Tracing the entry process of submicrometre plastics in soybean sprouts by leaf-derived fluorescent carbon dots.

As a global emerging contaminant, microplastics (MPs) in water or soil can accumulate in vegetables, making them easily ingested through the diet. With excellent and tunable optical properties, carbon dots (CDs) are highly advantageous for tracing the entry process of MPs. Originally, long-wavelength CDs were synthesized from leaf-derived extracts, and fluorescent submicrometer plastics (CDs-MPs) with clean surfaces and concentrated particle sizes were obtained by soap-free microemulsion polymerization. The concentration of CDs-MPs exhibits a significant linear relationship with long-wavelength fluorescence intensity (λEx/λEm: 415/676 nm). Soybean sprouts (SBS), as an important type of food, are susceptible to contamination of MPs due to their soft epidermis and rapidly growing biomass. The results showed that CDs-MPs could be embedded into the cortex of SBS and enter the plant with cell division and elongation, leading to an increase in pore size on the cell wall surface. After entering the root system, CDs-MPs will pass through the Casparian strip and migrate in the vessels. Then, CDs-MPs enter the leaves through vascular bundles, and the distribution and size of epicuticular wax on leaves have changed. Furthermore, SBS showed resistant growth and increased levels of oxidative response when exposed to MPs/CDs-MPs. It is the first study to demonstrate the application of leaf-derived CDs in the prevention of MPs pollution by revealing the migration behavior of submicrometre plastics in SBS.

Micro(nano)plastics: invisible compounds with a visible impact.

The plastic related research has been an epicentre in recent times. The presence and spread of micro (nano) plastics (MNPs) are well-known in the terrestrial and aquatic environment. However, the focus on the fate and remediation of MNP in soil and groundwater is limited. The fate and bioaccumulation of ingested MNPs remain unknown within the digestive tract of animals. There is also a significant knowledge gap in understanding the ubiquitous organic environmental pollutants with MNPs in biological systems. Reducing plastic consumption, improving waste management practices, and developing environmentally friendly alternatives are some of the key steps needed to address MNP pollution. For better handling and to protect the environment from these invisible substances, policymakers and researchers urgently need to monitor and map MNP contamination in soil and groundwater.

Biodegradability of bioplastics in different aquatic environments: A systematic review.

Bioplastics were first introduced as environmentally friendly materials, with properties similar to those of conventional plastics. A bioplastic is defined as biodegradable if it can be decomposed into carbon dioxide under aerobic degradation, or methane and CO2 under anaerobic conditions, inorganic compounds, and new cellular biomass, by the action of naturally occurring microorganisms. This definition however does not provide any information on the environmental conditions, timescale and extent at which decomposition processes should occur. With regard to the aquatic environment, recognized standards have been established to assess the ability of plastics to undergo biodegradation; however, these standards fail to provide clear targets to be met to allow labelling of a bioplastic as biodegradable. Moreover, these standards grant the user an extensive leeway in the choice of process parameters. For these reasons, the comparison of results deriving from different studies is challenging. The authors analysed and discussed the degree of biodegradability of a series of biodegradable bioplastics in aquatic environments (both fresh and salt water) using the results obtained in the laboratory and from on-site testing in the context of different research studies. Biochemical Oxygen Demand (BOD), CO2 evolution, surface erosion and weight loss were the main parameters used by researchers to describe the percentage of biodegradation. The results showed a large variability both in weight loss and BOD, even when evaluating the same type of bioplastics. This confirms the need for a reference range of values to be established with regard to parameters applied in defining the biodegradability of bioplastics.

Peptide-Decorated Microneedles for the Detection of Microplastics.

