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Interaction Between Microplastics and Antibiotics in Aquatic Environments and the Characteristics of Composite Pollution Removal by Coagulation and Advanced Oxidation Methods

Mianmo Li , Minghao Sui

Progress in Chemistry ›› 2025, Vol. 37 ›› Issue (1) : 124 -132.

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Progress in Chemistry ›› 2025, Vol. 37 ›› Issue (1) : 124-132 DOI: 10.7536/PC240617
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Interaction Between Microplastics and Antibiotics in Aquatic Environments and the Characteristics of Composite Pollution Removal by Coagulation and Advanced Oxidation Methods
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Abstract

As public concern regarding the safety of drinking water continues growing, microplastics and antibiotics have emerged as new contaminants of interest within the field of water treatment. Microplastics and antibiotics not only pollute aquatic environments and endanger both aquatic life and human health, but their coexistence in water can also lead to physical and chemical interactions, such as adsorption. These interactions are influenced by various factors, including the morphology, functional groups, and aging degree of microplastics, as well as the pH, temperature, salinity, heavy metal ions, and organic macromolecules in the water. The resulting microplastic-antibiotic complex pollutants exhibit greater toxicity and are more challenging to remove. This review discusses the hazards of microplastics and antibiotics in water, their interaction mechanisms, and influencing factors. It also highlights the removal characteristics of complex pollutants using two typical water treatment technologies: coagulation and advanced oxidation. The principles and degradation effects of these treatment processes are analyzed in detail.

Contents

1 Introduction

2 Hazards of microplastic-antibiotic composite pollutants

3 Mechanisms of interaction between microplastics and antibiotics

4 Factors influencing the interaction between micro- plastics and antibiotics

5 Coagulation removal of microplastic-antibiotic composite pollution

6 Advanced oxidation degradation of microplastic- antibiotic composite pollution

7 Conclusion and outlook

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Keywords

microplastics / antibiotics / adsorption mechanisms / composite pollution / coagulation / advanced oxidation process

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Mianmo Li, Minghao Sui. Interaction Between Microplastics and Antibiotics in Aquatic Environments and the Characteristics of Composite Pollution Removal by Coagulation and Advanced Oxidation Methods. Progress in Chemistry, 2025, 37(1): 124-132 DOI:10.7536/PC240617

