Characterization of the Morphological and Chemical Profile of Different Families of Microplastics in Samples of Breathable Air.

Microplastic (MP) contamination has become a problem of great interest to the community at large. The detection of these particles in different ecosystems and foods has been the subject of study. However, the focus of these investigations has been on the identification and quantification of PM by DSC and Pyr-GC/MS and not on how they are transported to reach the air we breathe. In this study, the values of morphological parameters for plastic particles in a range between 1 and 2000 µm, present in the breathable air of 20 neighborhoods in the city of Cartagena, Colombia, were obtained to determine the characteristics that make these particles airborne. The values of parameters were obtained, such as roundness, sphericity, curvature, and the convexity of the particle, as well as its compactness and size, which influence its transport through the air and its ability to be ingested and inhaled. The data obtained in this study allows for simulations and the analysis of the behavior of microplastics once in the environment to predict future settlements. The DSC showed us the melting temperatures of PP, PE, PET, and PS, the Pyr-GC/MS showed the fragmentation patterns, and the presence of these MPs in the samples was confirmed.

Identification and Quantification of Micro-Bioplastics in Environmental Samples by Pyrolysis-Gas Chromatography-Mass Spectrometry.

Bioplastics are materials that are biobased and/or biodegradable, but not necessarily both. Concerns about environmental plastic pollution are constantly growing with increasing demand for substituting fossil-based plastics with those made using renewable resource feedstocks. For many conventional bioplastics to completely decompose/degrade, they require specific environmental conditions that are rarely met in natural ecosystems, leading to rapid formation of micro-bioplastics. As global bioplastic production and consumption/use continue to increase, there is growing concern regarding the potential for environmental pollution from micro-bioplastics. However, the actual extent of their environmental occurrence and potential impacts remains unclear, and there is insufficient mass concentration-based quantitative data due to the lack of quantitative analytical methods. This study developed and validated an analytical method coupling pressurized liquid extraction and pyrolysis-gas chromatography-mass spectrometry combined with thermochemolysis to simultaneously identify and quantify five targeted micro-bioplastics (i.e., polylactic acid (PLA), polyhydroxyalkanoate, polybutylene succinate, polycaprolactone, and polybutylene adipate terephthalate (PBAT)) in environmental samples on a polymer-specific mass-based concentration. The recovery of spiked micro-bioplastics in environmental samples (biosolids) ranged from 74 to 116%. The limits of quantification for the target micro-bioplastics were between 0.02 and 0.05 mg/g. PLA and PBAT were commonly detected in wastewater, biosolids, and sediment samples at concentrations between 0.07 and 0.18 mg/g. The presented analytical method enables the accurate identification, quantification, and monitoring of micro-bioplastics in environmental samples. This study quantified five micro-bioplastic types in complex environmental samples for the first time, filling in gaps in our knowledge about bioplastic pollution and providing a useful methodology and important reference data for future research.

Quantification of microplastics in environmental samples via pressurized liquid extraction and pyrolysis-gas chromatography.

The quantification of microplastics (MP) in environmental samples is currently a challenging task. To enable low quantification limits, an analytical method has been developed combining pressurized liquid extraction (PLE) and pyrolysis GC-MS. The automated extraction includes a pre-extraction step via methanol followed by a subsequent PLE using tetrahydrofuran. For the most frequently used synthetic polymers polyethylene (PE), polypropylene (PP), and polystyrene (PS), limits of quantification were achieved down to 0.007 mg/g. Recoveries above 80% were attained for solid matrices such as soil and sediments. The developed method was applied for MP quantification in environmental samples such as sediment, suspended matter, soil, and sewage sludge. In all these matrices, PE and PP were detected with concentrations ranging from 0.03 to 3.3 mg/g. In sewage sludge samples, all three polymers were present with concentration levels ranging between 0.08 ± 0.02 mg/g (PP) and 3.3 ± 0.3 mg/g (PE). However, especially for solid samples, the analysis of triplicates revealed elevated statistical uncertainties due to the inhomogeneous distribution of MP particles. Thus, care has to be taken when milling and homogenizing the samples due to the formation of agglomerates. Graphical abstract.

Limited exposure of captive Australian marsupials to plastics.