The escalating utilization of plastics in daily life has resulted in pervasive environmental pollution and consequent health hazards. The challenge of detecting and capturing microplastics, which are imperceptible to the naked eye, is exacerbated by their diminutive size, hydrophobic surface properties, and capacity to absorb organic compounds. This study focuses on the application of peptides, constituted of specific amino acid sequences, and microneedles for the rapid and selective identification of microplastics. Peptides, due to their smaller size and greater environmental stability compared with antibodies, emerge as a potent solution to overcome the limitations inherent in existing detection methodologies. To immobilize peptides onto microneedles, this study employed microneedles embedded with gold nanorods, augmenting them with sulfhydryl (SH) groups at the peptides' termini. The sensor developed through this methodology exhibited efficient peptide binding to the microneedle tips, thereby facilitating the capture of microplastics. Raman spectroscopy was employed for the detection of microplastics, with the results demonstrating successful attachment to the microneedles. This novel approach not only facilitates localized analysis but also presents a viable strategy for the detection of microplastics across diverse environmental settings.

Synergistic interaction between scrap tyre and plastics for the production of sulphur-free, light oil from fast co-pyrolysis.

Fast co-pyrolysis offers a sustainable solution for upcycling polymer waste, including scrap tyre and plastics. Previous studies primarily focused on slow heating rates, neglecting synergistic mechanisms and sulphur transformation in co-pyrolysis with tyre. This research explored fast co-pyrolysis of scrap tyre with polypropylene (PP), low-density polyethylene (LDPE), and polystyrene (PS) to understand synergistic effects and sulphur transformation mechanisms. A pronounced synergy was observed between scrap tyre and plastics, with the nature of the synergy being plastic-type dependent. Remarkably, blending 75 wt% PS or LDPE with tyre effectively eliminated sulphur-bearing compounds in the liquid product. This reduction in sulphur content can substantially mitigate the release of hazardous materials into the environment, emphasizing the environmental significance of co-pyrolysis. The synergy between PP or LDPE and tyre amplified the production of lighter hydrocarbons, while PS's interaction led to the creation of monocyclic aromatics. These findings offer insights into the intricate chemistry of scrap tyre and plastic interactions and highlight the potential of co-pyrolysis in waste management. By converting potential pollutants into valuable products, this method can significantly reduce the release of hazardous materials into the environment.

Microplastics derived from plastic mulch films and their carrier function effect on the environmental risk of pesticides.

Plastic film mulching can maintain soil water and heat conditions, promote plant growth and thus generate considerable economic benefits in agriculture. However, as they age, these plastics degrade and form microplastics (MPs). Additionally, pesticides are widely utilized to control organisms that harm plants, and they can ultimately enter and remain in the environment after use. Pesticides can also be sorbed by MPs, and the sorption kinetics and isotherms explain the three stages of pesticide sorption: rapid sorption, slow sorption and sorption equilibrium. In this process, hydrophobic and partition interactions, electrostatic interactions and valence bond interactions are the main sorption mechanisms. Additionally, small MPs, biodegradable MPs and aged conventional MPs often exhibit stronger pesticide sorption capacity. As environmental conditions change, especially in simulated biological media, pesticides can desorb from MPs. The utilization of pesticides by environmental microorganisms is the main factor controlling the degradation rate of pesticides in the presence of MPs. Pesticide sorption by MPs and size effects of MPs on pesticides are related to the internal exposure level of biological pesticides and changes in pesticide toxicity in the presence of MPs. Most studies have suggested that MPs exacerbate the toxicological effects of pesticides on sentinel species. Hence, the environmental risks of pesticides are altered by MPs and the carrier function of MPs. Based on this, research on the affinity between MPs and various pesticides should be systematically conducted. During agricultural production, pesticides should be cautiously selected and used plastic film to ensure human health and ecological security.

Revealing chemical release from plastic debris in animals' digestive systems using nontarget and suspect screening and simulating digestive fluids.

