mL-1. The method was also validated against the presence of several interferents (i.e., salts, sugars, amino acids, and surfactants) and was proven practical, as evidenced by the detection of 800nm PSNSs in drinking and tap water (LODs of 1.47 and 1.55 μg mL-1, respectively).

Differential Photoaging Effects on Colored Nanoplastics in Aquatic Environments: Physicochemical Properties and Aggregation Kinetics.

Nanoplastics (NPs) have different colors, which could affect their photoaging processes in aquatic environments. This study investigated the effects of irradiation on physicochemical properties and aggregation kinetics of five colored NPs. Photodegradation rates and photooxidation degrees ranked white ≈ yellow > red > blue ≈ black NPs, indicating that NPs with longer color wavelengths photoaged faster. The discoloration process followed color fading (2-14 days, except for white NPs), yellowing (10-16 days), yellow fading (18 days), and turning transparent (20-22 days). White NPs exhibited a different photoaging sequence (C-H → C-OH → C═O → O-C═O) from others. Photodegradation was mainly controlled by singlet oxygen, producing 13 chemicals that were mostly organic acids. The overall colloidal stability of pristine NPs ranked blue > yellow > red > black > white. Irradiation for 16 days retarded aggregation of white and other NPs in NaCl solution, raising the critical coagulation concentration (CCC) by 82.14 and 0.85-7.90%, respectively. Contrarily, irradiation promoted aggregation in CaCl2 solution by reducing the CCC of white (67.37%) and other (33.33-37.58%) NPs. The findings demonstrate that colored NPs underwent photoaging processes different from white/transparent NPs, which were focused by previous work, highlighting the important role of color in their environmental fate and transport.

Molecular assembly of extracellular polymeric substances regulating aggregation of differently charged nanoplastics and subsequent interactions with bacterial membrane

Extracellular polymeric substances (EPS) represent an interface between microbial cells and aquatic environment, where nanoplastics acquire coatings to alter their fate and toxicity. However, little is known about molecular interactions governing modification of nanoplastics at biological interfaces. Molecular dynamics simulations combining experiments were conducted to investigate assembly of EPS and its regulatory roles in the aggregation of differently charged nanoplastics and interactions with bacterial membrane. Driven by hydrophobic and electrostatic interactions, EPS formed micelle-like supramolecular structures with hydrophobic core and amphiphilic exterior. Different components, depending on their hydrophobicity and charge, were found to promote or suppress EPS assembly. Neutral and hydrophobic nanoplastics showed unbiased adsorption of EPS species, while cationic and anionic nanoplastics were distinct and attracted specific molecules of opposite charges. Compared with isolated EPS, assembled EPS concealed hydrophobic groups to be less adsorbed by nanoplastics. Aggregation of nanoplastics was alleviated by EPS due to electrostatic repulsion plus steric hindrance. ESP suppressed binding of cationic nanoplastics to the bacterial membrane through reducing the surface charge. Neutral and anionic nanoplastics showed weak membrane association, but their binding interactions were promoted by EPS. The structural details revealed here provided molecular level insights into modifications of nanoplastics at the eco-environment interface.

Raman spectra characterization of size-dependent aggregation and dispersion of polystyrene particles in aquatic environments

Aqueous environments are generally thought to be a source of pooling and re-distribution for both micro-plastics (MPs) and nano-plastics (NPs); however, significantly less data on NPs than MPs have been reported. The occurrence of salts, proteins, and other organic matter may promote or inhibit the aggregation of NPs to form agglomeration particles, making their detection more difficult. In this study, 80 and 500 nm polystyrene nano-plastics (PS-NPs) modified by four different functional groups (PS-Bare, PS-COOH, PS-NH2, and PS–CHO–500 nm) were selected to mimic the flocculation and/or sedimentation of NPs in salts (NaCl, CaCl2, and Na2SO4) and protein solutions. The results showed that the 80 nm PS-NPs are only colloidal in pure water. All four strong electrolyte solutions that were tested significantly promoted the aggregation of PS-NPs, including those that were protein-coated. In addition, 500 nm PS-CHO did not flocculate but gradually settled into sedimentation. Therefore, Raman spectrometry can be used to analyze assembled PS-NPs, but is not suitable for analyzing normal PS-NPs. By combining fractal morphology, this study provides insight into the comprehensive analysis of PS-NPs in water solutions, including the digestion of biological samples.