The global concern regarding the ubiquitous presence of plastics in the environment has led to intensified research on the impact of these materials on wildlife. In the Australian context, marsupials represent a unique and diverse group of mammals, yet little is known about their exposures to plastics. This study aimed to assess the contamination levels of seven common plastics (i.e., polystyrene (PS), polycarbonate (PC), poly-(methyl methacrylate) (PMMA), polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE), and polyvinyl chloride (PVC)) in both the diet and faeces of kangaroos, wallabies and koalas sampled from a sanctuary in Northeastern Australia. Quantitative analysis was performed by pressurized liquid extraction followed by double-shot microfurnace pyrolysis coupled to gas chromatography mass spectrometry. Interestingly, the analysis of the food and faeces samples revealed the absence of detectable plastic particles; with this preliminary finding suggesting a relatively limited exposure of captive Australian marsupials to plastics. This study contributes valuable insights into the current state of plastic contamination in Australian marsupials, shedding light on the limited exposures and potential risks, and highlighting the need for continued monitoring and conservation efforts. The results underscore the importance of proactive measures to mitigate plastic pollution and protect vulnerable wildlife populations in Australia's unique ecosystems.

Mass quantification of nanoplastics at wastewater treatment plants by pyrolysis-gas chromatography-mass spectrometry.

Municipal wastewater treatment plants (WWTPs) play a crucial role in the collection and redistribution of plastic particles from both households and industries, contributing to their presence in the environment. Previous studies investigating the levels of plastics in WWTPs, and their removal rates have primarily focused on polymer type, size, shape, colour, and particle count, while comprehensive understanding of the mass concentration of plastic particles, particularly those <1 µm (nanoplastics), remains unclear and lacking. In this study, pyrolysis gas chromatography-mass spectrometry was used to simultaneously determine the mass concentration of nine selected polymers (i.e., polyethylene (PE), polypropylene (PP), polystyrene (PS), poly(ethylene terephthalate) (PET), nylon 6, nylon 66, polyvinylchloride (PVC), poly(methyl methacrylate) (PMMA) and polycarbonate (PC)) below 1 µm in size across the treatment processes or stages of three WWTPs in Australia. All the targeted nanoplastics were detected at concentrations between 0.04 and 7.3 µg/L. Nylon 66 (0.2-7.3 µg/L), PE (0.1-6.6 µg/L), PP (0.1-4.5 µg/L), Nylon 6 (0.1-3.6 µg/L) and PET (0.1-2.2 µg/L), were the predominant polymers in the samples. The mass concentration of the total nanoplastics decreased from 27.7, 18 and 9.1 µg/L in the influent to 1, 1.4 and 0.8 µg/L in the effluent, with approximate removal rates of 96 %, 92 % and 91 % in plants A, B and C, respectively. Based on annual wastewater effluent discharge, it is estimated that approximately 24, 2 and 0.7 kg of nanoplastics are released into the environment per year for WWTPs A, B and C, respectively. This study investigated the mass concentrations and removal rates of nanoplastics with a size range of 0.01-1 µm in wastewater, providing important insight into the pollution levels and distribution patterns of nanoplastics in Australian WWTPs.

Unscrambling why plastics aren't detectable in chicken eggs.

Several food groups have been reported to contain varying concentrations of plastics. This study was designed to quantitatively investigate for the first time in Australia the presence of plastics in store-bought chicken eggs. Three commonly consumed brands of free-range, free-range organic, barn-laid and backyard (home-laid) chicken egg samples were analyzed for seven common polymers (i.e., polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, poly-(methylmethacrylate) and polycarbonate)). Samples were extracted by enzyme digestion and pressurized liquid extraction, followed by quantitative analysis through double-shot microfurnace pyrolysis coupled to gas chromatography-mass spectrometry. No plastics were detected at concentrations >limit of detection (LOD) (from 0.04 µg/g for PS to 0.22 µg/g for PVC) in the egg samples analyzed, regardless of brand and category, suggesting limited exposure of Australians to plastics from consuming eggs This study provides valuable baseline data and underscores the importance of continued monitoring to ensure the safety and integrity of food supplies in the face of rising environmental plastic pollution.