Plastic debris in the environment are not only pollutants but may also be important sources of a variety of contaminants. This work simulated kinetics and potential of chemical leaching from plastic debris in animals' digestive systems by incubating polyvinyl chloride (PVC) cord particles in artificial digestive fluids combined with nontarget and suspect screening based on UHPLC-Orbitrap HRMS. Impacts of particle size, aging, and digestive fluid were investigated to elucidate mechanisms of chemical leaching. Thousands of chemical features were screened in the leachates of PVC cord particles in the artificial digestive fluids, among which >60% were unknown. Bisphenol A (BPA) and bis(2-ethylhexyl) phthalate (DEHP) were the dominant identified CL1 compounds. Finer size and aging of the PVC particles and prolonged incubation time enhanced chemical release, resulting in greater numbers, higher levels, and more complexity in components of the released chemicals. The gastrointestinal fluid was more favorable for chemical leaching than the gastric fluid, with greater numbers and higher levels. Hundreds to thousands of chemical features were screened and filtered in the leachates of consumer plastic products, including food contact products (FCPs) in the artificial bird gastrointestinal fluid. In addition to BPA and DEHP, several novel bisphenol analogues were identified in the leachate of at least one FCP. The results revealed that once plastic debris are ingested by animals, hundreds to thousands of chemicals may be released into animals' digestive tracts in hours, posing potential synergistic risks of plastic debris and chemicals to plastic-ingesting animals. Future research should pay more attentions to identification, ecotoxicities, and environmental fate of vast amounts of unknown chemicals potentially released from plastics in order to gain full pictures of plastic pollution in the environment.

Production of hydrogen-rich fuel gas from waste plastics using continuous plasma pyrolysis reactor.

There is a serious concern about the large amount of accumulated plastic waste all around the world. Synthetic polymers such as polyethylene terephthalate (PET), polypropylene (PP), and polyethylene (HDPE, LDPE) are substantially present in the plastic waste generated. There are various methods reported to minimise such plastics waste with certain limitations. To overcome such limitations the present study have been carried out in which thermal decomposition of plastic waste of PET, PP, HDPE, and LDPE studied using a novel plasma pyrolysis reactor. The major objective of this work is to investigate the viability of the continuous plasma pyrolysis process for the treatment of various plastic wastes with respect to waste volume reduction and production of combustible hydrogen-rich fuel gas. The effect of temperature and feed flow rate on product gas yield, product gas efficiency, solid residue yield, and H2/CO ratio has been evaluated. The experiments have been carried out at different temperatures within the range of 700-1000 °C. Plasma pyrolysis system exhibited combustible hydrogen-rich gas as a product and solid residue. Liquid products have not been observed during plasma pyrolysis, unlike conventional pyrolysis. The reaction mechanism of plastic cracking has been discussed based on literature and products obtained in the present work. The effects of feed flow rate and temperature on exergy efficiency were studied using the response surface method. The mass, energy, and exergy analyses have also been carried out for all the experiments, which are in the range of 0.95-0.99, 0.48 to 0.77, and 0.30 to 0.69, respectively.

Deciphering the seasonal dynamics of microplastic morphotypes and associated co-contaminants along the northwest coast of India.

In the present study, the northwest coast of India, bordering the Arabian Sea, was selected to evaluate the microplastic (MP) abundance. This is the first study to emphasize the effects of different seasons on MP distribution. The collected MPs were dried, segregated, and evaluated based on their morphotype, size, color, and polymer type. A total of 1756.6, 7326.6, and 202 particles/kg of sand were estimated in the pre-monsoon, monsoon and post-monsoon seasons, respectively, with a dominance of polypropylene (PP) type of plastic in the pre-monsoon and high-density polyethylene (HDPE) in monsoon and post-monsoon seasons. HDPE and PP collected MPs during the monsoon season were further characterized for associated contaminants. Metal absorbance was detected using SEM-EDX mapping and ICP-MS. The presence of organic compounds (OCs) was analyzed using GC-MS. MPs exhibit distinct associations with metals, among which the HDPE pellet morphotype exhibits a higher range of metal adsorption. Total 61 different OCs were associated with MPs. The HDPE pellets contained the highest amounts of hydrophobic organic compounds. PP pellets were found to contain triglycerides, fatty aldehydes, and alkaloids, along with HOCs. Among morphotypes, pellet forms of MPs were found to adsorb more contaminants. These co-contaminants infiltrate the study area through sewage runoff and shoreline debris deposition, subsequently interacting with MPs. Furthermore, the MP diversity was studied by employing the MP diversity integrated index, which suggests that most of the MP diversity was observed in the pre-monsoon period. The pollution load index employed an MP risk assessment, which presented a low degree of MP contamination. In contrast, the polymer hazard index was calculated as 21650.3 in post-monsoon, placing the area under the extreme danger category. It is evident from the data that the types of MP is more important than their number. Thus, MP morphotypes have importance in the adsorption of co-contaminants.