Sediment organic carbon dominates the heteroaggregation of suspended sediment and nanoplastics in natural and surfactant-polluted aquatic environments

The aggregation of nanoplastics (NPs) and suspended sediment (SPS) is the key to the transport and environmental fate of NPs. However, the influence of SPS composition and environmental conditions on this process and its mechanisms are still unclear. In this study, the heteroaggregation of NPs and SPS of different compositions is systematically explored under natural and surfactant-polluted aquatic environments (NaCl, humic acid, cetyltrimethylammonium bromide (CTAB)). The results showed that sediment organic carbon (SOC) dominates the aggregation and that different kinds of SOC (comprised of both amorphous organic carbon (AOC) and black carbon (BC)) contribute vary under distinct conditions. In natural freshwater, AOC represents a larger contribution to aggregation because of its weaker electrostatic repulsion compared to that of BC. However, BC represents a larger contribution in natural seawater resulting from decreased electrostatic repulsion and more hydrogen bonding. Conversely, in surfactant-polluted aquatic environments, both AOC and BC have a high contribution owing to the bridge effect plus hydrogen bonding. Notably, minerals’ contribution in aggregates remains low under all conditions. Furthermore, CTAB typically inhibits aggregation except under special conditions. The findings of this study contribute notably to a better understanding of the migration of nanoplastics in complex aquatic environments.

Aqueous aggregation and deposition kinetics of fresh and carboxyl-modified nanoplastics in the presence of divalent heavy metals

The presence of heavy metals alters the colloidal stability and deposition of nanoplastics (NPs) in urban waters. Such processes are important to assess the mobility and fate of NPs and their associated heavy metals. Up to date, few studies have reported the impact of heavy metals on the colloidal behaviors of NPs and the involved mechanisms. In the study, time-resolved dynamic light scattering (DLS) and quartz crystal microbalance with dissipation (QCM-D) methods were used to assess the aggregation and deposition kinetics of polystyrene nanospheres with divalent heavy metals. For comparison, carboxyl-modified polystyrene nanospheres were used. Results reveal that heavy metals destabilized NPs more significantly than calcium ions. Spectroscopy and transmission electron microscopy analysis propose that heavy metals destabilized NPs via inner-sphere coordination with carboxyl groups and cation-π interactions, further leading to the formation of different dimensional aggregates. QCM-D results suggest that the deposition rate, irreversibility, and film compactness of NPs on silica surfaces first increased but further decreased as heavy metal concentration increased. Such deposition behaviors depended on the bridging effects between NPs and silica and aggregation-induced diffusion limitation. In that case, the destabilization and retention ability of heavy metals for NPs were related to their electronegativity and hydration shell thickness. In urban waters, the presence of natural organic matter (NOM) decreased the destabilization and retention ability of heavy metals, whereas heavy metals with environmentally relevant concentrations still enhanced the aggregation and deposition of NPs compared with other environmental cations. This study highlights the impact of heavy metal property on the colloidal behaviors of NPs, thus deepening our understanding of the mobility and fate of NPs associated with heavy metals in urban waters.

Early molecular responses of mangrove oysters to nanoplastics using a microfluidic device to mimic environmental exposure

This study assessed the effects of nanoplastics (NPs) using for the very first time microfluidic devices (chip) mimicking transition waters. Three kinds of NPs were tested: crushed NPs from polystyrene pellets (NP-PS), or from Guadeloupe beaches (NP-G); and latex PS (PSL-COOH). The eluted fractions from the microfluidic device showed a low aggregation of NPs. They remained stable over time in the exposure media, with a stabilization of NPs of small sizes (< 500 nm). These chips were thus used for the toxicological assessment of NPs on swamp oysters, Isognomon alatus. Oysters were exposed for 7 days to the chip elution fraction of either NP-G, NP-PS or PSL-COOH (0.34–333 µg.L−1). Gene transcription analyses showed that the tested NPs triggered responses on genes involved in endocytosis, mitochondrial metabolism disruption, oxidative stress, DNA repair, and detoxification. Highest responses were observed after NP-G exposure at low concentrations (1 µg.L−1), as they are originated from the natural environment and accumulated contaminants, enhancing toxicological effects. As salinity influences aggregation and then the bioavailability of NPs, our results demonstrated the importance of using microfluidic devices for ecotoxicological studies on swamp or estuarine species.

Dissolved Organic Matter Enhanced the Aggregation and Oxidation of Nanoplastics under Simulated Sunlight Irradiation in Water.

