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Review

A Review of Eco-Corona Formation on Micro/Nanoplastics and Its Effects on Stability, Bioavailability, and Toxicity

by
Haohan Yang
1,*,
Zhuoyu Chen
1,
Linghui Kong
1,
Hao Xing
1,
Qihang Yang
2 and
Jun Wu
1
1
College of Environmental Science and Engineering, Yangzhou University, Yangzhou 225127, China
2
School of Chemistry and Chemical Engineering, Guangling College, Yangzhou University, Yangzhou 225002, China
*
Author to whom correspondence should be addressed.
Water 2025, 17(8), 1124; https://doi.org/10.3390/w17081124
Submission received: 10 March 2025 / Revised: 1 April 2025 / Accepted: 8 April 2025 / Published: 10 April 2025
(This article belongs to the Special Issue Environmental Fate and Transport of Organic Pollutants in Water)
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Abstract

:
Micro/nanoplastics (M/NPs) have become prevalent in aquatic environments due to their widespread applications. Likewise, ubiquitous ecological macromolecules can adsorb onto M/NPs to form an “eco-corona”, which significantly alters their environmental behaviors including aggregation dynamics, adsorption/desorption, and bioavailability. Therefore, it is necessary to analyze the role of eco-corona in assessing the environmental risks of M/NPs. This review systematically summarizes the formation mechanisms of eco-corona and evaluates its regulatory effects on the stability and ecotoxicity of M/NPs. Compared with other ecological macromolecules (e.g., natural organic matter and extracellular polymeric substances), humic acid (HA) tightly binds to M/NPs through electrostatic and hydrophobic interactions, significantly affecting their hetero-aggregation behavior and colloidal stability. In terms of bioavailability, the various functional groups on the HA surface can regulate the surface charge and hydrophobicity of M/NPs, thereby affecting their bioaccumulation and “Trojan horse” effect. Notably, the HA corona alleviates M/NPs-induced growth inhibition and oxidative stress. Genotoxicity assessment further showed that HA corona can regulate the expression of genes related to oxidative stress response and detoxification pathways. Future studies should focus on the synergistic effects between eco-corona and co-existing pollutants in complex aquatic environments to elucidate the long-term ecological risks associated with eco-corona formation.

1. Introduction

Plastic pollution, as a global environmental issue, has attracted significant attention from scholars both domestically and internationally in recent years. By 2022, global plastic production has surpassed 400 million tons, of which China accounts for 32% [1]. A significant amount of plastic waste enters aquatic environments and gradually decomposes into medium-sized plastics (5–40 mm), microplastics (MPs, 1–5000 µm), and nanoplastics (NPs, 1–100 nm) [2]. Among these, micro/nanoplastics (M/NPs) have been widely detected in aquatic environments such as rivers, oceans, lakes, and reservoirs [3,4,5], and are referred to as “aquatic PM2.5”. According to statistics, M/NPs have been detected in 100% of turtles, 59% of whales, 36% of seals, and 40% of seabirds [6]. Every year, up to 100,000 sea mammals and one million seabirds die due to plastic pollution [7]. Meanwhile, M/NPs could induce various stress effects such as behavioral changes [8], immunotoxicity [9], and reproductive defects [10], posing potential threats to the aquatic ecosystem and human health.
However, current research on the biological effects of M/NPs was mainly focused on the causal relationship between the pristine particles and biological responses, while systematic studies on their interfacial effects in real aquatic environments are rare. In fact, due to their high specific surface area, hydrophobicity, and stability, M/NPs can quickly interact with ecological macromolecules (e.g., humic acid (HA), fulvic acid (FA), extracellular polymeric substances (EPS), and proteins), eventually forming an organic shell of varying thickness on the particle surface, known as the “eco-corona” [11,12]. The formation of eco-corona significantly altered the surface properties and hetero-aggregation of M/NPs. Since M/NPs can similarly be regarded as colloidal particles, the hetero-aggregation stability is a key factor in evaluating the environmental behavior of M/NPs [13,14,15]. For example, the HA corona increased the electrostatic repulsion between polyethylene glycol terephthalate (PET) NPs by providing more negative charges and produced steric hindrance to limit the hetero-aggregation of PET NPs [16].
Meanwhile, eco-corona has been shown to alter the biological effects of M/NPs. Most studies reported that eco-corona reduced the ecological risk of M/NPs by inhibiting cell adhesion, reducing oxidative stress, and alleviating the expression of related genes [17]. However, some studies have found that eco-corona could exacerbate the negative effects of M/NPs, including prolonging their residence time in the intestine and inducing more severe oxidative stress [18,19]. Moreover, the eco-corona could act as a “Trojan horse” for certain functionalized biomolecules. As a result, M/NPs could be internalized by cells and enter the biological tissues of the gastrointestinal tract more easily [20]. Therefore, it is very important to systematically elucidate the biological effects of eco-corona.
Based on these facts, this review investigated the mechanisms by which the eco-corona affects the biological effects of M/NPs, mainly using natural organic matter (NOM) and EPS as the typical ecological macromolecules. First, the physicochemical properties of M/NPs were described. Then, the interactions between M/NPs and different ecological macromolecules were summarized systematically. The impact of eco-corona formation on the hetero-aggregation and stability of M/NPs was clarified. Finally, the effects of eco-corona formation on the bioavailability of M/NPs were analyzed. The results provided a scientific basis for the comprehensive evaluation of the ecological risks of M/NPs in natural aquatic environments.