Discrimination of plastic waste pyrolysis oil feedstocks using supercritical fluid chromatography.

Advanced chemical recycling techniques provide new avenues for handling and recycling mixed plastic waste; pyrolysis is a prominent approach involving heating plastic waste in an oxygen-free environment to create pyrolysis oils. Pyrolysis oils must be thoroughly characterized before being refined into fuels and chemical feedstocks. Here, a method based on supercritical fluid chromatography with ultraviolet detection was developed to analyze plastic waste pyrolysis oils. Multiple stationary phases were examined, and 2-ethyl pyridine was chosen as the best stationary phase for resolving pyrolysis oil components. Different standards and different plastic waste pyrolysis oils were compared across the different stationary phases. Up to three columns were serially coupled to increase efficiency and column capacity. It was found that a general method using ethanol as a modifier and two 2-ethyl pyridine columns could effectively resolve plastic waste pyrolysis oils. The potential for differentiating polyethylene and polypropylene feedstocks was demonstrated using principal component analysis.

Effects of primary leachates of conventional and alternative plastics in Cyprinodon variegatus fish larvae: Endocrine disruption and toxicological responses.

The inclusion of hazardous substances in the formulation of plastics raises significant concerns, particularly, if those substances are released as primary leachates during plastic degradation and/or fragmentation. In this sense, the production of degradable plastics holding deleterious additives can increase the release of harmful substances into the environment. Additionally, the effects of primary leachates of "eco-friendly" materials remain unexplored. To address this, we performed exposures to primary leachates of alternative polymers, and commercial bags to verify possible responses associated with endocrine disruption and/or activation of the detoxification pathway in larvae of the marine fish model Cyprinodon variegatus. The chemical characterization evidenced a great number of additives in the formulation of the materials analyzed in this study. Those include, except for the PLA sample, relevant levels of the hazardous phthalates DEHP and DiBP. Regarding the effects on marine fish larvae, exposure to leachates from alternative polymers (10 g/L) PHB and PHBV produced remarkable mortality (100%). While the exposure to bag leachates of all tested materials (1 and 10 g/L) produced alterations in biomarkers for steroidogenic and detoxification pathways. To a lesser extent (10 g/L), three materials produced significant alterations in estrogenic biomarkers (Home-compostable bag 1, LDPE and Recycled PE bags). Although the alterations in gene expression were not directly correlated to the amount of DEHP or DiBP, we can conclude that primary leachates of "eco-friendly" bags are harmful to marine vertebrates.

Advances in microbial exoenzymes bioengineering for improvement of bioplastics degradation.

Plastic pollution has become a major global concern, posing numerous challenges for the environment and wildlife. Most conventional ways of plastics degradation are inefficient and cause great damage to ecosystems. The development of biodegradable plastics offers a promising solution for waste management. These plastics are designed to break down under various conditions, opening up new possibilities to mitigate the negative impact of traditional plastics. Microbes, including bacteria and fungi, play a crucial role in the degradation of bioplastics by producing and secreting extracellular enzymes, such as cutinase, lipases, and proteases. However, these microbial enzymes are sensitive to extreme environmental conditions, such as temperature and acidity, affecting their functions and stability. To address these challenges, scientists have employed protein engineering and immobilization techniques to enhance enzyme stability and predict protein structures. Strategies such as improving enzyme and substrate interaction, increasing enzyme thermostability, reinforcing the bonding between the active site of the enzyme and substrate, and refining enzyme activity are being utilized to boost enzyme immobilization and functionality. Recently, bioengineering through gene cloning and expression in potential microorganisms, has revolutionized the biodegradation of bioplastics. This review aimed to discuss the most recent protein engineering strategies for modifying bioplastic-degrading enzymes in terms of stability and functionality, including enzyme thermostability enhancement, reinforcing the substrate binding to the enzyme active site, refining with other enzymes, and improvement of enzyme surface and substrate action. Additionally, discovered bioplastic-degrading exoenzymes by metagenomics techniques were emphasized.