Nanoplastics (NPs) have become a new type of pollutant of high concern that is ubiquitous in aqueous environments. However, the transport and transformation of NPs in natural waters are not yet fully understood. In this study, the aggregation and photooxidation of NPs were assessed with nanosized polystyrene (PS) as an example, and the effects of dissolved organic matter (DOM) were investigated with Suwannee River fulvic acid (SRFA) as representative DOM. The results showed that simulated sunlight irradiation exhibited negligible effects on the aggregation of PS, while SRFA enhanced its heteroaggregation through hydrophobic interactions. In SRFA solutions, photooxidation of PS with a particle size of 200 nm was observed, which led to an increase in the O/C ratio on its surface at a rate of (2.20 ± 0.40) × 10-2 h-1. This indicates the promotional effect of SRFA on the oxidation of nanosized PS, which is attributed to the generation of the excited triplet state (3SRFA*), hydroxyl radicals (•OH), and singlet oxygen (1O2). Among these reactive species, 1O2 played a crucial role in the oxidation of PS. The findings in this study are helpful for an in-depth understanding of the environmental behavior of NPs in natural waters.

Effects of temperature and particle concentration on aggregation of nanoplastics in freshwater and seawater

Microplastics have become a significant environmental problem worldwide. Compared with microplastics, nanoplastics are apparently more abundant and harmful but their environmental processes are less well understood. The fate and ecological impacts of nanoplastics in aquatic environments are largely determined by their aggregation properties, which were investigated here using pure water and artificial seawater prepared in the laboratory, as well as river water and coastal seawater collected from subtropical Hong Kong. The tests were carried out at an environmentally realistic temperature range (15–35 °C) with particle concentrations over four orders of magnitude (0.1–100 mg L−1). Under these experimental conditions, parameters of dynamic light scattering were used to determine the extent of aggregation and colloidal stability of polystyrene nanospheres (nPS), a common test model of nanoplastics. Our results showed that aggregation of nPS was minimal in pure water and river water, but became strong under the ionic strength of artificial seawater and coastal seawater, in which 70 nm nPS could aggregate to > 2000 nm, and this aggregation clearly increased with increase in temperature and particle concentration. The aggregates with increasing size and decreasing colloidal stability were deposited more quickly. Findings from this study imply an increased risk of nanoplastics to marine benthic organisms through the aggregation and deposition processes, particularly in warmer waters.

Metal oxide nanoparticles and polycyclic aromatic hydrocarbons alter nanoplastic’s stability and toxicity to zebrafish

Co-occurrence of nanoplastics (NPs) with metal oxide nanoparticles (nMOx) and polycyclic aromatic hydrocarbons (PAHs) have been widely reported. However, there is a scarcity of information on their interactions and combined toxic effects. In this study, we used two different sized NPs [55 nm (NP1) and 100 nm (NP2)] to understand the effect of nMOx (nCuO and nZnO) and PAHs [chrysene (Chr) and fluoranthene (Flu)] on NPs’ stability and toxicity to zebrafish. Results revealed that increasing the concentration of nMOx, zeta-potential increased, and charge reversal was observed in NPs suspension while PAH produced no major changes. Aggregation kinetics performed with nMOx exhibited higher aggregation of NPs in presence of NaCl that alleviated critical coagulation concentration. NP1 stabilized the size of otherwise unstable nMOx suspension in the tap-water for a longer period, whereas, aggregation was observed with NP2. The in vivo comet assay results showed that NP1 was more genotoxic than NP2 owing to their lower size. Interestingly the DNA damage was highest in NPs+nMOx followed by nMOx and NPs. Unlike nMOx, Chr/Flu+NPs showed reduced DNA damage as compared to NPs or PAH alone. Alteration in catalase activity and lipid peroxidation value indicated oxidative stress in all exposure groups.

Impact of different modes of adsorption of natural organic matter on the environmental fate of nanoplastics

Recently, the exposure of nanoplastics (NPs) in the environment has received extensive attention. Research concerning their fate and transport in the aquatic environment is very important and urgent. In this study, the influence of two sources of natural organic matter (NOM) on the behaviour of NPs were investigated in view of the complexity of NOM. Humic acid (HA), Suwannee River humic acid (SRHA) and Upper Mississippi River NOM (MRNOM) were chosen to represent pedogenic NOM, while bovine serum albumin (BSA) was on behalf of aquagenic NOM. The results showed that NOM could reduce the aggregation and sedimentation of NPs, exhibiting excellent stabilization effect. The stability effect was affected by the concentrations and the sources of NOMs. For pedogenic NOMs, the stabilization effect was caused by adsorption modes with different microscopic morphologies through specific functional groups, while it was induced by the mode of steric stabilization in the presence of BSA. Spectroscopic method and micromorphology study further provided a new insight into exploring the possible mechanism of the interaction between NPs and NOMs.