2. Physicochemical Properties of Typical Natural Organic Macromolecules

2.1. Natural Organic Matter

As the typical ecological macromolecules, NOM and EPS are the main components of the eco-corona in aquatic environments. NOM is a complex organic mixture in surface water or groundwater, which is from biological activities or external sources by the hydrological cycle. Thus, NOM is easily influenced by conditions of the climate and geological and topographical features. In natural water environments, the concentration of NOM varies from 0.5 mg·L−1 in seawater and groundwater to over 30 mg·L−1 in wetlands [21]. As shown in Figure 1, NOM was mainly composed of humic substances (e.g., HA, FA, humin) and non-humic components (such as carbohydrates, amino acids, and proteins) [22,23]. Notably, certain biopolymers like sodium alginate (SA)—a polysaccharide extracted from brown algae—were also classified as NOM [24]. Based on the particle size difference, NOM could be categorized into particulate organic matter and dissolved organic matter (DOM) [21]. Among them, HA is an important component of NOM with a concentration ranging from 1 to 15 mg·L−1 in freshwater [25,26]. Due to the presence of phenolic and carboxyl groups, HA contains both hydrophobic and hydrophilic properties [27]. Thus, HA could interact with organic pollutants, heavy metals, and M/NPs. Compared with HA, FA has a larger specific surface area and higher oxygen content, containing various reactive functional groups such as carboxylic acid, phenolic hydroxyl, hydroxyl, quinone, and amine. Due to the proton dissociation of these functional groups, FA can interact with metal ions and organic compounds through mechanisms such as hydrogen bonding and ion pairing [28]. SA is an anionic polysaccharide rich in hydroxyl and carboxyl groups. It is highly water-soluble and exhibits strong adsorption affinity for heavy metal ions and organic pollutants [29]. In addition, the research related to humin in the aquatic environments was limited due to the property of insoluble in water.

2.2. Extracellular Polymeric Substances

As another type of ecological macromolecules, EPS are mainly derived from the biological secretions of microorganisms (e.g., algae and bacteria) and invertebrates (e.g., Daphnia magna, D. magna) [30,31] (Figure 1). Generally, EPS could be divided into soluble EPS and bound EPS. Soluble EPS are dissolved in the liquid media such as mucus, soluble macromolecules, and colloids, which are loosely bound to the outer cell wall or completely dissolved in the solution. The bound EPS typically exhibited a bilayer structure, with the inner layer being tightly bound and the outer layer loosely bound, performing a more compact structure [32]. In terms of molecular composition, the EPS primarily consists of lipids, proteins, polysaccharides, DNA, and other natural polymers. These components could form highly hydrated, gel-like, three-dimensional matrices through van der Waals forces, hydrogen bonds, and electrostatic forces [33]. The composition and structure of EPS determined the unique physicochemical properties. The three-dimensional structure provided a high specific surface area, which enabled EPS to interact with compounds through adsorption. Due to the large number of negatively charged functional groups (e.g., amino, phosphate, carboxyl, and hydroxyl groups), EPS could adsorb cationic compounds via ion exchange [34]. Additionally, EPS contained various hydrophobic or hydrophilic functional groups (e.g., carbonyl, carbon–carbon or carbon–hydrogen bonds, carboxyl, and hydroxyl groups), given the hydrophobic or hydrophilic properties [35,36]. The hydrophilic–hydrophobic property aided in the accumulation and dissolution of environmental pollutants and facilitated microbial adhesion and pollutant attachment. Hence, the microbial colonization and pollutant migration were affected [32].
The natural aquatic environment contains numerous exogenous organic substances capable of acting as dispersants through adsorption onto M/NPs. Among these, bovine serum albumin (BSA) is a highly hydrophobic spherical macromolecule and is often used as a model protein [37]. Sodium dodecyl sulfate (SDS) is an anionic surfactant with high amphiphilicity and adsorption capacity [38]. In addition, cells or organisms release some small molecule metabolites during normal metabolism, such as Oryzias melastigma (O. melastigma) secretions (OMS) [39] and microcystin (MC), a metabolite of cyanobacteria [40,41].

3. Formation Mechanism of the Eco-Corona

Currently, various M/NPs have been used to investigate their interactions with diverse ecological macromolecules [42,43,44,45,46]. As shown in Table 1, the interaction modes of the eco-corona formation mainly included surface electrostatic interactions, hydrophobic interactions, van der Waals forces, ligand exchange interactions, hydrogen bonding, and other high-energy adsorption chemical bonds. Among them, electrostatic and hydrophobic interactions are the two most common mechanisms.

3.1. Electrostatic and Hydrophobic Interactions

The electrostatic interactions between the charged M/NPs and biomolecules were driven by the electrostatic force [63,64]. For example, the HA exposes negatively charged carboxyl groups, which can electrostatically attract positively charged polystyrene (PS) NPs-NH2 to form an eco-corona while repelling negatively charged PS NPs-COOH [65]. Similarly, negatively charged EPS and SA have a more significant modifying effect on positively charged M/NPs than on negatively charged ones. The hydrophobic interactions referred to the tendency of non-polar molecules to aggregate and move away from the aqueous phase. The pristine NPs primarily form eco-coronas with biomolecules through the hydrophobic interactions. For example, high-protein EPS formed eco-corona with raw PS NPs through hydrophobic adhesion on marine phytoplankton [66]. Meanwhile, Feng et al. [65] reported that the neutral PS NPs adsorbed the aromatic rings of HA through hydrophobic interactions to form an eco-corona.

3.2. Hydrogen Bonding and van der Waals Forces

As for weaker intermolecular forces, hydrogen bonding commonly occurs between molecules containing functional groups like hydroxyl groups. Van der Waals forces are the attractive forces caused by polarization fluctuations between atoms, while π–π interactions occur as weak interactions between molecules containing aromatic rings. For example, oxygen-containing groups (e.g., -OH, C=O) on aged polyethylene (PE) and polypropylene (PP) MPs bound EPS polysaccharides via hydrogen bonding [67,68]. Meanwhile, PS MPs interacted with EPS through π–π interactions between their benzene rings and EPS aromatic structures, with N/O groups serving as key binding sites [11]. Degradable polylactic acid (PLA) MPs also utilized hydrogen bonding for EPS adsorption, while non-degradable PS MPs additionally formed π–π complexes with FA [69]. Van der Waals forces contributed to interactions in Scenedesmus obliquus EPS-PS NPs systems, alongside electrostatic/hydrophobic effects [47]. Meanwhile, the ligand exchange was referred to as the replacement or binding between biomolecules and active sites on the particle surface to form a more stable structure. Ligand exchange occurred when low-binding-energy citrate coatings on Ag NPs were replaced by NOM during eco-corona formation [70].