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1 Introduction

Microplastics (MPs) refer to plastic films, fragments, particles, and fibers with a particle size less than 5 mm[1]. The discarded plastics generated from human production and life degrade into smaller-sized microplastics through weathering, direct sunlight, and microbial decomposition. Microplastics not only have the persistent pollution characteristics of ordinary plastics but also, due to their small size and easy migration, can be widely distributed in the natural environment. Currently, microplastics have been detected in water bodies, the atmosphere, soil, and even in the human body[2]. The main types of microplastics detected in aquatic environments include polyethylene (PE), polyamide (PA), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), and polyethylene terephthalate (PET)[2-3]. Microplastics are difficult to be completely degraded in the natural environment and can stably exist in surface waters such as rivers and lakes for a long time. Rodrigues et al.[4] analyzed water samples from the Thames River in the UK and the Antu River in Portugal, and found microplastic pollution in both. Tong et al.[5] studied water samples from different cities in China and found that the main forms of microplastics in water were fibrous and fragmentary, with PP and PE being the predominant components. Microplastics can even enter groundwater[6]. Table 1 summarizes the specific pollution situations of microplastics in some freshwater bodies in China.
In recent years, with the detection of microplastics in tap water[12], the potential risks they pose to human health have garnered particular attention. Research suggests that, at current levels in drinking water, microplastics are unlikely to cause significant health damage in the short term, but this does not mean that their biological toxicity can be ignored[13]. Microplastics have been found in the human gastrointestinal system and lymphatic system[14]. Studies have shown that microplastics in the intestines can disrupt the balance of gut microbiota, leading to symptoms such as malnutrition and developmental delays in organisms[15]. Nanoscale microplastics can enter the circulatory system, spread throughout the body via the lymphatic system, and even penetrate biological membranes, causing inflammatory reactions and damaging immune cells[16]. In addition to their inherent biological toxicity, microplastics, due to their large specific surface area, easily adsorb heavy metals and persistent organic pollutants (POPs) from the environment, leading to complex contamination. This means that microplastics can transfer toxic organic compounds through the food chain to aquatic organisms, ultimately accumulating in the human body. The toxicity of composite pollutants formed by the combination of microplastics and organic pollutants is more complex than that of individual pollutants. This complexity arises from the composition of the composite pollutants and the interactions between the toxicity mechanisms of microplastics and different pollutants (synergistic, antagonistic, or enhancing), which may amplify their negative effects on organisms, triggering more severe molecular, cellular, and tissue changes[17]. Rochman et al.[18] found that the adsorption of POPs by microplastics in freshwater environments results in combined toxicity, disrupting the endocrine systems and damaging the reproductive systems of fish, potentially having a profound impact on fish reproduction. Additionally, after adsorbing POPs, microplastics can desorb them. It has been found that the amount of some POPs desorbed in the intestines of organisms is 30 times higher than in seawater[19]. Studying the processes of adsorption and desorption of other pollutants by microplastics and understanding the mechanisms of their interactions is essential for assessing the environmental risks of microplastics.
Antibiotics have been frequently detected in aquatic environments in recent years[20]. Based on their chemical structures, antibiotics can be broadly categorized into groups such as macrolides, tetracyclines, sulfonamides, and quinolones. In addition to their use in human medicine, antibiotics are also widely used as growth promoters in aquaculture, livestock farming, and fisheries, leading to a significant amount of antibiotics being discharged into natural water bodies in their original and metabolized forms, causing pollution[21]. After entering the aquatic environment, antibiotics undergo migration and transformation through various pathways, with adsorption being a key process in their environmental movement[22]. The adsorption of antibiotics onto environmental media is closely related to their own structural and functional group properties. Studies have shown that quinolone and tetracycline antibiotics, due to having more polar functional groups (carboxyl, hydroxyl), are easily adsorbed by particulate matter in the environment; whereas sulfonamide antibiotics, which typically have only two ionic functional groups (amide and aniline), have weaker adsorption capabilities[23].
Generally, the content of antibiotics in aquatic environments is relatively low and typically does not cause acute toxic effects on humans. However, under natural conditions, microorganisms find it difficult to degrade antibiotics, and most antibiotics can persist in water bodies for a long time. They accumulate through the food chain, eventually reaching critical levels in higher trophic level animals, causing damage[24]. Moreover, microorganisms in the natural environment are affected by antibiotics, with their physiological activities being inhibited and evolving towards developing resistance. Liu et al.[25] pointed out that antibiotics in the environment alter the community structure of microorganisms, eliminating individuals that have not developed resistance.
Accurately assessing the toxicity and environmental risks of microplastic-antibiotic composite pollutants and clarifying the interactions between microplastics and antibiotics are prerequisites for developing removal technologies for composite pollutants. Therefore, this paper analyzes the hazards of their composite pollution, systematically summarizes the interaction mechanisms between microplastics and antibiotics, and the factors affecting these interactions. The composite pollution of the two exhibits different characteristics in the process of removal during water treatment compared to individual pollution. This paper introduces the removal characteristics of microplastic-antibiotic composite pollution using two typical water treatment technologies (coagulation and advanced oxidation methods).