Effects of soil particles and convective transport on dispersion and aggregation of nanoplastics via small-angle neutron scattering (SANS) and ultra SANS (USANS).

Terrestrial nanoplastics (NPs) pose a serious threat to agricultural food production systems due to the potential harm of soil-born micro- and macroorganisms that promote soil fertility and ability of NPs to adsorb onto and penetrate into vegetables and other crops. Very little is known about the dispersion, fate and transport of NPs in soils. This is because of the challenges of analyzing terrestrial NPs by conventional microscopic techniques due to the low concentrations of NPs and absence of optical transparency in these systems. Herein, we investigate the potential utility of small-angle neutron scattering (SANS) and Ultra SANS (USANS) to probe the agglomeration behavior of NPs prepared from polybutyrate adipate terephthalate, a prominent biodegradable plastic used in agricultural mulching, in the presence of vermiculite, an artificial soil. SANS with the contrast matching technique was used to study the aggregation of NPs co-dispersed with vermiculite in aqueous media. We determined the contrast match point for vermiculite was 66% D2O / 33% H2O. At this condition, the signal for vermiculite was ~50-100%-fold lower that obtained using neat H2O or D2O as solvent. According to SANS and USANS, smaller-sized NPs (50 nm) remained dispersed in water and did not undergo size reduction or self-agglomeration, nor formed agglomerates with vermiculite. Larger-sized NPs (300-1000 nm) formed self-agglomerates and agglomerates with vermiculite, demonstrating their significant adhesion with soil. However, employment of convective transport (simulated by ex situ stirring of the slurries prior to SANS and USANS analyses) reduced the self-agglomeration, demonstrating weak NP-NP interactions. Convective transport also led to size reduction of the larger-sized NPs. Therefore, this study demonstrates the potential utility of SANS and USANS with contrast matching technique for investigating behavior of terrestrial NPs in complex soil systems.

Impacts of nanoplastics on bivalve: Fluorescence tracing of organ accumulation, oxidative stress and damage

The outcomes of this research offer novel insights into the toxic effects of nanoparticles (i.e., nanoplastics or other nanomaterials) on the benthos. Herein, this study aimed to evaluate the accumulation pathway, distribution characteristics and potential biotoxicity of polystyrene nanoplastics in C. fluminea. The results revealed that nanoplastics could accumulate in the mantle through adherence, in the visceral mass through ingestion and in the gill through respiration. The gill, intestine and stomach were the main accumulation organs for nanoplastics. The aggregation of nanoplastics was observed in C. fluminea, which may exacerbate their biotoxicity. Moreover, oxidative stress was observed in the visceral mass, gill and mantle. Liver damage, neurotoxicity and intestinal inflammation were caused by imbalance in the antioxidation system. Analysis of IBR values showed that the visceral mass had a more effective response to oxidative stress than the gill and mantle after exposure to nanoplastics.

Effects of inorganic ions and natural organic matter on the aggregation of nanoplastics

The aggregation of nanoplastics (NPs) is a key issue in understanding the dynamic nature of NPs in the environment. The aggregation of NPs under various environmental conditions has not yet been studied. We investigated the influences of inorganic ions and natural organic matter (NOM) on polystyrene (PS) NPs aggregation in solutions. Results showed that PS NPs remained stable in wide ionic strength solutions of NaCl (1–100 mM) and CaCl2 (0.1–15 mM), and only in low ionic strength FeCl3 solutions (0.01 mM). However, obvious PS NPs aggregation was observed in FeCl3 solutions with an increase in ionic strength (0.1 and 1 mM). Moreover, NOM had a negligible effect on PS NPs aggregation in all ionic strengths of NaCl and CaCl2 solutions and in low ionic strength FeCl3 solutions (0.01 mM). However, NOM reduced PS NPs aggregation in an intermediate ionic strength FeCl3 (0.1 mM) solution and increased aggregation in a high ionic strength FeCl3 (1 mM) solution. Based on the theoretical analysis of interaction forces among PS NPs, the Derjaguin–Landau–Verwey–Overbeek force was a contributor governing PS NPs aggregation either in the absence or presence of NOM. In addition, other factors, including electrostatic heterogeneity of PS NPs surfaces, steric repulsion induced by NOM, and clusters formed via bridging effect in the presence of NOM also contributed to altered PS NPs aggregation under selected conditions. The PS NPs-NOM clusters were directly observed using a cryogenic scanning electron microscope.