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Microplastics (MPs), which have recently threatened living organisms, are widely distributed throughout the world’s fresh waters, oceans, and seas. HDPEs and PETs are produced and used in significant quantities in plastics. High-density polyethylene (HDPE) and polyethylene terephthalate (PET), which can survive in the natural environment for many years, are resistant to thermal, mechanical, and biological effects. This study examined the current developments in the sources of high-density polyethylene microplastics (mHDPE) and polyethylene terephthalate microplastics (mPET), and their disposal and properties. mHDPE and mPET microplastics consist of several sources, including their debris that breaks down their waste into smaller pieces as a result of physical and chemical processes, as well as micro-sized pieces of plastic commonly applied in personal care products or synthetic textiles. mHDPE and mPET pollution has become an important environmental problem with the potential to harm human health by entering the human and animal food chain. mHDPEs and mPETs, which enter the living organism through ingestion, inhalation, and dermal contact in general, adversely affect the cellular mechanisms in different parts of the body. In addition, they are decomposed into free radicals by the effects of external factors such as light and temperature, as well as biological agents and chemical wastes in the environment, which significantly affects the sustainability of the ecological environment.
*Address all correspondence to: mikailolam@gmail.com;, 152120203@firat.edu.tr
1. Introduction
Microplastics (MP) are defined as smaller pieces of synthetic plastic polymers, which are between 1 μm and 5 mm [1, 2]. MPs are used in many areas such as personal care products and synthetic textile products. However, MPs, also formed by the breakdown of plastic waste in the environment, are a global concern in today’s world, where they are ubiquitous in all environmental environments [3]. They are commonly found in air, soil, and water [4, 5, 6]. MPs are highly discussed due to their adverse effects on the ecological environment, social economy, and human health. However, despite their negative effects on the environment, they are frequently used in fields such as medicine and industry. MPs are divided into two groups as primary and secondary [7]. The primary group is the industrial production of plastic microbeads of different sizes. These products are widely used in areas such as raw materials in the manufacturing industry, personal care products, and sandblasting media [8, 9]. The secondary MPs are formed both during the use of products and when plastic wastes are broken down into smaller sizes depending on weather conditions that are exposed to light, heat, and mechanical stress [10]. However, the properties of plastics such as thermal, mechanical, electrical, and physical may vary depending on the production processes and the raw material used [11, 12]. Therefore, their mechanical and chemical properties may vary. Zhang et al. [13] reported that the glass transition temperature (Tg), melting temperature (Tm), and tensile strength values of the polylactic acid (PLA) filament, which was purchased from the NatureWorks company, were 61°C, 153°C, and 84 MPa, respectively. Olam and Tosun [14] showed that Tg, Tm, and tensile strength values of PLA, which was purchased from the PLA Max company, were 66°C, 160°C, and 53 MPa, respectively.
Plastics are used effectively in almost all industries, including construction, packaging, textiles, transportation, education, electricity, electronics, consumer products, and industrial machinery [15, 16]. Since the use of plastics is increasing day by day, their production is also increasing [17, 18]. According to ASTM D883 80c, plastics are divided into two groups; they are thermoset plastics and thermoplastics according to their chemical and mechanical properties [19, 20]. Thermoplastics are resins that liquefy when heated and harden when cooled [21]. Thermosets, on the other hand, do not reform under heat and pressure after they are produced [22]. Thermosetting plastics are alkyds, amine, silicones, allylics, phenolics, epoxies, urethanes, and polyester [23]. Thermoplastics are polypropylene (PP), polyamide (PA), polycarbonate (PC), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polystyrene (PS), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyetherimide (PEI), polyamide imide (PAI), acrylic (PAA), acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), polyvinyl chloride (PVC), polyurethanes (PUR), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (Teflon) [24, 25, 26]. PP, LDPE, PVC, HDPE, and PET constituted significant proportions in the world plastic production in 2021 (Figure 1).
Figure 1.
Distribution of the global plastics production by type in 2021 [27].