Development and application of a novel extraction protocol for the monitoring of microplastic contamination in widely consumed ruminant feeds.

Plastics and, in particular, microplastics (MPs) (< 5 mm) are emerging environmental pollutants responsible for interconnected risks to environmental, human, and animal health. The livestock sector is highly affected by these contaminants, with 50-60 % of the foreign bodies found in slaughtered domestic cattle being recognized as plastic-based materials. Additionally, microplastics were recently detected inside ruminant bodies and in their feces. MPs presence in ruminants could be explained by the intensive usage of plastic materials on farms, in particular to store feeds (i.e. to cover horizontal silos and to wrap hay bales). Although feed could be one of the main sources of plastics, especially of microplastics, a specific protocol to detect them in ruminant feeds is not actually present. Hence, the aim of this study was to optimize a specific protocol for the extraction, quantification, and identification of five microplastic polymers (high-density polyethylene, low-density polyethylene, polyamide fibers/particles, polyethylene terephthalate and polystyrene) from feeds typically used in ruminant diets (corn silage, hay, high protein feedstuff and total mixed ration). Several combinations of Fenton reactions and KOH digestion were tested. The final extraction protocol involved a KOH digestion (60 °C for 24 h), followed by two/three cycles of Fenton reactions. The extraction recoveries were of 100 % for high-density, low-density polyethylene, polyamide particles, and polystyrene and higher than 85 % for polyethylene terephthalate and polyamide fibers. Finally, the optimized protocol was successfully applied in the extraction of microplastics from real feed samples. All the feeds contained microplastics, particularly polyethylene, thus confirming the exposure of ruminants to MPs.

Plastic pollution in Moreton Bay sediments, Southeast Queensland, Australia.

The mounting issue of plastic waste in the aquatic ecosystem is a growing source of concern. Most plastic waste originates on land and a significant proportion of this eventually finds its way into the marine environment, which is widely regarded as a major repository for plastic debris. Currently, there exists a substantial gap in our understanding of how much plastic, the main polymer types, and the distribution of plastic in the marine environment. This study aimed to provide information on mass concentrations of a range of plastics in the surface sediments in the semi-enclosed Moreton Bay, just offshore the large city of Brisbane, Southeast Queensland, Australia. Surface sediment samples were quantitatively analysed for a suite of 7 common plastic polymer types (i.e., polystyrene (PS), polycarbonate (PC), poly-(methyl methacrylate) (PMMA), polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE) and polyvinyl chloride (PVC)) using a pressurized liquid extraction (PLE) followed by double-shot microfurnace pyrolysis coupled to gas chromatography mass spectrometry (Pyr-GC/MS). The advantage of this approach is that it can measure plastics below the limit of visual detection. The study revealed that Σ7plastics were consistently present in the samples, although the concentrations displayed a wide range of concentrations from 3.3 to 2194.2 µg/g across different sites. Among the polymers analysed, PE and PVC were found at the highest concentrations, ranging from 2.3 to 1885.9 µg/g and 3.0-979.5 µg/g, respectively. Based on the average concentrations of plastics measured, the dry bulk density and volume of sediments within the top 10 cm of the bay, it was estimated that there is a minimum of 7000 t of plastics stored in the surface sediments of the bay. This study is the first to report the mass concentrations of identified plastics and identify the main polymer types in Moreton Bay. This is important information to develop management plans to reduce the plastic waste entering the coastal marine environment.

Mass quantification of microplastic at wastewater treatment plants by pyrolysis-gas chromatography-mass spectrometry.