Exploring the hidden environmental pollution of microplastics derived from bioplastics: A review.

Bioplastics might be an ecofriendly alternative to traditional plastics. However, recent studies have emphasized that even bioplastics can end up becoming micro- and nano-plastics due to their degradation under ambient environmental conditions. Hence, there is an urgent need to assess the hidden environmental pollution caused by bioplastics. However, little is known about the evolutionary trends of bibliographic data, degradation pathways, formation, and toxicity of micro- and nano-scaled bioplastics originating from biodegradable polymers such as polylactic acid, polyhydroxyalkanoates, and starch-based plastics. Therefore, the prime objective of the current review was to investigate evolutionary trends and the latest advancements in the field of micro-bioplastic pollution. Additionally, it aims to confront the limitations of existing research on microplastic pollution derived from the degradation of bioplastic wastes, and to understand what is needed in future research. The literature survey revealed that research focusing on micro- and nano-bioplastics has begun since 2012. This review identifies novel insights into microbioplastics formation through diverse degradation pathways, including photo-oxidation, ozone-induced degradation, mechanochemical degradation, biodegradation, thermal, and catalytic degradation. Critical research gaps are identified, including defining optimal environmental conditions for complete degradation of diverse bioplastics, exploring micro- and nano-bioplastics formation in natural environments, investigating the global occurrence and distribution of these particles in diverse ecosystems, assessing toxic substances released during bioplastics degradation, and bridging the disparity between laboratory studies and real-world applications. By identifying new trends and knowledge gaps, this study lays the groundwork for future investigations and sustainable solutions in the realm of sustainable management of bioplastic wastes.

Environmental condition-dependent effects of aquatic humic substances on the distribution of phenanthrene in microplastic-contaminated aquatic systems.

Numerous studies have focused on the interaction between microplastics (MPs) and phenanthrene (PHE) in aquatic environments. However, the intricate roles of aquatic humic substances (HS), which vary with environmental conditions, in influencing PHE-MP interactions are not yet fully understood. This study investigates the variable and environmentally sensitive roles of HS in modifying the interactions between PHE and polyethylene (PE) MPs under laboratory-simulated aquatic conditions with varying solution chemistry, including pH, HS types, HS concentrations, and ionic strength. Our findings show that the presence of HS significantly reduces the adsorption of PHE onto both pristine and aged PE MPs, with a more pronounced reduction observed in aged PEs. This effect is highlighted by a notable decrease in the partitioning coefficient (Kd) of PHE, which falls from 2.60 × 104 to 1.30 × 104 L/kg on MPs in the presence of HS. The study also demonstrates that alterations in the net charge of HS solutions are crucial in modifying PHE distribution onto PEs. An initial decrease in Kd values at higher pH levels is reversed when HS is introduced. Furthermore, an increase in HS concentrations is associated with lower Kd values. In conditions of higher ionic strength, the retention of PHE by HS is intensified, likely due to an enhanced salting-out effect. This research highlights the significant role of aquatic HS in modulating the distribution of PHE in MP-polluted waters, which is highly influenced by various solution chemistry factors. The findings are vital for understanding the fate of PHE in MP-contaminated aquatic environments and can contribute to refining predictive models that consider diverse solution chemistry scenarios.

Rapid biodegradation of microplastics generated from bio-based thermoplastic polyurethane.