2 The Hazards Of Microplastic-Antibiotic Complex Pollutants

Microplastics in water bodies may act as carriers for antibiotics, and the combination of organic pollutants with microplastics can enhance their toxicity[26]. The composite pollution generated by microplastics and antibiotics is mainly due to the adsorption of antibiotics by microplastics, followed by their migration in the environment, which alters the spatial distribution of both[27]. This migration includes aquatic animals ingesting microplastics and simultaneously taking in antibiotics, leading to the accumulation of pollutants and an increase in toxicity. For example, Fonte et al.[28] found that the presence of PE microplastics in water enhanced the toxicity of cephalexin to goby fish, and the combined pollution affected the feeding performance and acetylcholinesterase levels of the goby fish, showing differences compared to single pollution. Antibiotics on microplastics directly influence the expression of antibiotic resistance genes (ARGs) in bacterial communities also adsorbed on the microplastics, thereby selecting for communities of antibiotic-resistant bacteria (ARBs)[29]. Studies have shown that the concentration of ARBs in biofilms aggregated on the surface of microplastics is 100 to 5,000 times higher than in the surrounding water environment[30].
Currently, most of the toxicity studies on microplastic-antibiotic composite pollutants have focused on aquatic organisms such as algae and fish. Zhang et al.[31] found that the combined exposure to roxithromycin (ROX) and aged microplastics inhibited the activity of Na+/K+-ATPase in the gills and kidneys of carp. The pathological effects on the liver, brain, and gills were also greater than those from exposure to ROX or microplastics alone. Han et al.[32] used three antibiotics—oxytetracycline (OTC), florfenicol (FLO), and sulfamethoxazole (SMX)—along with PS microplastics to study the impact of microplastic and antibiotic pollution on mussels. The results showed that, compared to single contaminants, the composite pollution exhibited synergistic immunotoxicity in mussels, leading to a decrease in hemocyte viability and downregulation of immune-related genes.

3 The Interaction Mechanism Between Microplastics And Antibiotics

The interaction between microplastics and antibiotics is mainly through adsorption[33]. This is because the amorphous regions of plastic polymers, with their disordered and highly mobile molecular arrangements, provide space for pollutants such as antibiotics to attach[34]. Hydrophobic interactions, π-π interactions, hydrogen bonds, van der Waals forces, and electrostatic interactions are the primary mechanisms by which microplastics bind to antibiotics[35].
Hydrophobic interactions are forces that occur in polar solvents (typically water). They cause two nonpolar solutes to come closer and aggregate[36]. Most microplastics in aquatic environments are hydrophobic, which makes hydrophobic interactions the primary mechanism for the binding of microplastics with organic pollutants such as antibiotics[37]. When discussing the adsorption capacity of microplastics for antibiotics, the equilibrium partition coefficient (Kd) between microplastics and water can be used to express it. The higher the Kd value, the stronger the hydrophobicity of the antibiotic[38]. Li et al.[39] studied the adsorption process of five antibiotics (sulfadiazine, amoxicillin, tetracycline, ciprofloxacin, and trimethoprim) on microplastics in both seawater and freshwater, and measured the corresponding Kd values. The results showed that the adsorption capacity of microplastics for different antibiotics is proportional to the hydrophobicity of the antibiotics.
Electrostatic interactions include electrostatic adsorption and electrostatic repulsion. When microplastics and antibiotic molecules carry opposite charges, electrostatic adsorption occurs; conversely, electrostatic repulsion happens[40]. The specific type of electrostatic force is determined by the environmental pH, the pKa of the antibiotics, and the point of zero charge (pHPZC) of the microplastics[41]. Razanajatovo et al.[42] studied the adsorption of three antibiotics (sulfamethoxazole, propranolol, and sertraline) by PE in freshwater environments. In the experiment, the solution's pH was approximately 6.85, while the pKa values of the three antibiotics were 1.90, 9.42, and 9.85, respectively. Therefore, sulfamethoxazole carried a negative charge, while propranolol and sertraline carried positive charges. The pHPZC of PE was 4.3, indicating that PE also carried a negative charge. The experimental results showed that PE indeed had a higher adsorption capacity for the two positively charged antibiotics, demonstrating the influence of electrostatic interactions on the adsorption of antibiotics.
π-π interactions, hydrogen bonds, and van der Waals forces are also commonly involved in the adsorption of antibiotics and microplastics, although these interactions are weaker than covalent bonds[43]. Studies have found that van der Waals forces exist between antibiotics and various types of microplastics[44]. As a special type of dispersion force derived from van der Waals forces, π-π interactions generally occur between microplastics and antibiotics containing aromatic structures or double bonds. For example, PS (polystyrene) microplastics can act as electron donors during the adsorption process, forming π-π interactions with pollutants containing benzene rings or double bonds, such as tetracycline[45]. The formation of hydrogen bonds can enhance the adsorption of hydrophilic pollutants by microplastics. Hydrogen bonds and polar interactions typically occur in the adsorption process involving aged microplastics, which contain more hydroxyl, carbonyl, and other groups, and hydrophilic organic pollutants[46]. In reality, the actual adsorption process is often facilitated by the combined action of several mechanisms. For instance, studies have found that the adsorption mechanism of nano-scale PS for quinolone antibiotics (such as levofloxacin and norfloxacin) includes hydrogen bonding, polar interactions, and electrostatic interactions[47]. Some of the adsorption mechanisms between microplastics and antibiotics are illustrated in Figure 1.