Municipal wastewater treatment plants (WWTPs) are a central point of collection of plastic particles from households and industry and for their re-distribution into the environment. Existing studies evaluating levels of plastics in WWTPs, and their removal rates have reported and used data on polymer type, size, shape, colour, and number of plastic particles, while the total mass concentration of plastic particles (especially >1 µm) remains unclear and unknown. To address this knowledge gap, raw influent, effluent, and reference water samples from three WWTPs in Australia were collected to analyse the mass concentrations and removal rates of seven common plastics (>1 µm in size) across the treatment schemes. Quantitative analysis was performed by pressurized liquid extraction followed by pyrolysis coupled to gas chromatography mass spectrometry. Results showed that the total plastic content in the WWTPs raw influent samples was between 840 and 3116 µg/L, resulting in an inflow of between about 2.1 and 196.4 kg/day of the total measured plastics. Overall, >99 % by mass of the plastics entering the three WWTPs from the raw influent was removed during the pre-treatment stages, presumably ending up in the sewage sludge, which means emissions (via treated effluent) from the treatment plants are low. Compared with the raw influent, the plastic mass concentrations in the treated effluents (i.e., Class C, A, and final effluent) from the three WWTPs, as well as the reference water samples within their catchments were below the limits of reporting. Of the five quantified plastic types, polyethylene (PE, 76.4 %), and polyvinylchloride (PVC, 21 %) dominated by mass, while polyethylene terephthalate (PET, 1.9 %), polypropylene (PP, 0.4 %) and polymethyl methacrylate (PMMA, 0.3 %) accounted for a small proportion of the total. Overall, this study investigated the mass concentrations of plastic particles above 1 µm in wastewater and their removal, which provided valuable information regarding the pollution level and distribution characteristics of plastic polymers in Australian WWTPs.

Does size matter? Quantification of plastics associated with size fractionated biosolids.

This study investigated the occurrence and contribution of plastic particles associated with size fractionated biosolids to the total concentration in biosolids (treated sewage sludge) samples collected from 20 wastewater treatment plants (WWTP) across Australia. This was achieved through sequential size fractionation of biosolids samples to quantify the mass concentration of 7 common plastics across a range of biosolids size fractions, including below 25 µm which has not been assessed in many previous studies. Quantitative analysis was performed by pressurized liquid extraction followed by pyrolysis coupled to gas chromatography - mass spectrometry. Of the total quantified plastics (Σ7plastics), the greatest proportion (27%) of the total mass were identified in the nominal <25 µm sized biosolids fraction. Polyethylene dominated the polymer mass in every size fraction, even though profiles varied between WWTPs. When comparing the sum of all sites for each sized biosolids fraction, the plurality of the polyethylene, polyvinyl-chloride, polystyrene, polypropylene, polycarbonate, and polyethylene-terephthalate concentrations were associated with the smallest size fraction (<25 µm). We confirm for the first time the presence of plastic particles in biosolids below a size fraction that is not captured by many methods. This is important, because of the potential greater significance of plastics in the low sizes to environmental and human health.

A Novel Analytical Approach to Assessing Sorption of Trace Organic Compounds into Micro- and Nanoplastic Particles.

Assessing the sorption of trace organic compounds (TOrCs) into micro- and nanoplastic particles has traditionally been performed using an aqueous phase analysis or solvent extractions from the particle. Using thermal extraction/desorption-gas chromatography/mass spectrometry (TD-Pyr-GC/MS) offers a possibility to analyze the TOrCs directly from the particle without a long sample preparation. In this study, a combination of two analytical methods is demonstrated. First, the aqueous phase is quantified for TOrC concentrations using Gerstel Twister® and TD-GC/MS. Subsequently, the TOrCs on the particles are analyzed. Different polymer types and sizes (polymethyl methacrylate (PMMA), 48 µm; polyethylene (PE), 48 µm; polystyrene (PS), 41 µm; and PS, 78 nm) were analyzed for three selected TOrCs (phenanthrene, triclosan, and α-cypermethrin). The results revealed that, over a period of 48 h, the highest and fastest sorption occurred for PS 78 nm particles. This was confirmed with a theoretical calculation of the particle surface area. It was also shown for the first time that direct quantification of TOrCs from PS 78 nm nanoparticles is possible. Furthermore, in a mixed solute solution, the three selected TOrCs were sorbed onto the particles simultaneously.

Quantification of selected microplastics in Australian urban road dust.