HDPEs and PETs, which have a significant usage rate today, have an important ratio among the microplastics existing in the environment. The presence of mHDPE and mPET is commonly detected by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy [28, 29]. Removal of MPs is mostly done by coagulation, filtration, adsorption, oxidation, and photocatalysis methods. However, these methods are rarely used [30, 31]. There is a need to increase the prevalence of the use of the methods and to develop new methods. Due to their small size, MPs can easily enter the environment and living organisms through air and contact [32]. If these wastes are disposed of, it is obvious that it will have many negative effects on the environment and life.
Polyethylene is used commonly as several types that grouped by density. These are high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and very low-density polyethylene (VLDPE) [33]. The mechanical properties of PE are highly dependent on variables like its crystal structure, molecular weight, and extent and type of branching. Physical and thermal properties of HDPE are given in Table 1; mechanical and electrical properties are given in Table 2. Although the O2 permeability of HDPE is higher than most plastics such as PLA, PVC, PET, and PVDC, its water permeability is quite low [50]. The thermal conductivity of HDPE is about 0.5 W/mK at 23°C, while that of PLA, ABS, and PP is 0.2 W/mK, and PA is 0.3 W/mK [51]. However, its Tm temperature is 134°C, which is low compared to other plastics (>200°C) [52]. Although this limits HDPE’s use at high temperatures, it is still a thermoplastic with adequate mechanical and thermal properties for many applications. Although its tensile strength is as good as PA, PC, and PS, it is one of the polymers with the highest impact strength value [53]. Due to HDPE’s low water absorption (<0.4), high glass transition temperature (102°C) and hardness (94), satisfactory tensile strength (18 MPa), antibacterial properties, and chemical and UV resistance, it is widely used in the chemical and food packaging industry.
Polymers, which are used as one of the materials in the manufacture of implants, are one of the most popular synthetic materials [54]. They are preferred because of their low price, good electrical properties, chemical inertness, and easy processing [55]. PE is also used in the medical sector, both in the production of medical equipment and in the production of implants. HDPEs are commonly used for catheters, facial restoration, acetabular endoprosthesis, ear reconstruction, nasal dorsal augmentation, mandibular contours, facial contouring, orbital floor, and socket reconstruction (Figure 2a) [58, 59, 60, 61, 62, 63]. High-density polyethylene (HDPE) is also preferred as a low-cost alternative material to replace the lost tissue in living tissue (Figure 2b) [64].
Thermoplastic matrix composites are used in semi-structural and engineering applications. HDPE-based hollow particle-filled composite materials can be produced using the polymer injection molding process (Figure 3a) [70, 71]. In addition, HDPE is used in products such as storage boxes, beverage bottles, consumer electronics products, and cases for automotive molded parts. HDPE with good dielectric property is used as electronic material in the form of microduct (Table 2) (Figure 3b). HDPE is used as a pipe due to its good mechanical properties such as impact strength, hardness, and tightness (Tables 1 and 2). HDPE pipes, unlike ferrous pipe systems, does not corrode, so there is no structure that will create internal resistance against the liquid flowing through it (Figure 3c). Therefore, it is preferred due to features such as long service life, high flow capacity, and ease of assembly. In addition to good barrier properties against oxygen and water vapor, packaging materials must also have antibacterial properties to preserve the physicochemical and organoleptic properties of food and beverages [72]. Since HDPE meets these features, it has an important use in the packaging industry (Figure 3d).
