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Poly(Ethylene Terephthalate) Microplastics
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The high PET production volume and the waste mismanagement of PET litter make it one of the most polluting plastic material. Its diffusion in marine litter is widely assessed according to public opinion and documented in the literature. The major sources of PET microplastics in the marine environment are bottles and fibers. The role of PET micro/nanoplastics of vector of toxic chemicals, their fate and the negative effects on the environment and human health is still under discussion.

marine litter ocean pollution microplastics model nanoplastics adsorption kinetics PET organic contaminants release degradation transport phenomena
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    1. Introduction

    Currently, the massive population expansion and the daily use of polymers for producing and consuming non-reusable objects for different applications (packaging, cosmetics, textiles, detergents, greenhouses, mulches, fishing nets, coating and wiring, trays and bottles, covers, bags, and containers) cause wild waste accumulation, with consequent significant complications owing to its management and disposal [1][2][3][4]. In specific, the municipal solid waste worldly production passed from 1.3 billions of tons in 1990 to 3.81 billions tons after 25 years [5][6]. Even if the waste flow comes from different sources [7][8], plastics represent a substantial portion of the municipal solid waste. In 2016, about 27.1 million metric tons (Mt) of plastic litters were stored in the European Union (EU), of which 31.1%, 41.6%, and 27.3%, were recycled, reused (for energy production), and dumped again in landfill sites, respectively [9]. Among polymer materials, the greatest contribution is provided by thermoplastic polymers, whose consumption (about 80% of all synthetic polymers) is mostly attributable to packaging and containers, as well as the production of textile fibers [10]. Hence, plastics can be considered highly responsible for waste management issues, not only because of their extensive usage but also because of their short service life together with their long (bio)degradation time [11].

    In addition, a great universal worry is due to the plastics’ storage in landfills because of their easy accessibility in the environment. In particular, mismanaged plastic waste of polyethylene containers and Poly(Ethylene terephthalate) bottles of beverages, the most common polymers found in urban waste, leads to a huge amount of surface water and seabed marine litter [12].

    Poly(Ethylene terephthalate), generally labeled as PET, is a thermoplastic polymer of the polyesters family produced by the reaction of ethylene glycol and terephthalic acid under high temperatures and low vacuum pressure. The resulting polyester polymer is characterized by high strength and stiffness, low density, good creep behavior, high chemical resistance, and low cost [13].

    Today, PET is one of the world’s most commonly used and versatile materials. Global Poly(Ethylene terephthalate) production was 30.3 million tons in 2017 [14], while European PET demand was about 4 million tons in 2018, as compared to the global plastics production of nearly 360 million tons [9]. It is used for bottles, food containers, and synthetic fiber production. It is forecasted that 583 billion PET bottles will be produced in 2021 [15], and for this reason it could be considered one of the most responsible polymers in marine pollution [2]. PET is used not only in the food packaging and textile fields but also in agriculture, electrical applications, and several composite applications in combination with reinforcement fibers for various industrial and civil engineering applications that typically require higher strength and/or higher heat resistance [16][17][18]. Recently, the interest in fiber-reinforced PET has increased due to its benefits, as compared with thermoset composites, such as damage tolerance, high impact resistance, chemical and solvent resistance, unlimited shelf life, low storage costs, welding ability, and recyclability [19][20][21].

    Plastic pollution in the marine environment has recently been recognized as one of the most impacting threats for the environment, causing numerous hazardous and ecologically negative consequences, such as the entanglement of the marine species within the plastic or their ingestion [22][23]. In particular, juvenile fish, reptiles (i.e., turtles, etc.), and mammals often become entangled in plastic waste with consequent severe damage for the animal growth [24][25] and restriction of movement precluding them from correctly feeding and, in the case of mammals, breathing [26][27]. A wide variety of species have been reported to be harmfully crushed by plastic trash, such as for example marine birds [28][29], sea turtles [30], cetaceans [31], fur seals [24], sharks [25], and filter feeders [32]. Marine birds are very prone to the ingestion of plastic objects that they mistake for food [28][29]. Plastic ingested by these marine organisms remains in the digestive tract and can lead to reduced feeding stimuli, gastrointestinal obstruction, decreased secretion of gastric enzymes, and lower levels of steroid hormones, causing reproduction difficulties [5]. Specific classes of litter found in the oceans, involving the Antarctic [33], have been observed in the sea for at least four decades [34][35][36].