The accumulation of microplastics in various ecosystems has now been well documented and recent evidence suggests detrimental effects on various biological processes due to this pollution. Accumulation of microplastics in the natural environment is ultimately due to the chemical nature of widely used petroleum-based plastic polymers, which typically are inaccessible to biological processing. One way to mitigate this crisis is adoption of plastics that biodegrade if released into natural environments. In this work, we generated microplastic particles from a bio-based, biodegradable thermoplastic polyurethane (TPU-FC1) and demonstrated their rapid biodegradation via direct visualization and respirometry. Furthermore, we isolated multiple bacterial strains capable of using TPU-FC1 as a sole carbon source and characterized their depolymerization products. To visualize biodegradation of TPU materials as real-world products, we generated TPU-coated cotton fabric and an injection molded phone case and documented biodegradation by direct visualization and scanning electron microscopy (SEM), both of which indicated clear structural degradation of these materials and significant biofilm formation.

Biodegradable plastics fragments induce positive effects on the decomposition of soil organic matter.

The escalating accumulation of plastic waste in ecosystems poses a significant health concern to soil environment, yet the environmental effects of plastics remains largely unexplored. Biodegradable plastics could offer a viable alternative to conventional persistent plastics, but our understanding of their potential benefits or detrimental effects on the decomposition of plant debris by soil biomass is limited. In this study, we conducted a year-long field experiment to examine the environmental response and impact on plant debris decomposition in the presence of varying quantities of persistent versus biodegradable plastics. Our findings indicate that the decomposition rate decreased by 2.8-4.9% for persistent plastics, while it increased by 1.3-4.2% for biodegradable plastics. Persistent plastics primarily induced adverse effects, including a reduction in soil nutrients, microbial diversity, bioturbation, enzyme activity, easily decomposable carbon, and microbial biomass carbon in plant debris. In contrast, biodegradable plastics resulted in beneficial effects such as an increase in enzyme activity, microbial biomass carbon, and easily decomposable carbon. We also observed that the decomposition rate of plant residues and nutrient release are closely associated with changes in the organic carbon chemical structure induced by different plastic film fragments. A significant shift in alkoxy carbon content facilitated the release of nutrients and soluble carbon, while modifications in carboxyl and aromatic carbon content hindered their release. Overall, our study reveals over one year that biodegradable plastics primarily induce positive effects on the decomposition of soil organic matter.

A non-invasive method of microplastics pollution quantification in green sea turtle Chelonia mydas of the Mexican Caribbean.

Due to the amply exposure of marine turtles to marine plastic pollution, this is a reason that the green sea turtle Chelonia mydas makes a good candidate species as a bioindicator for plastic pollution. Turtle feces were collected at Isla Blanca on the northeast Caribbean coast of the Yucatan Peninsula, Mexico. Microplastic extraction was done following Hidalgo-Ruz et al. (2012) and Masura et al. (2015) methods. After organic matter degradation of the feces samples, microplastics were identified and quantified by stereomicroscope. Their morphostructure was analyzed by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, while their composition was determined by Fourier transform infrared spectroscopy and Raman spectroscopy. Microplastics (MP) abundance ranged from 10 ± 2 MP·g-1 to 89 ± 3 MP·g-1. Kruskal Wallis test (KW = 70.31, p < 0.001) showed a significant difference between 22 green turtles analyzed. Most of the microplastics were fiber type. Blue, purple, and transparent fibers were the most abundant. The identified microplastics were nylon (polyamide), PVC, polypropylene, polyester, and viscose (cellulose). The non-invasive method used here allowed the detection of microplastic pollution and is promising for long-term microplastic pollution monitoring.

Microplastic shape influences fate in vegetated wetlands.

Coastal areas are prone to plastic accumulation due to their proximity to land based sources. Coastal vegetated habitats (e.g., seagrasses, saltmarshes, mangroves) provide a myriad of ecosystem functions, such as erosion protection, habitat refuge, and carbon storage. The biological and physical factors that underlie these functions may provide an additional benefit: trapping of marine microplastics. While microplastics occurrence in coastal vegetated sediments is well documented, there is conflicting evidence on whether the presence of vegetation enhances microplastics trapping relative to bare sites and the factors that influence microplastic trapping remain understudied. We investigated how vegetation structure and microplastic type influences trapping in a simulated coastal wetland. Through a flume experiment, we measured the efficiency of microplastic trapping in the presence of branched and grassy vegetation and tested an array of microplastics that differ in shape, size, and polymer. We observed that the presence of vegetation did not affect the number of microplastics trapped but did affect location of deposition. Microplastic shape, rather than polymer, was the dominant factor in determining whether microplastics were retained in the sediment or adhered to the vegetation canopy. Across the canopy, microfibre concentrations decreased from the leading edge to the interior which suggests that even on a small-scale, vegetation has a filtering effect. The outcome of this study enriches our understanding of coastal vegetation as a microplastics sink and that differences among microplastics informs where they are most likely to accumulate within a biogenic canopy.