Microplastics (1 - 5000 µm) are pervasive in every compartment of our environment. However, little is understood regarding the concentration and size distribution of microplastics in road dust, and how they change in relation to human activity. Within road dust, microplastics move through the environment via atmospheric transportation and stormwater run-off into waterways. Human exposure pathways to road dust include dermal contact, inhalation and ingestion. In this study, road dust along an urban to rural transect within South-East Queensland, Australia was analysed using Accelerated Solvent Extraction followed by pyrolysis Gas Chromatography-Mass Spectrometry (Pyr-GC/MS). Polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, poly (methyl methacrylate) and polyethylene were quantified. Microplastic concentrations ranged from ~0.5 mg/g (rural site) to 6 mg/g (Brisbane city), consisting primarily of polyvinyl chloride (29%) and polyethylene terephthalate (29%). Size fractionation (< 250 µm, 250-500 µm, 500-1000 µm, 1000-2000 µm and 2000-5000 µm) established that the < 250 µm size fraction contained the majority of microplastics by mass (mg/g). Microplastic concentrations in road dust demonstrated a significant relationship with the volume of vehicles (r2 = 0.63), suggesting traffic, as a proxy for human movement, is associated with increased microplastic concentrations in the built environment.

Plastics in biosolids from 1950 to 2016: A function of global plastic production and consumption.

Plastics are ubiquitous contaminants that leak into the environment from multiple pathways including the use of treated sewage sludge (biosolids). Seven common plastics (polymers) were quantified in the solid fraction of archived biosolids samples from Australia and the United Kingdom from between 1950 and 2016. Six plastics were detected, with increasing concentrations observed over time for each plastic. Biosolids plastic concentrations correlated with plastic production estimates, implying a potential link between plastics production, consumption and leakage into the environment. Prior to the 1990s, the leakage of plastics into biosolids was limited except for polystyrene. Increased leakage was observed from the 1990s onwards; potentially driven by increased consumption of polyethylene, polyethylene terephthalate and polyvinyl chloride. We show that looking back in time along specific plastic pollution pathways may help unravel the potential sources of plastics leakage into the environment and provide quantitative evidence to support the development of source control interventions or regulations.

New methodologies for the detection, identification, and quantification of microplastics and their environmental degradation by-products.

Sampling, separation, detection, and characterization of microplastics (MPs) dispersed in natural water bodies and ecosystems is a challenging and critical issue for a better understanding of the hazards for the environment posed by such nearly ubiquitous and still largely unknown form of pollution. There is still the need for exhaustive, reliable, accurate, reasonably fast, and cost-efficient analytical protocols allowing the quantification not only of MPs but also of nanoplastics (NPs) and of the harmful molecular pollutants that may result from degrading plastics. Here a set of newly developed analytical protocols, integrated with specialized techniques such as pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), for the accurate and selective determination of the polymers most commonly found as MPs polluting marine and freshwater sediments are presented. In addition, the results of an investigation on the low molecular weight volatile organic compounds (VOCs) released upon photo-oxidative degradation of microplastics highlight the important role of photoinduced fragmentation at a molecular level both as a potential source of hazardous chemicals and as accelerators of the overall degradation of floating or stranded plastic debris.

Polymer Identification and Specific Analysis (PISA) of Microplastic Total Mass in Sediments of the Protected Marine Area of the Meloria Shoals.

Microplastics (MPs) quantification in benthic marine sediments is typically performed by time-consuming and moderately accurate mechanical separation and microscopy detection. In this paper, we describe the results of our innovative Polymer Identification and Specific Analysis (PISA) of microplastic total mass, previously tested on either less complex sandy beach sediment or less demanding (because of the high MPs content) wastewater treatment plant sludges, applied to the analysis of benthic sediments from a sublittoral area north-west of Leghorn (Tuscany, Italy). Samples were collected from two shallow sites characterized by coarse debris in a mixed seabed of Posidonia oceanica, and by a very fine silty-organogenic sediment, respectively. After sieving at <2 mm the sediment was sequentially extracted with selective organic solvents and the two polymer classes polystyrene (PS) and polyolefins (PE and PP) were quantified by pyrolysis-gas chromatography-mass spectrometry (Pyr-GC/MS). A contamination in the 8-65 ppm range by PS could be accurately detected. Acid hydrolysis on the extracted residue to achieve total depolymerization of all natural and synthetic polyamides, tagging of all aminated species in the hydrolysate with a fluorophore, and reversed-phase high performance liquid chromatography (HPLC) (RP-HPLC) analysis, allowed the quantification within the 137-1523 ppm range of the individual mass of contaminating nylon 6 and nylon 6,6, based on the detected amounts of the respective monomeric amines 6-aminohexanoic acid (AHA) and hexamethylenediamine (HMDA). Finally, alkaline hydrolysis of the residue from acid hydrolysis followed by RP-HPLC analysis of the purified hydrolysate showed contamination by polyethylene terephthalate (PET) in the 12.1-2.7 ppm range, based on the content of its comonomer, terephthalic acid.