PET is a thermoplastic with high resistance to most solvents, weak acids, and bases; strength; gloss; high impact resistance; and hardness [73]. It is also resistant to many other chemicals such as hexane, methanol, sulfur dioxide, and solutions with low acid concentrations [74, 75, 76]. The physical and chemical properties of PET are examined in Table 3; it is a valuable hydrocarbon containing 62% C, 4% H, and 34% O and has a high calorific value. PETs are self-extinguishing and have very low gas permeability, good adhesion and weldability, high hardness, good refractive index, and good resistance to ultraviolet [89]. They have very low O2 and water permeability compared to most plastics (PS, PVC, etc.) [97]. The thermal conductivity of PET is also very low compared to PLA, ABS, HDPE, PP, and PA. Although it is a fairly transparent and colorless material, it usually appears opaque and off-white as the thickness increases. Depending on the thermal and process conditions, it can be found in semicrystalline or amorphous form. Because of this, it may appear dull, white, or glassy. It depends on process parameters such as crystal structure, processing temperature, cooling rate, and stretching. Crystallization is an important parameter that affects the properties of polymers. The benzene ring in the main chain of PET provides both slow crystallization during cooling and hardness. This adversely affects the spinning process of high-speed fibers [98]. Glass transition temperature (Tg) is an important value that affects the material properties and potential applications of a polymer [99]. Mechanical properties (deformation modulus, etc.) and physical properties (density, volume, specific heat, etc.) of polymers in glass transition state are not. Due to the Tg temperature, PET loses its glassy property and becomes viscous at 67–80°C; its cold crystallization (Tcc) is in the range of 115–140°C, melting temperature is 248–250°C, and enthalpy of melting (∆Tm) is 35–50 J/g; its hot crystallization temperature (Tc) is 194–205°C, and its enthalpy (∆Tc) is 29–55 J/g (Table 3) [100]. PETs begin to thermally degrade at temperatures above 340°C [101]. Although the melting temperature (Tm) of PET is not as high as PEEK (334°C), it is higher than that of PP (170°C), LDPE (134°C), PS (106°C), and PVC (199°C) [102].
PETs have excellent mechanical properties, creep resistance, fatigue resistance, friction resistance, and dimensional stability over wide temperature ranges (Table 4) [99, 110]. However, the disadvantages of slow crystallization rate, machining difficulties, high molding temperature, and poor impact performance limit their use [111]. The storage modulus of PET, which is the plastic deformation energy of a polymeric material, is 2000–4200 MPa at 25°C and 242 MPa at 80°C [112]. Tensile strength, flexural strength, Young’s modulus, elongation at break, impact strength, flexural modulus, and hardness of PET are approximately 40–60 MPa, 55–100 MPa, 1000–3500 MPa, 19–46 MPa, 4.6 kJ/m2, 2000–3500 MPa, and 96, respectively (Table 4). PET’s tensile strength (26 MPa) at 77 K is higher than PA (14.5 MPa), PC (13.5 MPa), Teflon (4.3 MPa), and PVC (9.5 MPa), and its elongation at break value is higher than theirs [113].
Dielectric is an important property of insulating materials. When an ever-increasing voltage is applied to an insulating material, it eventually reaches a point where its electrical properties deteriorate, causing a drop in resistance, and it begins to lose dielectric strength. PET shows a dielectric property of 150–200 kV/cm (Table 4).
3.2 PET applications
PET has wide use in many fields (packaging, textile, medical, etc.) due to its satisfactory properties [114, 115, 116]. In fact, PETs that have completed their useful life (waste) are ground to micron sizes and used as concrete additives [117]. Micro PETs are generally produced and used in spherical and fibrous structures [118]. They are used in protective fabrics, filters, wound dressings, drug delivery, and scaffolds [119, 120, 121]. Because of PET’s properties such as biocompatibility, high uniformity, mechanical strength, and chemical resistance, it has been successfully used in vascular prostheses for large vascular grafts and in various surface modification methods to improve the cell adhesion properties (Figure 4a) [127]. PETs are also used in a variety of biomedical applications such as implants, heart valves, sutures, scaffolds, surgical nets, and urinary and blood circulation catheters [122, 128]. Micro PET fibers are the most widely used synthetic fibers in textile yarn production, and their consumption is expected to be 50 Mton/year by 2050 (Figure 4b) [129, 130]. However, although PET’s usage has become widespread in many special applications (Figure 4a and b), it is mostly used in food and beverage packaging (Figure 4c and d) [131].