4 Factors Influencing the Interaction Between Microplastics and Antibiotics

The interaction between microplastics and antibiotics in water bodies is influenced by various factors. First, the impact of the microplastics themselves: the morphology and types of functional groups carried by different kinds of micro/nanoplastics vary greatly, which leads to differences in their mechanisms of interaction with antibiotics, thus affecting the adsorption effect. Guo et al.[48] conducted adsorption experiments on tylosin (TYL) using four types of microplastics (PE, PS, PVC, and PP), and the results showed that PVC had the best adsorption effect. The reason is that the surface of PVC has protrusions, and its structure is looser, providing more adsorption sites for antibiotics, thus exhibiting better adsorption capacity. Li et al.[39] found that when studying the adsorption effects of five antibiotics on different microplastics, PA had the strongest adsorption ability, due to its surface having more pores, and its functional groups being capable of forming hydrogen bonds, making it easier to adsorb antibiotics.
In addition to the morphology of microplastics, their particle size and whether they aggregate also affect their adsorption capacity for antibiotics. Generally speaking, the smaller the particle size of micro/nanoplastics, the larger the specific surface area, and the more adsorption sites available, leading to a stronger adsorption capacity[49]. The adsorption capacity of nano-PS for antibiotics is much higher than that of micro-PS, mainly due to the difference in specific surface area. However, as research progresses, it has been found that the adsorption capacity does not always increase with the decrease in the particle size of microplastics. Yu et al.[50] conducted an adsorption experiment of tetracycline using PE of different particle sizes. The results showed that as the particle size of PE decreased, its equilibrium adsorption amount of tetracycline gradually increased, but when the particle size reached the level of tens of nanometers, the adsorption amount instead decreased. This may be because when the particle size of micro/nano-PE is too small, its existence in water becomes unstable, and it tends to undergo aggregation reactions, forming larger aggregates, which leads to a decrease in the specific surface area, thereby affecting the adsorption effect.
Another influencing factor is the aging of microplastics themselves. Microplastics in the environment undergo changes in surface morphology under the influence of light, weathering, or environmental media[51]. Environmental factors such as high temperatures and oxygen can accelerate the aging of microplastics. After aging, the surfaces of micro- and nanoplastics develop numerous wrinkles and grooves, and their internal structures may also change, such as the formation of functional groups like hydroxyl, carboxyl, and carbonyl, which can also alter the crystallinity of the microplastics, ultimately leading to a series of changes in their chemical properties[52]. The crystallinity of aged microplastics decreases; generally, the lower the crystallinity, the stronger the adsorption capacity for hydrophobic organic pollutants. However, the newly formed carbonyl and carboxyl groups on the surface enhance the hydrophilicity of the microplastics, resulting in a greater adsorption capacity for hydrophilic pollutants than for hydrophobic ones[53]. The reason may be that the hydrogen bonding between oxygen-containing functional groups has a greater effect than the influence of crystallinity.
The influence of environmental conditions on the adsorption of microplastics and antibiotics, such as pH, temperature, salinity, and the presence of coexisting organic macromolecules, cannot be overlooked. In recent years, more and more attention has been paid to the impact of pH on the adsorption of antibiotics by microplastics. Zhang et al.[47] studied the effect of pH on the adsorption of quinolone antibiotics by nano-PS, finding that the adsorption amount first increased and then decreased with the increase in pH. This trend is related to the influence of pH on the surface charge of PS and the existence form of antibiotics. Puckowski et al.[54] investigated the effect of pH on the adsorption of norfloxacin onto different types of microplastics. The results showed that the maximum adsorption of norfloxacin on PE occurred at a pH of 4, while the maximum adsorption on PP and PVC was observed at a pH of 12. This variation in results due to changes in pH also indicates that pH affects the adsorption of microplastics and antibiotics through electrostatic interactions[55].
Temperature is also one of the main factors affecting adsorption efficiency. For most antibiotics, as water temperature decreases, the solubility of the antibiotics decreases and their hydrophobicity increases, making them more likely to be adsorbed by microplastics; when the temperature rises, the solubility of the antibiotics increases, and molecular thermal motion intensifies, making the adsorption less stable. However, Chen et al.[56] found that the adsorption of tylosin (TYL) by polyethylene (PE) increases with rising temperature. This is because the adsorption of TYL on PE disrupts the hydration shell around the microplastics, thereby increasing the system's entropy (an entropy-increasing process). Thus, raising the temperature can enhance the adsorption of TYL by PE. This also indicates that the effect of temperature is not absolute but depends on the properties of the microplastics and antibiotics themselves.Salinity can either promote or inhibit the adsorption of different organic pollutants. For antibiotics, it mainly manifests as an inhibitory effect by competing for adsorption sites. As salinity increases, since most microplastics carry a negative charge, positively charged ions (such as sodium, magnesium, and calcium ions) can attach to the surface of microplastics through electrostatic attraction, occupying adsorption sites and thus inhibiting the adsorption of antibiotics by microplastics. Positively charged ions may also replace the oxygen-containing groups on microplastics through electrostatic adsorption, hindering the formation of hydrogen bonds and reducing adsorption efficiency[57].The influence of large organic molecules is similar to that of salinity. Generally, soluble large organic molecules have a higher affinity for microplastics than antibiotics, but some organic substances can also promote the adsorption of antibiotics. Zhang et al.[58] found that humic acid significantly promoted the adsorption of oxytetracycline by polystyrene (PS) microplastics. The reason may be that humic acid acts as a bridge in the adsorption process through forces such as π-π conjugation and hydrogen bonding.
The impact of microplastic biofilms on the adsorption of antibiotics onto microplastics has also been a focus of attention in recent years. Microplastics in aquatic environments can provide a suitable substrate for the colonization of various microorganisms in water (including fungi, algae, protozoa, and bacteria, etc.), forming biofilms that are typically composed of multiple microorganisms and their secreted extracellular polymeric substances[59]. Both laboratory and field studies have shown that microplastic biofilms have a stronger adsorption capacity for antibiotics compared to pristine microplastics[60]. Wu et al.[61] found that after the formation of a biofilm on the surface of PE microplastics, new functional groups such as carbonyls were generated, which enhanced the hydrogen bonding between PE and ciprofloxacin, thereby increasing their adsorption. Extracellular polymeric substances produced by microorganisms, such as proteins and polysaccharides, can also enhance the biofilm's adsorption capacity for organic compounds through mechanisms like hydrophobic interactions[62].