4. Effects of Eco-Corona Formation on the Hetero-Aggregation Stability of M/NPs

4.1. Applications and Limitations of DLVO and XDLVO Theories

When M/NPs interact with natural organic macromolecules in water to form an eco-corona, their functionalization, surface charge, and hydrophobicity undergo significant changes (Figure 2). These alterations affect the hetero-aggregation and stability of M/NPs. The Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, a colloidal dispersion stability theory, is widely used to evaluate the hetero-aggregation stability of colloidal particles. However, since it only incorporates electrostatic repulsion and van der Waals attraction generated by counter ions in the electric double layer, predictions may exhibit substantial deviations. Consequently, the extended DLVO (XDLVO) theory, which accounts for additional potential forces, can more accurately predict hetero-aggregation stability between colloidal particles [71]. As shown in Table 2, the presence of an eco-corona can influence M/NP hetero-aggregation behaviors and stability through electrostatic interactions, steric hindrance, or molecular bridging.

4.2. Regulatory Mechanisms of Eco-Corona on Hetero-Aggregation of M/NPs

For the electrostatic interactions, the zeta (ζ) potential was a key parameter determining the electrostatic repulsion between particles [77]. This interaction could be easily influenced by various factors (e.g., particle characteristics, pH conditions, and environmental media) [78]. Thereby, the stability of M/NPs hetero-aggregation was affected. For example, EPS could inhibit the hetero-aggregation of PS MPs by reducing the ζ potential of PS MPs to increase the electrostatic repulsion. However, PS NPs were shown a higher affinity for tryptophan, tyrosine, and humic acid-like substances in the EPS compared to MPs due to the larger specific surface area. As a result, the hetero-aggregation of NPs was promoted by the reduction in electrostatic repulsion [84]. Meanwhile, the environment-related pH values and the presence of electrolytes could affect the charge states of M/NPs, significantly affecting the hetero-aggregation of plastic particles. Generally, higher pH values increased the electrostatic repulsion between NPs, thereby inhibiting hetero-aggregation. In saline media, the adsorption of NOM on NPs reduced hetero-aggregation and sedimentation, exhibiting good stabilization effects [60]. For instance, Liu et al. [37] found that HA and EPS enhanced the stability of PS NPs as the pH increased in a salt solution containing NaCl and CaCl2. Kong et al. [89] found that HA enhanced the stability of PS NPs in NaCl solutions but reduced the stability in CaCl2 solutions. This might be due to the stronger charge-shielding effect of multivalent cations on the surface of NPs, which enhanced their hetero-aggregation. However, the experimental conditions mainly involved NaCl and CaCl2 solutions, which may not fully simulate the more complex ionic composition, and the interaction of particulate matter in natural water bodies.
Comparatively, the effect of steric hindrance was due to the occupation of space on the surface of M/NPs by the eco-corona. As a result, the direct contacts between particles were prevented to reduce the hetero-aggregation of M/NPs. For instance, Chen et al. [90] found that the additional steric hindrance improved the stability of PS NPs in the presence of HA corona. The adsorption of EPS reduced the hetero-aggregation rates of PS NPs due to the enhanced steric hindrance [91]. Additionally, the aggregates formed by SA adsorbing and bridging PSL NPs-COOH and PS NPs were stable due to the steric hindrance [79,92]. In aged NPs, Li et al. [48] reported that the presence of NOM reduced the hetero-aggregation of ozone-aged PS NPs, leading to enhanced stability by steric hindrance. As PS NPs aged, the steric hindrance caused by HA weakened, thereby reducing the inhibition effect of HA on the hetero-aggregation of PS NPs [93]. Additionally, Wu et al. [94] reported that the HA corona stabilized three types of negatively charged PS NPs (PS, PS-COOH, n-PS-NH2) through steric hindrance under high salinity conditions.
The molecular bridging effects were the connection of ecological macromolecules with M/NPs through the multiple binding sites to promote the formation of aggregates. For example, HA could bind to the hydroxyl groups of oxidized PET NPs through its carboxyl groups, and the hetero-aggregation of colloidal particles was promoted [95]. In addition, the presence of cations altered the charge of particles through the electrostatic interactions in electrolyte solutions, and divalent cations (primarily Ca2+) can also enhance the hetero-aggregation of M/NPs through molecular bridging. For NOM, high concentrations of NOM and HA could strengthen the hetero-aggregation of PS NPs in CaCl2 solutions through the bridging effects [83,96]. Liu et al. [37] found that SA enhanced the hetero-aggregation of PS NPs in CaCl2 solutions through the increased molecular bridging effects. Most studies on the bridging mechanism of Ca2+ to EPS have focused on the evaluation of the hetero-aggregation of metal nanoparticles [80,85,97], with relatively little research on M/NPs. Xiong et al. [98] investigated the effects of EPS on the hetero-aggregation of PS MPs in the presence of Ca2+ and found that the EPS corona enhanced the hetero-aggregation with PS MPs through molecular bridging of Ca2+. In fact, the hetero-aggregation and stability of M/NPs in the presence of eco-corona were affected by the combined effects of the above-mentioned effects. Ruan et al. [81] and Li et al. [86] found that the promotion or inhibition of the hetero-aggregation of PS NPs depended on the balance between the steric hindrance and bridging effects in the existence of NOM corona. Likewise, the hetero-aggregation behaviors of 100 nm PS NPs in HA and FA were also determined by the surface charge heterogeneity of PS NPs, steric hindrance, and bridging effects [99]. Studies on other biomolecules (FA, EPS) also obtained the same conclusion, indicating that this phenomenon is widely universal [71,100]. In addition, Sun et al. [101] found that hydration layer repulsion greatly influenced the hetero-aggregation of M/NPs. For HA corona, the steric hindrance was the main mechanism for the enhanced stability of NPs, and hydration layer exclusion also played a certain role.