Mechanistic interpretation of the sorption of terbuthylazine pesticide onto aged microplastics.

Microplastics (MPs) pose a global concern due to their ubiquitous distribution. Once in the environment, they are subject to aging, which changes their chemical-physical properties and ability to interact with organic pollutants, such as pesticides. Therefore, this study investigated the interaction of the hydrophobic herbicide terbuthylazine (TBA), which is widely used in agriculture, with artificially aged polyethylene (PE) MP (PE-MP) to understand how aging affects its sorption. PE was aged by an accelerated weathering process including UV irradiation, hydrogen peroxide, and ultrasonic treatment, and aged particles were characterized in comparison to pristine particles. Sorption kinetics were performed for aged and pristine materials, while further sorption studies with aged PE-MP included determining environmental factors such as pH, temperature, and TBA concentration. Sorption of TBA was found to be significantly lower on aged PE-MP compared to pristine particles because aging led to the formation of oxygen-containing functional groups, resulting in a reduction in hydrophobicity and the formation of negatively charged sites on oxidized surfaces. For pristine PE-MP, sorption kinetics were best described by the pseudo-second-order model, while it was intra-particle diffusion for aged PE-MP as a result of crack and pore formation. Sorption followed a decreasing trend with increasing pH, while it became less favorable at higher temperatures. The isotherm data revealed a complex sorption process on altered, heterogeneous surfaces involving hydrophobic interactions, hydrogen bonding, and π-π interactions, and the process was best described by the Sips adsorption isotherm model. Desorption was found to be low, confirming a strong interaction. However, thermodynamic results imply that increased temperatures, such as those resulting from climate change, could promote the re-release of TBA from aged PE-MP into the environment. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed TBA sorption onto PE.

Development and validation of an analytical pyrolysis method for detection of airborne polystyrene nanoparticles.

Microplastic is ubiquitous in the environment. Recently it was discovered that microplastic (MP, 1 µm-5 mm) contamination is present in the atmosphere where it can be transported over long distances and introduced to remote pristine environments. Sources, concentration levels, and transportation pathways of MP are still associated with large uncertainties. The abundance of atmospheric MP increases with decreasing particle size, suggesting that nanoplastics (NP, <1µm) could be of considerable atmospheric relevance. Only few analytical methods are available for detection of nanosized plastic particles. Thermoanalytical techniques are independent of particle size and are thus a powerful tool for MP and NP analysis. Here we develop a method for analysis of polystyrene on the nanogram scale using pyrolysis gas chromatography coupled to mass spectrometry. Pyrolysis was performed using a slow temperature ramp, and analytes were cryofocused prior to injection. The mass spectrometer was operated in selected ion monitoring (SIM) mode. A lower limit of detection of 1±1 ng and a lower limit of quantification of 2±2 ng were obtained (for the trimer peak). The method was validated with urban matrices of low (7 µg per sample) and high (53 µg per sample) aerosol mass loadings. The method performs well for low loadings, whereas high loadings seem to cause a matrix effect reducing the signal of polystyrene. This effect can be minimized by introducing a thermal desorption step prior to pyrolysis. The study provides a novel analysis method for qualitative and semi-quantitative analysis of PS on the nanogram scale in an aerosol matrix. Application of the method can be used to obtain concentration levels of polystyrene in atmospheric MP and NP. This is important in order to improve the understanding of the sources and sinks of MP and NP in the environment and thereby identify routes of exposure and uptake of this emerging contaminant.