5 Coagulation Removal Of Composite Pollution Of Microplastics And Antibiotics

Coagulation is a widely used conventional water treatment process, known for its mature technology, simple operation, and low cost. It also exhibits superior performance in the removal of microplastics. Generally, for composite pollutants of microplastics and antibiotics, the main mechanism of coagulation removal is charge neutralization. Coagulants neutralize the surface charges of the pollutants, reducing electrostatic repulsion, thus allowing them to aggregate into larger flocs that can be removed by sedimentation[63]. In laboratory conditions simulating the coagulation process for removing microplastics, the optimal removal rate can exceed 90%, but this is difficult to achieve in actual water treatment plants. Traditional aluminum and iron salt coagulants in water treatment plants have a removal efficiency of 29.70% to 70.70% for low-density microplastics (such as PE), while the removal rate for high-density microplastics (such as PS, PET) reaches 77.83% to 99.40%. This may be due to the more pronounced settling properties of high-density microplastics[64]. Compared to the treatment of single microplastic pollution, the situation with composite pollution of microplastics and antibiotics is more complex. The interactions between different components can alter the behavior of the pollutants, thereby having unpredictable effects on the coagulation process. Lu et al.[65] studied the coagulation removal of tetracycline and PET composite pollutants, finding that compared to the coagulation of PET and tetracycline alone, the removal rate of PET decreased by 9%, while the removal rate of tetracycline increased by 13%. To further understand the coagulation mechanism of microplastic-antibiotic composite pollutants, He et al.[66] conducted coagulation experiments using polyaluminum chloride (PAC) as the coagulant and polyacrylamide (PAM) as the coagulant aid for PE-norfloxacin (NOR). The results showed that compared to the treatment of PE or NOR alone, the presence of NOR significantly increased the removal rate of PE by about 19.5%; while the presence of PE slightly reduced the removal rate of NOR by about 4.1%. Analysis of the mechanism indicated that the main mechanisms for the coagulation removal of PE-NOR composite pollutants are charge neutralization, adsorption bridging, and sweep flocculation. In this process, the adsorption bridging effect of the PE-NOR-Al complex was the reason for the increased removal rate of PE, while PE reduced the removal rate of NOR through competitive charge neutralization. Figure 2 shows the specific PE/NOR removal mechanisms in the coagulation system.
The results show that the removal efficiency is better in neutral and weakly alkaline environments compared to weakly acidic environments. Moreover, metal ions such as Ca2+ and Mg2+ in water significantly reduce the removal rate of composite pollutants, which corroborates the influence of pH and salinity on the adsorption of microplastics and antibiotics mentioned above. When HA is present in the water, the removal rates of PE and NOR increase rapidly. As the concentration of HA increases from 0 to 10 mg/L, the removal rate of PE increases from 56.3% to 95.8%, and the removal rate of NOR increases from 20.4% to 51.1%. This is due to the interaction between HA and aluminum-based coagulants[67].