HDPE microplastics (mHDPE) and PET microplastics (mPET) are discharged into the environment in two ways [132]. The first of these is that they are fabricated by producers in <5 mm dimensions in the form of granules, powders, or pellets for later use in applications [133]. During the production process and during their use in the application areas, they are discharged into the environment through the disposal in air, wastewater, and other waste. The second is formed by the degradation of HDPEs and PETs under environmental conditions, which have reached the end of their useful life and are collected directly into the environment as waste or in municipal waste collection areas [134]. In nature, HDPE and PETs are resistant to chemical degradation and take decades for theenvironmental residues to decompose completely [135]. This degradation is the reduction of molecular weight as a result of chemical changes in the structure of the polymer [136]. Waste HDPE and PET exposed to sunlight undergo photooxidation as a result of the absorption of high-energy wavelengths of the ultraviolet (UV) spectrum [137]. As long as decomposition continues in the presence of oxygen, temperature-dependent thermo-oxidative reactions may occur. In addition, degradation may occur due to both biological and mechanical stresses. As a result, these decomposed HDPE and PET wastes become brittle and gradually break up into smaller pieces of micron size [138].
Photodegradation is one of the common degradation processes of polymers, which provokes cross-linking and chain scission reactions [139]. In the photooxidation mechanism that occurs during the UV-irradiation period, first carbonyl groups are formed; then, vinyl and hydroxyl/hydroxyperoxide groups are formed, and these chemical changes can be observed by FTIR spectroscopy [140, 141]. In the FTIR spectra of HDPE, its peaks are occurred at 3300–3600 cm−1 of hydroxyl groups (∙OH), 1700–1800 cm−1 of carbonyl groups (>C〓O), and 1600–1650, 989 and 908 cm−1 of vinyl groups (∙C〓C∙) [142, 143]. The effect of UV irradiation on polymers, carbonyl, vinyl, and hydroxyl groups is studied as an indicator of polymer basic scission [144]. Since the main photooxidation product groups of HDPE are carbonyl and vinyl, the effect of UV radiation can be examined by looking at the carbonyl index and vinyl index [145]. When HDPEs in thin film form are exposed to UV irradiation at 280 nm at a light intensity of 500 W/m2 at 25°C and 50% constant relative humidity, the carbonyl and vinyl indexes increase over time [139, 142]. After 30 days, the carbonyl and vinyl indexes of HDPE increase significantly [61, 140, 144]. As a result, it can be said that waste HDPEs, which are exposed to UV irradiation in nature, start to decompose after 30 days and turn into smaller particles. However, the carbonyl index of PET does not change significantly over time [146]. It can be said that PET is more resistant to UV irradiation than HDPE. In short, waste PETs take more time to decompose in nature by UV irradiation compared to HDPE.
The degradation of plastics, which exist as waste in nature, by using microorganisms is of great interest. Biological agents (bacterial and fungal species) and their metabolic enzymes, which are abundant in nature, have different degradation abilities for natural and synthetic polymers [147]. The biodegradation process of HDPE in nature is quite slow [148]. Therefore, it is necessary to recover HDPE wastes by appropriate methods such as physical, chemical, and biological processes [149]. Moog et al. [150] highlighted the potential for biodegradation of waste PETs and stated that PET substrates under varying conditions have enzyme functionality, secretion, and production of recombinant proteins. Shabbir et al. [151], in their experimental study with PE, PET, and PP microplastics, stated that there was weight loss in all MPs, indicating structural, morphological, and chemical changes, and confirmed this situation with SEM and FTIR analyses. Farzi et al. [152] investigated the biodegradation of mPETs by streptomyces bacterial species at laboratory scale and stated that the degradation is slow compared to physicochemical methods, and additional physical/chemical methods should be applied to increase the degradation rate. The biodegradation of 500 m particle size HDPE under laboratory conditions is approximately 10% in 24 days [153].
Mechanical degradation of polymers is typically limited to chain scission [154]. As given in Tables 2 and 4, due to the good mechanical properties of PET and HDPE such as tensile strength and elongation at break, they are slow to decompose as waste by mechanical forces in nature.
However, although the mechanical, biological, and chemical degradation times of mPET and mHDPE, which exist as waste in nature, are long separately, this time becomes shorter when it is considered that they occur together. As the use of PET and HDPE increases day by day, it creates more waste in nature, and accordingly, more microplastics are formed.