5. Effects of Eco-Corona on the Bioavailability of M/NPs

The biological effects of M/NPs would be responded to because of the presence of eco-corona due to the alterations of interfacial properties. Thus, as shown in Figure 3, the roles of eco-corona on the bioavailability of M/NPs were summarized from bioaccumulation, biological effects, and molecular mechanisms, respectively.

5.1. Bioaccumulation

Generally, receptor-mediated active endocytosis is the primary pathway for cells to uptake the M/NPs in aquatic environments [89,102]. Before that, cell adhesion is the key step in the endocytosis process [103]. Recent studies have revealed that M/NPs could adhere to the lipid bilayer of the cell membrane through receptor–ligand interactions, electrostatic interactions, and hydrophobic interactions. Moreover, M/NPs with high hydrophobicity and positive charges are more likely to adhere to the cell surface and penetrate the lipid bilayer [104,105]. However, the formation of eco-corona modified the surface characteristics of M/NPs, thereby affecting the uptake, accumulation, and bioavailability of aquatic organisms (Figure 4).

5.1.1. Algae

For algae, due to the accumulation of numerous carboxyl, hydroxyl and amine functional groups on the surface, the algal cell membrane is mostly negatively charged [106]. The electrostatic repulsion and the prevention of direct contact were the main routes of eco-corona to modify the uptake processes of the charged and uncharged M/NPs, respectively (Figure 3B). For example, HA includes various functional groups, such as ketones, hydroxyls, thiol, methoxyl and phenolic compounds. The adsorption of these functional groups reversed the surface charge of PS NPs-NH2 and increased the electrostatic repulsion between the particles and the negatively charged polysaccharide membrane of Chlorella vulgaris (C. vulgaris), which effectively reduced the bioaccumulation of PS NPs-NH2 [43,107]. Similarly, the negatively charged EPS corona generated significant electrostatic repulsion between PS NPs-NH2 and S. obliquus, resulting in the inhibition of the contact of PS NPs with the cell membrane [108]. Therefore, it is reasonable to speculate that the negatively charged functional groups of NOM and EPS could improve the electrostatic repulsion and then inhibit the internalization of the positively charged M/NPs by algal cells. For uncharged particles, the eco-corona could block the direct contact between M/NPs and algal cells. The EPS released by algae acted as an extracellular protective barrier, preventing direct contact between the PS NPs and Chlorella sp., significantly reducing the bioavailability of PS NPs [109,110]. However, the bioavailability of negatively charged particles was relatively less by the impact of eco-corona due to the pre-existing repulsive effect of the same charge as the cell membrane. For example, the adsorption of negatively charged PS NPs-COOH on Phaeodactylum tricornutum (P. tricornutum) was found to be negligible, while the presence of EPS corona did not change the bioavailability of PS NPs-COOH [74].

5.1.2. Invertebrates

As for aquatic invertebrates, they mainly ingest M/NPs into the intestine through the filter-feeding process [111]. Similarly to algae, invertebrates (e.g., D. magna) can secrete EPS in the form of polysaccharides or proteins in response to environmental stimuli or metabolism. The adsorption of these EPS on the M/NPs surface caused an increase in particle size, making them more readily ingested by D. magna [31]. Upon ingestion, the presence of the EPS corona made plastic particles remain in the intestine longer and more difficult to eliminate. After 6 h of exposure, 20% of PS NPs coated with EPS corona remained in the intestine of D. magna, while only 15% of the original PS NPs remained [31]. It is worth noting that the secretion of EPS was essentially a defense mechanism of invertebrates, but the bioaccumulation of M/NPs was unexpectedly enhanced in this process. Different from endogenous EPS, Wu et al. [112] found that the NOM corona around PS NPs and PS NPs-NH2 cut off the contact between NPs and the intestinal tissue of D. magna. At the same time, HA enhanced the hydrophilicity of the plastic particles, ultimately preventing NPs from passing through the intestinal epithelial cells and entering the biological tissue. This difference suggests that the biotic/abiotic properties of eco-corona determine the direction of its regulation on the accumulation of M/NPs. The formed eco-corona gave M/NPs a new biological identity, thereby affecting the response at the cellular level. Compared with the exogenous environmental substance NOM, as a biological metabolite, the EPS corona had biological similarities with cells, making M/NPs more likely to accumulate in invertebrates [113].