6 Advanced Oxidation Methods For The Degradation Of Microplastic-Antibiotic Complex Pollution

Advanced oxidation processes (AOPs) are a type of water treatment technology widely used for the degradation and removal of refractory pollutants in the environment, including Fenton oxidation, persulfate methods, and catalytic ozonation. The core principle of AOPs is to generate highly reactive free radicals with strong oxidizing properties that can decompose refractory organic pollutants into low-toxicity or non-toxic small molecules, and in some cases, directly degrade them into carbon dioxide and water[68]. Compared to traditional water treatment processes, AOPs have advantages such as high reactivity, broader application range, and more thorough treatment effects, making them particularly advantageous in the degradation of emerging contaminants.
The principle of the Fenton process is to generate hydroxyl radicals (HO·) through the catalysis of Fe2+ on H2O2. The advantages of this process include fast reaction speed, simplicity, and low energy consumption. Furia et al.[69] used an activated Fenton process to treat medical wastewater containing high concentrations of antibiotics, with significant results. As a non-selective radical, HO· not only attacks microplastics but also indiscriminately attacks other pollutants. Meanwhile, microplastics can adsorb Fe2+ and Fe3+ in water, acting as carriers, which may affect the removal efficiency of composite pollutants by the Fenton process. After treatment, the surface of the remaining microplastics will undergo further changes, altering their physicochemical properties[70]. Yao et al.[71] studied the impact of microplastics on the Fenton process for treating antibiotics, using polypropylene (PP) and sulfonamide antibiotics as experimental subjects. They characterized the changes in microplastics before and after Fenton process treatment using scanning electron microscopy (SEM). It was found that after the reaction, floc and debris adhered to the surface of the microplastics, and granular substances filled the pores. Energy dispersive X-ray spectroscopy (EDS) analysis showed that the relative contents of iron and sulfur on the surface of the microplastics increased from 0.35% to 1.81% and from 1.48% to 4.29%, respectively, after Fenton process treatment. These results indicate that microplastics indeed adsorb Fen+, sulfonamide antibiotics, and their derivatives such as Fen+ during the Fenton reaction, and the adsorption effect as a carrier is enhanced. The consumption of HO· by PP also affected the removal and mineralization rates of sulfonamide antibiotics, and the fragmentation, hydrophilicity, and adsorption capacity of PP itself were all increased.
Photocatalytic degradation, as a green pollutant treatment technology, has become a research hotspot in the field of microplastic and antibiotic pollution control in aquatic environments. Its principle is that under the irradiation of ultraviolet (UV) or visible light, the internal electrons of the catalyst gain energy and are excited to undergo transition. After the transition, there are photogenerated electrons (e-) and photogenerated holes (h+) inside the catalyst. The electron-hole pairs can directly participate in the redox degradation of pollutants, and they can also react with oxygen and water molecules to produce free radicals such as O2•− and HO·, which cleave polymer macromolecules and mineralize them into carbon dioxide and water[72]. The mechanism of photocatalytic degradation of microplastic-antibiotic composite pollution is shown in Figure 3.
Titanium dioxide (TiO2) is a commonly used ultraviolet photocatalyst. Nabi et al.[73] used ultraviolet light to irradiate TiO2 nanoparticle films for the catalytic oxidative degradation of PE and PS. The results showed that after 3-6 hours of irradiation, the morphology and size of PS changed significantly, and within 12 hours, 98.4% of 400 nm PS was completely mineralized. Infrared spectroscopy analysis indicated that microplastics were ultimately converted into CO2 through photocatalytic degradation. Fu et al.[74] found that K2S2O8 combined with ultraviolet light of wavelength < 270 nm could completely remove tetracycline at a concentration of 15 mg/L, degrading it into small molecular acids, CO2, etc. Ye[75] used a UV/H2O2 combined photocatalytic process to remove antibiotics from raw water. Compared with conventional and advanced treatment processes in water plants, the removal rates of tetracycline and sulfonamide antibiotics increased by 75.5% and 68.4%, respectively. As the UV irradiation dose increased, the removal rate of most antibiotics also significantly improved. Based on practical conditions, the recommended irradiation dose was 1400-1500 mJ/cm2. However, increasing the H2O2 dosage had little effect on the degradation efficiency, and the utilization rate decreased as the dosage increased. The optimal dosage determined experimentally was 3 mg/L.