4.1 The effect of mHDPE and mPET on nature and life
Plastics are the most useful synthetic polymers used in packaging industries, agriculture, household applications, and many similar applications [155]. The unpredictable use of these synthetic polymers leads to an ever-increasing accumulation of solid waste in the natural environment [156]. This causes soil and water pollution at alarming rates, affecting the natural system and creating various environmental hazards [157]. Plastics, which are resistant to environmental influences, are seen as an environmental threat. MPs, both leaching into the environment in micron sizes during the production and usage processes by the manufacturers and occurring as small-sized plastic particles by the degradation of plastics found as waste in the environment, can lead to potential ecotoxicological effects [158, 159]. In general, the densities of microplastics found in nature vary in the range of 0.8–2 gcm−3. The microplastic particle has the average weight of 12.5 μg, volume of 0.011 mm3, and density of 1.14 gcm−3 [160]. Therefore, MPs can enter the body through airborne inhalation and food intake, which exist in many places in atmospheric environments today. When inhaled, they may cause inflammation or other biological responses in the lung [161]. In addition, they can cause health effects such as genotoxicity, which is due to the desorption of pollutants associated with polycyclic aromatic hydrocarbons (PAH); reproductive toxicity, which is due to the plastic itself and additives (plasticizers, dyes, etc.); mutagenicity; and carcinogenicity [161, 162]. Khalid et al. [163] stated that there are various inorganic and organic chemicals absorbed on MPs and that this poses a greater threat to living things than to MPs. In addition, MPs affect some plant community structure [164]. Issac et al. [165] stated that PE (about 54%) is the most abundant microplastic floating in the ocean.
Cheng et al. [166] investigated the effect of HDPE (25 μm) and PP (13 μm) microplastics on earthworms (Metaphire guillelmi) using Nile red fluorescent staining and observed ingestion by earthworms exposed to HDPE and PP microplastics. PP microplastics significantly reduced bacterial diversity and changed the bacterial community structure in the soil. Bringer et al. [167] exposed oyster embryos to different sizes of mHDPE for 24 hours and observed that the mHDPEs bind to the locomotor eyelashes of oyster D-larvae, influencing the swimming activity and development of oyster D-larvae. Kim et al. [168] conducted an experimental study using the nematode caenorhabditis elegans and zebra fish to determine the effects of mHDPEs on human health. They stated that it affected caenorhabditis elegans reproduction and zebra fish larval death at a concentration of more than 200,000 particles/mL. Jemec et al. [169] observed that mpETs, formed by abrasion and washing of textiles, were ingested by daphnia magna and increased the death rate of daphnia magna in their guts. Shen et al. [170] observed that the higher the concentration of mPETs, the more pronounced was the negative effect on Drosophila, with reduced egg production of the female flies and lower lipid, glucose content, and starvation resistance of the male flies. Najahi et al. [170] studied the effects of mPETs on human bone marrow mesenchymal stromal cells and adipose mesenchymal stromal cells. They found that it caused an approximate 30% reduction in proliferating cells associated with the onset of senescence or an increase in apoptosis.
Existing studies on mPETs and mHDPEs show that there is a lot of evidence that these wastes have a negative impact on living life. However, this does not cover all living things. Weber et al. [171] investigated the effect of the freshwater invertebrate amphipod Gammarus pulex exposed to mPETs for 48 hours and observed that the survival, development, metabolism, and nutritional activity of Gammarus pulex did not change significantly depending on the amount of mPET and the age of Gammarus pulex.
Microplastics are pollutants that accumulate in large quantities in the environment with each passing day and cause significant pollution. In addition to leaking into the environment during the production and usage processes of MPs, they can be formed by the mechanical, thermal, and biological decomposition of plastics, which are discharged into the environment after the completion of their useful life. HDPE and PETs, which have significant usage and application areas among plastics, have a very long life in the natural environment due to their chemical and mechanical resistance. In the current studies, it was seen that mHDPEs and mPETs indirectly or directly affect the habitat characteristics of living things and basic ecosystem functions. mHDPEs and mPETs can affect the living organism in which they are infested directly with their function and properties, as well as with the impurities they absorb. Although mPETs and mHDPEs do not cover all living organisms in the world, they adversely affect life and the environment. However, more scientific studies are needed to predict this situation.
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Written By
Mikail Olam
Submitted: 03 November 2022Reviewed: 06 February 2023Published: 21 March 2023
Open access peer-reviewed chapter