5.1.3. Fish

With regard to fish, M/NPs were able to be absorbed on gill filaments through filtration or accumulated in the intestinal lumen through oral administration [114]. The formation of eco-corona significantly changed the biosorption and clearance behavior of M/NPs, and this effect was tissue-specific: accumulation was inhibited in the gills, while accumulation was enhanced in the intestine. For example, Zheng et al. [115] used Oreochromis niloticus (O. niloticus) as the test organism to evaluate the effects of DOM on the bioavailability of PA MPs. The results indicated that the HA corona on the surface of PA MPs inhibited the accumulation of PA MPs by hindering direct contact with gill tissues and increasing electrostatic repulsion [116,117]. However, the formed eco-corona reduced the ability of fish to clear M/NPs in the intestine. The formation of the BSA corona increased the apparent viscosity of PS MPs and promoted the bioaccumulation of PS MPs in the intestine of Danio rerio (D. rerio) [118]. Once the accumulation of MPs in the oral cavity exceeds a tolerance threshold, and then the fish could expel the MPs by coughing [119]. HA corona reduced the coughing behavior in fish, lowered the clearance rate of MPs, and further increased the number of MPs swallowed into the gut [115].
Meanwhile, surface aging of M/NPs (such as photooxidation and NOM-driven aging) aggravates the interactions with biological tissues and affects their bioaccumulation by changing physicochemical properties (such as roughness and oxygen-containing functional groups). For example, the small-sized PA MPs could accelerate their excretion from the intestine of D. rerio by activating the activity of efflux pump proteins [120]. The presence of NOM changed the particle size and edge properties of PA MPs by driving the photoaging process, significantly increasing the accumulation of MPs in the intestine [18,121]. The interaction between PA MPs and the intestinal villi was intensified due to the rough surface and cracks [122]. Aged PS MPs with serrated edges retain longer in the intestine of D. rerio larvae than spherical MPs [123]. Additionally, NOM aging incorporated numerous oxygen-containing functional groups on MPs surface, promoting the binding of large molecular MPs to the intestinal mucus gel layer through hydrogen bonding, making it difficult for D. rerio to excrete MPs directly [124]. Intestinal tissue damage promoted the diffusion of M/NPs through epithelial cells into the circulatory system or diffusion between adjacent cells at tight junctions, ultimately crossing biological barriers and depositing in the liver and brain [18,115,125].
Additionally, NPs could transfer heavy metals and other harmful chemicals into organisms and various environments through the “Trojan horse” effect, resulting in greater toxic effects than MPs. The adsorption and release of pollutants by NPs depended on the competition between pollutants, organisms, and the environment, in which ecological macromolecules could interfere with the “Trojan horse” effect of NPs by competing for binding sites and enhancing electrostatic repulsion. For example, PS NPs increased the absorption and accumulation of phenanthrene in the gills and liver of Oncorhynchus mykiss, but the addition of NOM decreased phenanthrene absorption by 70%. This reduction was attributed to NOM competing with phenanthrene for adsorption sites on the surface of PS NPs, weakening the “Trojan horse” effect of PS NPs by lowering their transport of phenanthrene [126]. Monikh et al. [127] investigated the “Trojan horse” effect of nanoplastic debris and found that NPs fragments increased the bioavailability of Ag+ by altering the uptake pathway and promoting its transport to the organs of D. magna. The presence of NOM prevented Ag+ from binding to toxic action sites, reducing the bioavailability of Ag+. However, some studies suggested that NOM could increase the accumulation of heavy metals by changing the surface properties of NPs. For instance, Qiao et al. [128] found that NOM promoted the adsorption of Cu2+ onto PS MPs, increasing the accumulation of Cu2+ in the liver and intestine of D. rerio. This was attributed to the aromatic structure of NOM interacting with MP to form a highly conjugated co-polymer, which increased the electron density and made it easier for MPs to adsorb heavy metal ions [129]. Additionally, the Cu2+ concentration (50 µg/L) used in the experiment may exceed typical levels found in most natural water bodies. Such high-concentration exposure could amplify toxic effects, potentially limiting the applicability of the experimental findings to real-world environmental conditions.

5.2. Biological Effects

Studies have shown that M/NPs could damage the cell structure and cause multilevel biological effects. Eco-corona significantly altered the original toxicity of M/NPs through multiple routes such as physical barrier effect, biomolecular regulation, and oxidative stress intervention. Relevant studies about the impact of eco-corona formation on the biological effects of diverse M/NPs are shown in Table 3.

5.2.1. Growth Inhibition and Oxidative Stress

Firstly, the formation of eco-corona effectively alleviated the inhibition of algal photosynthesis and growth caused by M/NPs (Figure 3C). Its protective mechanism was mainly reflected in (1) blocking the direct contact between M/NPs and cell membrane and (2) activating the compensatory stress response of the organism. For example, PS NPs-NH2 covering the surface of C. vulgaris reduced the efficiency of photosynthesis, disrupted cellular material exchange, and even led to cell apoptosis. The presence of HA corona upregulated the contents of chlorophyll a and b and effectively alleviated the toxicity of PS NPs-NH2 by enhancing the self-regulation ability of C. vulgaris [132]. Additionally, HDPE MPs acted as a barrier to block the minimum light intensity required by Chlamydomonas reinhardtii, leading the cells to produce EPS and increase cell density to relieve cell stress [133]. Low concentrations of PS NPs could directly damage the cell membrane of Microcystis aeruginosa and inhibit photosynthesis. However, increased concentrations of PS NPs induced the release of MC from algal cells. The MC corona reduced the accumulation of PS NPs and alleviated growth inhibition, ultimately allowing algae to recover quickly after the inhibition period [134,135].
Secondly, at the cellular level, M/NPs could stimulate cells to generate excessive ROS by reacting with oxygen and damaging cell structures [136]. Excessive accumulation of ROS in cells could reduce membrane fluidity, disrupt metabolism and gene expression, destroy cell structure, and ultimately induce cell apoptosis [137,138]. The presence of eco-corona could alleviate oxidative damage by reducing the probability of contact between M/NPs and cell structures [139] and directly exerting free radical scavenging function [140]. For example, both the BSA and HA corona significantly downregulated the level of ROS induced by PS NPs, thereby alleviating apoptosis of D. rerio [55]. Notably, the EPS corona could not only reduce the transmembrane input of ROS by consuming extracellular oxidation reaction sites, but also directly remove free radicals through active groups such as phenolic hydroxyl groups, ultimately reducing the toxicity of PS NPs to P. tricornutum [74] and Chlorella sp. [141].