Ultraviolet light-driven catalysts suffer from low utilization of light energy and a narrow wavelength absorption range, which has led to the expansion of research and development of visible light catalysts. Commonly used visible light catalysts currently include zinc oxide (ZnO), biochar, and organic semiconductors, which possess excellent optical properties. Jiang et al.[76] used a soluble BiOCl-OH semiconductor organic framework as a visible light catalyst, with a xenon lamp as the light source, to study the photocatalytic degradation of PS microplastics and tetracycline in a composite pollution system. The results showed that appropriate concentrations and sizes of PS promote the degradation of tetracycline and alter the degradation pathways. The presence of tetracycline promotes the aging of PS in the system, causing fragmentation on its surface, indicating a synergistic effect between the two in photocatalytic degradation. Mechanistic studies revealed that PS accelerates charge transfer and radical generation in the system, while tetracycline alters the interfacial charge distribution and enhances light absorption.
The photocatalytic degradation of microplastic-antibiotic composite pollution is influenced by factors such as the shape and particle size of the microplastics. Jiang et al.[76] studied the effect of different sizes (100 nm to 10 μm) of PS on the photocatalytic degradation of tetracycline, finding that the smaller the PS size, the better the adsorption effect on tetracycline, and the higher the degradation efficiency. External factors such as pH and temperature should also affect the photocatalytic degradation of composite pollutants, but research in this area is currently somewhat lacking.
In addition to hydroxyl radicals, advanced oxidation processes (AOPs) based on sulfate radicals (SO4•−) have received considerable attention in recent years. The common generation methods for SO4•− involve the activation of persulfate (PS) and peroxymonosulfate (PMS) through photocatalysis, transition metal catalysis, and other means. Compared with the Fenton process, persulfate oxidation has a wider pH application range[77]. Zhu et al.[78] used nanocomposites of FeCo2O4/Co3O4 to activate persulfate for tetracycline treatment, achieving a 91.63% removal rate of tetracycline within 120 minutes. Wei et al.[79] investigated the impact of PP and PE microplastics on the degradation of tetracycline hydrochloride (TCH) in a CoFe2O4/PMS AOP system. They found that when the concentration of PP and PE was 100 mg/L, it promoted TCH degradation by 4.3% and 3.5%, respectively, and unaged microplastics had a more significant promoting effect than aged ones. Fourier transform infrared spectroscopy (FTIR) analysis of the surface functional groups of PP and PE microplastics before and after the reaction revealed the appearance of new symmetrical/asymmetrical carboxyl and hydroxyl groups, indicating that the microplastics consumed radicals in the CoFe2O4/PMS system, competing with TCH; however, the microplastics also served as carriers for CoFe2O4, distributing the catalyst more evenly and enhancing TCH degradation, suggesting that the interactions between microplastics and antibiotics during AOPs may be complex[80]. Using liquid chromatography-mass spectrometry (LC-MS) to analyze the joint degradation products of PP, PE, and TCH, combined with chemical calculations, the degradation pathways of the composite pollutants were inferred: hydroxy substitution and double bond cleavage ring-opening were the main pathways, followed by de-acidification and radical addition. The results also indicated that the microplastics altered the molecular structure, electrophilic reaction sites, and free radical attack sites of TCH, thereby affecting its degradation pathway.