    Microplastics (MPs) are generally defined as polymer particles with a regular or irregular shape and a size ranging between 5 mm and 1 µm and are insoluble in water [37], while bigger particles, such as pellets, are called mesoplastics [26][38][39]. However, a clear and accepted terminology and classification is still under discussion, as well as a standardization of the plastic collection and analysis methods [40]. Microfibers (MFs), very fine fibres (approx. 3–10 μm in diameter), spun as endless filaments can be of both synthetic and natural origin. The size to diameter ratio is also quite high, on the order of 103, which is an additional crucial property of MFs [41]. The most common constituents of MPs include polyethylene (PE), polystyrene (PS), polyethylene terephthalate (PET), polyvinylchloride (PVC), and polypropylene (PP), [34][42][43]. MPs generally arise from the plastic pollution of seaside and beaches, deriving from fragmentation phenomena or from powders employed, for example, in cosmetics [44][45]. Both microplastic and mesoplastic litters can be eaten by marine species and, thus, can reach the marine food network. In contrast to macroscopic plastic litters, MPs on the seaside, seabed, or surface water, frequently combined with sand, are complicated to be stored and, at present, there is not an easy and universal method for the calculation of their amount [46]. Furthermore, the degradation of marine MPs due to prolonged external light exposure, mechanical abrasion, and biodegradation can cause the creation of nanoplastics (NPs) with sizes lower than 1 μm [47][48][49][50][51]. In particular, marine MPs were investigated by several researchers, and their presence has widely been proven in coastal environments [52][53][54]. The freshwater system is also considered a potential sink of MPs [55][56][57][58][59]. Zbyszewski and Corcoran [60] reported for the first time the presence of MPs in the freshwater system during the coastline of Lake Huron, Canada. Very recently, Li et al. [61] evidenced that there are different concentrations of MPs in Australia, Asia, North America, and Europe. The current literature underlines that MPs are found in every sea basin around the world, with higher concentrations occurring in intense human activity areas demonstrating that plastic debris transport can be extremely efficient and that the prediction of the plastics’ fate is of paramount importance [62]. Additionally, the study and modeling of the transport of MPs in the marine environment has attracting increasing interest [63]. MPs have been detected also in urban atmospheres as well as in remote and pristine environments, showing that atmospheric transport of MPs is also very significant [64][65].

    2. Poly(Ethylene Terephthalate) Microplastics

    Despite PET representing 10% of plastic production, its diffusion in marine litter is widely assessed according to public opinion and documented in the literature. The major sources of PET microplastics in the marine environment are bottles and fibers. Bottled water is one sector of the beverage industry that has recently experienced substantial growth, and the consumption of plastic bottles is expected to increase by 20% by 2021 [66]. It is estimated that 500 billion plastic bottles are used every year, but less than half are recycled [67]. Unfortunately, due to waste mismanagement and illegal dumping, PET bottles are highly present in the marine litter, despite PET being more widely recycled than other polymers. According to the report of Ocean Conservancy International Coastal Cleanup [68], plastic bottles are the third most littered item collected in 2019 around the world. Several beach litter surveys highlight the presence of PET bottles in coastal pollution, with different percentages depending on the climatic period, tourism exploitation, disposal regulation, etc. [69][70]. For instance, according to Simeonova and Chuturkova [71], plastic drink bottles represent by weight about 44% of the Bulgarian Black Sea coastal pollution. Brouwer et al. [72] performed social research in European countries bordering the Mediterranean Sea, Black Sea, and the North Sea. They reported that after cigarette butts, the most frequently recorded litter type by beach visitors is plastic bottles.

    Waste with a density higher than that of seawater sinks to the bottom of the sea. For this reason, PET bottles are abundant among deep-sea litter items, as reported for different geographical places, for example in the Caribbean Sea [73], the Mediterranean Sea [74][75], the East China Sea [76], etc. However, PET bottles with closed caps can float and make a long journey, as demonstrated by Duncan et al. [77], who released PET bottles, equipped with GPS and satellite tags, into the Ganges River and the Bay of Bengal. Carried by coastal currents, the bottles released into the ocean travelled long distances of up to 2845 km in 94 days before being dispersed. This demonstrates that plastic pollution is a truly global issue, as a plastic bottle dropped in a river or ocean can travel thousands of miles in a few months.

    Recently, PET fibers, which account for 70% of all synthetic fibers [78] with a global consumption of about 50 Mton/year [79], have been recognized as an emerging source of pollution. They are released in relatively large amounts in wastewaters of common laundry cycles and escape removal from wastewaters in treatment plants due to the very low dimensions (diameters in the 10–20 μm range and masses between 1.7 and 7.0 μg) [79]. PET fibers can generate microfibers through fragmentation and degradation. After entering freshwater and seawater, they may be transported by currents and turbulent hydrodynamic conditions before sinking in the water column [36] and ending up in marine sediments, where they can be ingested by aquatic organisms [80]. Geyer et al. [81] estimated that 5.6 Mt of synthetic microfibers were emitted from apparel washing between 1950 and 2016. Half of this amount was emitted during the last decade, with a compound annual growth rate of 12.9%.Despite PET being more widely recycled than other polymers, the recycling volume is quite different across countries depending on their policies. There are still several countries where PET recycling is low. Moreover, even if PET is recycled, illegal dumping in the sea is a big problem; additionally, a bottle made of recycled PET can be illegally dumped in the ocean, making all recycling efforts useless. Therefore, the high volume of production of PET and waste mismanagement make PET one of the most polluting plastic materials. The abundance of PET microplastics and their continuous degradation in the marine environment to nanoplastics have raised concerns due to their entering the food chain through multiple routes, increased bioavailability, their impact on low-trophic organisms through the uptake of toxic chemicals, and the increased risks for human health [82]. The issues related to PET MPs/NPs have been less studied than those related to more abundant polymers such as polyethylene (PE) or polystyrene (PS), but interest in research on this topic has been greatly increasing in the last three years, as proved by the very recent literature.


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