5.2.2. Photoaging M/NPs

When M/NPs were exposed to ultraviolet (UV) radiation in sunlight, their surface properties and toxicological effects changed significantly [130]. UV radiation broke M/NPs into fragments with more oxygen functional groups, higher roughness, and larger specific surface area [142]. Ecological macromolecules in aquatic environments could accelerate the photoaging of M/NPs by affecting the penetration depth of ultraviolet light and participating in free radical reactions. During the NOM-driven photoaging process, hydroxyl radicals formed on the surface increased the oxidative potential of M/NPs, which stimulated D. rerio intestinal cells to produce more ROS, leading to more severe oxidative stress and intestinal damage [51]. Compared to the pristine PA MPs, NOM-driven photoaged PA MPs unbalanced the redox status of the D. rerio intestine, leading to the shedding of intestinal epithelial cells and thinning of the intestinal wall [18]. Notably, the rough surface and newly added oxygen-containing functional groups produced by the photoaging process significantly enhanced the adsorption capacity of M/NPs for coexisting pollutants. Taking PVC MPs as an example, the aged PVC MP has more adsorption sites for pollutants, significantly enhancing the toxicity of tetrabromobisphenol A to S. obliquus [143]. However, Giri and Mukherjee [47] found that the EPS-driven aging process alleviated the toxicity of PS NPs to S. obliquus. This was due to EPS increasing the particle size by promoting the hetero-aggregation of PS NPs, thereby preventing cellular uptake and reducing ROS production.
In fact, the impact of eco-corona on the biological effects of M/NPs depended on the characteristics of M/NPs and the composition of eco-corona. Among these properties, particle sizes were an important factor with regard to the characteristics of M/NPs due to the differences in toxic mechanisms [144]. Larger MPs, for example, could obstruct light transmission and impair photosynthesis in S. obliquus, whereas smaller MPs tended to adhere to cell membranes, compromising their structural integrity. The presence of HA corona mitigated the toxicity of small MPs by preventing their adhesion to algal surfaces but did not counteract the light-blocking effects of larger MPs [19]. Similarly, the OMS corona has been found to alleviate immune and energy metabolism suppression caused by 5 μm PS MPs, but it exacerbated the immunotoxicity of 50 nm PS NPs. This heightened toxicity of smaller NPs is attributed to their increased ability to penetrate the chorion and disrupt inflammatory responses and immune enzyme activity [39]. Furthermore, the eco-corona formed by different ecological macromolecules affected the biological effects of M/NPs in distinct ways. For instance, the BSA corona aggravated oxidative stress and heart rate abnormalities in D. rerio embryos exposed to PET NPs, exhibiting a stronger toxicity-enhancing effect than the SDS corona [145]. The greater dispersibility and smaller size of BSA-PET NPs facilitated their penetration through embryonic membranes, leading to more pronounced damage to cell membranes and mitochondria compared to SDS-PET NPs.

5.3. Molecular Mechanism

After entering cells, M/NPs interfered with gene transcription and induced the expression of specific genes by excessive ROS production or crossing the nuclear membrane to damage DNA [146,147,148]. Eco-corona activates the detoxification and antioxidant defense systems in organisms by regulating the expression of oxidative stress-related genes (Figure 3D). Glutathione-S-transferase (GST) [149], glutathione peroxidase (GPx) [150], and catalase (CAT) [151] are key antioxidant enzymes that resist oxidative stress and are considered biomarkers for oxidative stress assessment. Heat shock protein (HSP70) and P-glycoprotein (P-GP) are responsible for exporting various harmful compounds out of cells and are the most common stress-induced chaperone [152,153]. The NOM and HA corona alleviated the upregulation of detoxification and oxidative stress-related genes (GST, CAT, HSP70, and P-GP) induced by PS NPs, significantly reducing the oxidative damage caused by M/NPs to D. magna [61,154]. Notably, the FA corona with a more negative charge exacerbated the upregulation of gene expression and effectively alleviated the toxicity of PS NPs by regulating the activities of antioxidant enzymes such as GPx, CAT, and SOD [154,155]. Similarly, melanocortin 2 receptor (MC2R) [156] and interleukin 10 (IL10) [157] have anti-inflammatory effects and are crucial in stress response and immune regulation. Short-term exposure to PS NPs induced anti-inflammatory and oxidative stress responses in Dicentrarchus labrax. PS NPs coated with NOM corona showed synergistic anti-inflammatory properties by activating anti-inflammatory factors such as MC2R and IL10, restoring the levels of inflammatory markers to normal [158].
Although eco-corona generally exhibited toxicity mitigation effects, some studies have shown that they might enhance the genotoxicity of M/NPs by exacerbating oxidative stress. NRF2 and its inhibitor KEAP1 are key components of the Nrf2-Keap1-ARE signaling pathway and are essential to the antioxidant system [159,160]. Luo et al. [118] found that the BSA corona induced excessive ROS production by increasing the accumulation of MPs, further aggravating the inhibition of NRF2 and KEAP1 gene expression in the intestine of D. rerio, and seriously damaging the protective function of the antioxidant system. UDP-glucuronosyltransferase (ugt) is a microsomal glycosyltransferase that transforms lipophilic molecules (e.g., bilirubin, steroids, and hormones) into water-soluble excretory metabolites [161]. Similarly, HA corona significantly inhibited the expression of ugt genes (ugt1a1, ugt2a4, etc.) and GST genes (gsta.2, gsto2, etc.) of D. rerio embryos by increasing the particle size of NPs to allow them to adsorb more pollutants, causing more severe oxidative damage and metabolic disorders [18].

6. Perspectives

Ecological macromolecules have been demonstrated to be essential in modulating the stability and biological effects of M/NPs. Current research has made significant progress in understanding the ecological impacts of eco-corona on aquatic organisms such as algae, invertebrates, and fish. However, given the intricacies of environmental factors and the characteristics of ecological macromolecules, further studies are necessary to elucidate the formation mechanism of eco-corona and its subsequent toxic effects in diverse aquatic environments. Future research should prioritize the following aspects:
(1)
The properties of the environmental medium significantly determine the aggregation state, stability, and bioavailability of contaminants in aquatic environments. For instance, higher ionic strength could reduce the electrostatic repulsion of TiO2 NPs and increase particle aggregation [162]. Higher temperatures not only facilitate the formation of EPS corona on Ag NPs surfaces but also significantly enhance the structural stability of the EPS-Ag NPs composite system [163]. So far, only the effects of salinity, pH, and different electrolytes on the formation of eco-corona on the surface of M/NPs have been studied, while the role of other influencing factors (such as temperature, conductivity, ion valence, etc.) deserves further investigation.
(2)
In aquatic environments, the interaction between M/NPs and co-pollutants could influence the uptake and accumulation of plastics or contaminants in aquatic organisms. Current studies have demonstrated that the formation of eco-corona altered the adsorption and desorption behavior of M/NPs toward heavy metal ions [164]. However, little is known about the effects of eco-corona on the interaction of M/NPs with other types of pollutants (e.g., metal nanoparticles, persistent organic pollutants, pharmaceutical pollutants), and further investigation of potential interfacial reactions is needed.
(3)
When M/NPs coated with eco-corona migrate from the external water environment into organisms or cells, the affinity of ecological macromolecules to the M/NPs may change with the changes due to the environment [165]. If biomolecules such as lipids, proteins, and nucleic acids within the organism exhibit a higher affinity for M/NPs, these biomolecules can be exchanged with the adsorbed components on the eco-corona [166]. However, it remains unclear which specific biomolecules would cover or replace the ecological macromolecules adsorbed on the surface of M/NPs, thereby forming a new eco-corona. The consequences of biomolecule replacement and its interaction process are also unclear. Therefore, further research is needed on the fate and transformation of the corona in cells or organisms, which is crucial for evaluating the biological effects of M/NPs.
(4)
Currently, knowledge of the biological effects and mechanisms of eco-corona is relatively limited. Studies on the biological effects of M/NPs by eco-corona have mainly centered on membrane adhesion, cellular uptake, growth inhibition, and oxidative stress. However, the impact of eco-corona on genotoxicity and reproductive toxicity has only recently started to be investigated. Therefore, beyond specific toxic endpoints such as DNA damage and apoptosis, the mechanisms of intracellular responses, including enzyme inactivation, cell differentiation, epigenetic modifications, and gene mutations, should be thoroughly explored.