7 Conclusions and Prospects

In recent years, the hazards of microplastics and antibiotics in water bodies to the environment and human health have received widespread attention. Due to the structural characteristics of microplastics, they can act as carriers for antibiotics in the environment, adsorbing them. The main principles of adsorption between the two include hydrophobic interactions, hydrogen bonding, π-π interactions, van der Waals forces, and electrostatic interactions. The toxicity of the resulting microplastic-antibiotic complex pollutants may be even stronger. Factors affecting the adsorption of microplastics and antibiotics include the morphology and size of the microplastics themselves, environmental pH, temperature, salinity, and organic macromolecules.
The removal of microplastics and antibiotics in water is also becoming a hot topic in water treatment. As a traditional water treatment process, coagulation and sedimentation has shown excellent performance in removing microplastics/antibiotics. Advanced oxidation processes have also attracted the attention of scholars due to their good treatment effects and diverse oxidation methods. Commonly used advanced oxidation processes include Fenton oxidation, photocatalytic oxidation, and persulfate oxidation, among others. Analyzing the treatment effects of different processes on composite pollution and the various factors affecting the process is one of the current research focuses. It should be noted that existing water treatment processes are not specifically designed for the removal of microplastics and antibiotics in water, and most of the research on the removal of microplastics/antibiotics is still at the laboratory stage, far from large-scale application. Improving existing water treatment processes and advancing research on the removal of microplastic-antibiotic composite pollutants should be an important topic in future water treatment directions.

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Funding

National Natural Science Foundation of China(2019YFC0408801)

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