Airborne emissions of microplastic fibres from domestic laundry dryers.

An emission source of microplastics into the environment is laundering synthetic textiles and clothing. Mechanical drying as a pathway for emitting microplastics, however, is poorly understood. In this study, emissions of microplastic fibres were sampled from a domestic vented dryer to assess whether mechanical drying of synthetic textiles releases microplastic fibres into the surrounding air or are captured by the inbuilt filtration system. A blue polyester fleece blanket was repeatedly washed and dried using the 'Normal Dry' program of a common domestic dryer operated at temperatures between 56 and 59 °C for 20 min. Microfibres in the ambient air and during operation of the dryer were sampled and analysed using microscopy for particle quantification and characterisation followed by Fourier-Transform Infrared Spectroscopy (FTIR) and Pyrolysis Gas Chromatography-Mass Spectrometry (Pyr-GC/MS) for chemical characterisation. Blue fibres averaged 6.4 ± 9.2 fibres in the room blank (0.17 ± 0.27 fibres/m3), 8.8 ± 8.5 fibres (0.05 ± 0.05 fibres/m3) in the procedural blank and 58 ± 60 (1.6 ± 1.8 fibres/m3) in the sample. This is the first study to measure airborne emissions of microplastic fibres from mechanical drying, confirming that it is an emission source of microplastic fibres into air - particularly indoor air.

Identification and quantification of selected plastics in biosolids by pressurized liquid extraction combined with double-shot pyrolysis gas chromatography-mass spectrometry.

The identification and quantification of selected plastics (polystyrene (PS), polycarbonate (PC), poly-(methyl methacrylate) (PMMA), polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE) and polyvinyl chloride (PVC)) in biosolids (treated sewage sludge) was performed by pressurized liquid extraction (PLE) combined with double-shot pyrolysis gas chromatography-mass spectrometry. Validation of the method yielded recoveries of between 85 and 128% (mean RSD 11%) at a linear range of between 0.01 and 2 µg. The distribution of plastics within 25 biosolid samples from a single wastewater treatment plant in Australia was assessed. The mass concentration of PE, PVC, PP, PS and PMMA was between 0.1 and 4.1 mg/g dry weight (dw) across all samples, with a total plastic concentration Æ©Plastics of between 2.8 and 6.6 mg/g dw (median = 4.1 mg/g dw). PE was the predominant plastic detected (mean concentration of 2.2 mg/g dw), contributing to 50% of the total of all plastics. Overall, this study demonstrates that pressurized liquid extraction (PLE) combined with double-shot pyrolysis gas chromatography-mass spectrometry can be used to identify and quantify PE, PP, PVC, PS, and PMMA in biosolids.

Pyr-GC/MS analysis of microplastics extracted from the stomach content of benthivore fish from the Texas Gulf Coast.

Fish ingestion of microplastic has been widely documented throughout freshwater, marine, and estuarine species. While numerous studies have quantified and characterized microplastic particles, analytical methods for polymer identification are limited. This study investigated the applicability of pyr-GC/MS for polymer identification of microplastics extracted from the stomach content of marine fish from the Texas Gulf Coast. A total of 43 microplastic particles were analyzed, inclusive of 30 fibers, 3 fragments, and 10 spheres. Polyvinyl chloride (PVC) and polyethylene terephthalate (PET) were the most commonly identified polymers (44.1%), followed by nylon (9.3%), silicone (2.3%), and epoxy resin (2.3%). Approximately 42% of samples could not be classified into a specific polymer class, due to a limited formation of pyrolytic products, low product abundance, or a lack of comparative standards. Diethyl phthalate, a known plasticizer, was found in 16.3% of the total sample, including PVC (14.3%), silicone (14.3%), nylon (14.3%), and sample unknowns (57.2%).