7. Conclusions

This review elucidates the critical role of ecological macromolecules in modulating the environmental behaviors and biological impacts of M/NPs. In aquatic environments, ecological macromolecules are adsorbed on the surface of M/NPs through electrostatic interactions, hydrophobic interactions, hydrogen bonding, ligand exchange, and van der Waals forces to form an eco-corona. Eco-corona alters the hetero-aggregation and stability of M/NPs through mechanisms such as electrostatic interactions, steric hindrance, and molecular bridging. Regarding bioavailability, the feeding behavior and body size of aquatic organisms across different trophic levels shape the effects of eco-corona on the bioaccumulation and toxicity of M/NPs. The formation of the eco-corona reduces the uptake of M/NPs by algae and fish, but makes M/NPs more difficult to be removed from the intestines of fish and invertebrates. Notably, eco-corona competitively binds to coexisting pollutants through electrostatic repulsion and site competition, thereby weakening the “Trojan horse” effect of M/NPs. Meanwhile, eco-corona alters the various toxic effects of M/NPs, including growth inhibition, oxidative stress, and immunosuppression. Genotoxicity assessments reveal that regulating gene expression levels is an important way for eco-corona to change the biological effects of M/NPs. Future research should focus on comprehensively exploring the mechanisms and ecological risks of eco-corona and coexisting pollutants, and provide a scientific basis for pollution mitigation strategies.

Author Contributions

H.Y.: Investigation, Methodology, Validation, Resources, Visualization, Supervision, Project Administration, Funding Acquisition, and Writing—Reviewing and Editing. L.K. and Z.C.: Conceptualization, Investigation, Formal Analysis, Data Curation, Writing—Original Draft, and Writing—Review and Editing. H.X. and Q.Y.: Writing—Review and Editing and Supervision. J.W. Writing—Review and Editing. All authors have read and agreed to the published version of the manuscript.

Funding

This study was supported by the National Natural Science Foundation of China (42307464) and the Natural Science Foundation of Jiangsu Province, China (KZ20221144).

Conflicts of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Figure 1. Main components and structure of eco-corona.
Figure 1. Main components and structure of eco-corona.
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Figure 2. TEM characterization of PS NPs with distinct surface functionalization and eco-corona formation mediated by ecological macromolecules: (a) pristine of PS NPs, (b) pristine of PS NPs-NH2, (c) pristine of PS NPs-COOH, (d) aged plain PS NPs, (e) PS NPs coated with EPS corona, (f) PS NPs coated with HA corona, (g) PS NPs coated with FA corona, (h) PS NPs coated with NOM corona [51,72,73,74,75].
Figure 2. TEM characterization of PS NPs with distinct surface functionalization and eco-corona formation mediated by ecological macromolecules: (a) pristine of PS NPs, (b) pristine of PS NPs-NH2, (c) pristine of PS NPs-COOH, (d) aged plain PS NPs, (e) PS NPs coated with EPS corona, (f) PS NPs coated with HA corona, (g) PS NPs coated with FA corona, (h) PS NPs coated with NOM corona [51,72,73,74,75].
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Figure 3. The formation of eco-corona and the toxicity of M/NPs coated with eco-corona to aquatic organisms. (A) Formation of eco-corona. (B) Effects the adhesion of M/NPs to the cell surface. (C) Protecting algae from damage by M/NPs. (D) Effects on M/NPs-induced cytotoxicity and gene expression. Created using Biorender online tool (www.biorender.com).
Figure 3. The formation of eco-corona and the toxicity of M/NPs coated with eco-corona to aquatic organisms. (A) Formation of eco-corona. (B) Effects the adhesion of M/NPs to the cell surface. (C) Protecting algae from damage by M/NPs. (D) Effects on M/NPs-induced cytotoxicity and gene expression. Created using Biorender online tool (www.biorender.com).
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Figure 4. Effects of eco-corona formation on surface properties and bioaccumulation of M/NPs. Created using Biorender online tool (www.biorender.com).
Figure 4. Effects of eco-corona formation on surface properties and bioaccumulation of M/NPs. Created using Biorender online tool (www.biorender.com).
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Table 1. Formation mechanisms of eco-corona on M/NPs with distinct surface functionalization.
Table 1. Formation mechanisms of eco-corona on M/NPs with distinct surface functionalization.
M/NPsOriginal Surface StateEcological
Macromolecules		Formation MechanismsReferences
PS NPsPristineEPSHydrogen bonding[11]
PE, PP, PS, PET MPsPristineSuwannee River FA, HA, NOMHydrophobic interactions[42]
Polyvinyl chloride (PVC) MPs, PS MPsPristineHAElectrostatic interactions, hydrogen bonding, π–π and hydrophobic interactions [44]
PLA MPsPristineHAHydrophobic interactions, hydrogen bonding[45]
PS NPs, PS NPs-COOH, PS NPs-NH2Pristine and functionalizedEPSElectrostatic interactions, hydrophobic interactions, and van der Waals forces[47]
PS NPsAgedHAElectrostatic interactions and van der Waals forces[48]
PS NPs, PS NPs-COOH, PS NPs-NH2Pristine and functionalizedSuwannee River NOMElectrostatic interactions[49]
PS NPsPristine and agedHAElectrostatic, hydrophobic interactions[50]
PS NPsPristineSuwannee River FAHydrophobic interactions[51]
Polystyrene latex (PSL) NPs, PSL NPs-NH2, PSL NPs-COOHPristine and functionalizedFAElectrostatic interactions[52]
High-density polyethylene (HDPE), PP, PET, PS MPsPristineNOMElectrostatic and hydrophobic interactions[53]
PS MPsPristineFA, HA Hydrophobic interactions[54]
PS NPsPristineHAElectrostatic interactions[55]
PS, PVC M/NPsPristineHAHydrophobic interactions[56]
PS NPsPristineEPSElectrostatic interactions and van der Waals forces[57]
Polyamide (PA), PP MPsPristineHAElectrostatic, hydrophobic interactions[58]
Acrylonitrile butadiene styrene, PA, PVC, PS, PET MPsPristineHAElectrostatic interactions[59]
PP MPsPristineSuwannee River HA, Pony Lake FAElectrostatic, hydrophobic interactions[60]
PS NPs-NH2, PS MPs-NH2FunctionalizedHAElectrostatic interactions[61]
PS NPsPristineHAElectrostatic interactions[62]
Table 2. Regulatory mechanisms of eco-corona on hetero-aggregation stability of M/NPs.
Table 2. Regulatory mechanisms of eco-corona on hetero-aggregation stability of M/NPs.
Theoretical CalculationM/NPsEcological MacromoleculesRegulatory MechanismsReferences
DLVOPS NPsHA, SAElectrostatic interactions, molecular bridging[62]
PS NPs, PS NPs-NH2, PS NPs-COOHHAElectrostatic interactions, molecular bridging[76]
Aged PET NPsHAElectrostatic interactions[77]
PS NPs, PS NPs-NH2, PS NPs-COOHNOMElectrostatic interactions[78]
PS NPs, PS NPs-NH2, PS NPs-COOHEPSElectrostatic interactions, molecular bridging[79]
PS NPsHA, FAElectrostatic interactions[80]
PS NPsHA, SAElectrostatic interactions[81]
PS NPsHA, SAElectrostatic interactions[82]
XDLVOPS NPsHA, BSAElectrostatic interactions, steric hindrance, molecular bridging[37]
Aged PS NPsHA, SAElectrostatic interactions, steric hindrance, molecular bridging[48]
PS M/NPsEPSElectrostatic interactions, steric hindrance[83]
PS NPsEPSElectrostatic interactions, steric hindrance[84]
PS NPsHAElectrostatic interactions, steric hindrance[85]
PS NPsNOMSteric hindrance, molecular bridging[86]
PS NPsBSASteric hindrance, molecular bridging[87]
PS NPs, PS NPs-NH2, PS NPs-COOHBSAElectrostatic interactions, steric hindrance[88]
Table 3. Toxicological alternations induced by the formation of eco-corona.
Table 3. Toxicological alternations induced by the formation of eco-corona.
Biotrophic LevelToxicity Enhancement/
Reduction Mechanisms		M/NPsEcological
Macromolecules		Test OrganismsReferences
AlgaeAlleviate oxidative stressPS MPsEPSS. costatum[11]
Prevent cell uptake, reduced ROS productionPS NPsEPSS. obliquus[47]
Alleviate oxidative stress by scavenging free radicalsPS NPs-COOHEPSP. tricornutum[74]
Reduce electrostatic attraction between NPs and algal cellsPS NPsHAC. vulgaris[107]
Alleviate oxidative stressPS NPs-COOH, PS NPs-NH2EPSS. obliquus[108]
Alleviate oxidative stressPS NPs, PS NPs-COOH, PS NPs-NH2EPSChlorella sp. [130]
Reduce ROS productionPS NPsEPSChlorella sp. [131]
InvertebratesDamage feeding capacityPS NPs-COOH, PS NPs-NH2ProteinsD. magna[31]
Reduce the entanglement and body burden of NPs PS NPs, PS NPs-COOH, PS NPs-NH2HAD. magna[112]
FishCause poor lipid adsorption and growth inhibitionPA MPsHA, FAD. rerio[18]
Damage the immune system and induce immune suppressionPS M/NPsEPSO. melastigma[39]
Alleviate hepatic lipid peroxidation and protein damagePA MPsHAO. niloticus[115]
Increase accumulation of MPs in the intestine, inhibit food intake, and promote ROS productionPS MPsBSAD. rerio[118]
Enhance oxidative stressPS MPsNOMD. rerio[126]
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Yang, H.; Chen, Z.; Kong, L.; Xing, H.; Yang, Q.; Wu, J. A Review of Eco-Corona Formation on Micro/Nanoplastics and Its Effects on Stability, Bioavailability, and Toxicity. Water 2025, 17, 1124. https://doi.org/10.3390/w17081124

AMA Style

Yang H, Chen Z, Kong L, Xing H, Yang Q, Wu J. A Review of Eco-Corona Formation on Micro/Nanoplastics and Its Effects on Stability, Bioavailability, and Toxicity. Water. 2025; 17(8):1124. https://doi.org/10.3390/w17081124

Chicago/Turabian Style

Yang, Haohan, Zhuoyu Chen, Linghui Kong, Hao Xing, Qihang Yang, and Jun Wu. 2025. "A Review of Eco-Corona Formation on Micro/Nanoplastics and Its Effects on Stability, Bioavailability, and Toxicity" Water 17, no. 8: 1124. https://doi.org/10.3390/w17081124

APA Style

Yang, H., Chen, Z., Kong, L., Xing, H., Yang, Q., & Wu, J. (2025). A Review of Eco-Corona Formation on Micro/Nanoplastics and Its Effects on Stability, Bioavailability, and Toxicity. Water, 17(8), 1124. https://doi.org/10.3390/w17081124

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