Bioaccumulation and dietary bioaccessibility of microplastics composition and cocontaminants in Mediterranean mussels.

Microplastics (MPLs) are contaminants of emerging concern (CECs) ubiquitous in aquatic environments, which can be bioaccumulated along the food chain. In this study, the accumulation of polyethylene (PE), polystyrene (PS) and polyethylene terephthalate (PET) microplastics (MPLs) of sizes below 63 µm was assessed in Mediterranean mussels (Mytilus galloprovincialis spp). Moreover, the potential of mussels to uptake and bioaccumulate other organic contaminants, such as triclosan (TCS) and per- and polyfluoroalkyl substances (PFASs), was evaluated with and without the presence of MPLs. Then, the modulation of MPLs in the human bioaccessibility of co-contaminants was assessed by in vitro assays that simulated the human digestion process. Exposure experiments were carried out in 15 L marine microcosms. The bioaccumulation and bioaccessibility of PE, PS, PET, and co-contaminants were assessed by means of liquid chromatography -size exclusion chromatography-coupled to high-resolution mass spectrometry (LC(SEC)-HRMS). Our outcomes confirm that MPL bioaccumulation in filter-feeding organisms is a function of MPL chemical composition and particle sizes. Finally, despite the lower accumulation and bioaccumulation of PFASs in the presence of MPLs, the bioaccessibility assays revealed that PFASs bioaccessibility was favoured in the presence of MPLs. Since part of the bioaccumulated PFASs are adsorbed onto MPL surfaces by hydrophobic and electrostatic interactions, these interactions easily change with the pH during digestion, and the PFASs bioaccessibility increases.

Exposure to micro(nano)plastics polymers in water stored in single-use plastic bottles.

Human exposure to micro (nano)plastics (MNPLs) has become a significant concern as a potential health threat. Exposure routes include ingestion, inhalation, and dermal contact, being food and drinking water the primary sources of oral exposure. Here we present the quantification of polymers of MNPLs particles from 700 nm to 20 µm in bottled water commercialised in Spain, including an estimation of the potential risk for daily consumers. We evaluated samples from 20 popular brands in 0.5 and 1.5 L plastic bottles. A double-suspect screening approach developed and validated in our research group for drinking water was adapted for bottled water samples. The identification and quantification of MNPLs-polymers in mass units and the tentative identification of plastic additives (PA) until the second level of confidence was carried out based on high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS). The results showed the presence of polypropylene (PP), polyethylene (PE) and polypropylene terephthalate (PET) in the samples. Among them, PE was the most frequently detected and quantified polymer (55% of samples) followed by PET which was detected in 33% of the samples and showing the highest concentration (4700 ng L-1). The median value of the sum of polymer concentrations was 359 ng L-1. In addition, 28 plastic additives were detected, where at least one of them was present in 100% of the samples. Stabilizers and plasticisers were the most frequently identified. A prioritisation study was performed using a multi-QSAR modelling software, where bis(2-ethylhexyl) adipate and bis(2-ethylhexyl) phthalate were estimated as the most potentially harmful compounds for human health. Overall, findings suggest that bottled water is a non-negligible route to exposure to MNPLs.

Micro(nano)plastics in the atmosphere of the Atlantic Ocean.

The occurrence, long-range atmospheric transport and deposition of micro and nano plastics (MNPLs) remains un-quantified for the oceanic atmosphereopen ocean. Here we show the characterisation of MNPLs and the aerosol composition (PM10) in a north-south Atlantic transect from Vigo (Spain) to Punta Arenas (Chile). The analytical procedure to assess the composition of MNPLs consisted of a double suspect screening approach of the polymers and additives, the two constituents of plastics. Polymers were analysed by size exclusion chromatography coupled with high-resolution mass spectrometry using an atmospheric pressure photoionization source operated in positive and negative conditions (HPLC(SEC)-APPI(+/-)-HRMS). Plastic additives were screened with high-performance liquid chromatography coupled to high-resolution mass spectrometry using an electrospray ionisation source (HPLC-ESI(+/-)-HRMS). The most common polymers were polyethylene (PE), polypropylene (PP), polyisoprene (PI), and polystyrene (PS), with the highest polymer concentration being 51.7 ng·m-3 of PI. The air mass back trajectories showed the variable influence of oceanic and terrestrial air masses. These differences were reflected in the aerosol composition with different contributions of Saharan dust, sea spray aerosol, organic/elemental carbon, and MNPLs. Results showed that samples largely influenced by sea-spray and air masses originating from coastal South America and the north Atlantic subtropical gyre were more contaminated by MNPLs. Moreover, this information was complemented by the characterisation of the largest particles using scanning electron microscopy (SEM) and µ-Fourier Transform Infrared Spectroscopy (µ-FTIR). This work provides the first field evidence of the long-range transport of MNPLs in most of the Atlantic Ocean, as the result of dynamic coupling between the lower atmosphere and the surface ocean. Sea-spray formation arises as a key driver for the aerosolisation of MNPLs, and atmospheric transport followed by dry deposition may modulate the occurrence of MNPLs in large oceanic regions, issues that will require future research efforts.

Polymers of micro(nano) plastic in household tap water of the Barcelona Metropolitan Area.

Microplastics (MPLs) are emerging persistent pollutants affecting drinking water systems, and different studies have reported their presence in tap water. However, most of the work has a focus on particles in the 100-5 µm range. Here, a workflow to identify and quantify polymers of micro and nanoplastics (MNPLs), with sizes from 0.7 to 20 µm in tap water, is presented. The analytical method consisted of water fractionated filtration followed by toluene ultrasonic-assisted extraction and size-exclusion chromatography, using an advanced polymer chromatography column coupled to high-resolution mass spectrometry with atmospheric pressure photoionization source with negative and positive ionization conditions (HPLC(APC)-APPI(±)-HRMS) and normal phase chromatography HILIC LUNA® column and electrospray ionisation source in positive and negative mode (HPLC(HILIC)-ESI(±)-HRMS). The acquisition was performed in full scan mode, and the subsequent tentative identification of MNPLs polymers has been based on increasing the confirmation level, including the characterisation of monomers by using Kendrick Mass Defect (KMD) analysis, and confirmation and quantification using standards. This approach was applied to assess MNPLs in tap water samples of the Barcelona Metropolitan Area (BMA), that were collected from August to October 2020 from home taps of volunteers distributed in the 42 postal codes of the BMA. Polyethylene (PE), polypropylene (PP), polyisoprene (PI), polybutadiene (PBD), polystyrene (PS), polyamide (PA), and polydimethylsiloxanes (PDMS) were identified. PE, PP, and PA were the most highly detected polymers, and PI and PBD were found at the highest concentrations (9,143 and 1,897 ng/L, respectively). A principal component analysis (PCA) was conducted to assess differences in MNPLs occurrence in drinking water, that was provided from the two drinking water treatment plants (DWTPs) suppliers. Results showed that no significant differences (at 95% confidence level) were established between the drinking water supplies to the different areas of the BMA.

Screening of suspected micro(nano)plastics in the Ebro Delta (Mediterranean Sea).

This is the first work reporting the use of a double suspect-screening to assess most common polymers and additives in micro(nano)plastics (NPLs/MPLs) found in environmental waters. The method consisted of water filtration followed by ultrasonic-assisted extraction with toluene and analysis employing size exclusion chromatography using an advanced polymer chromatography column coupled to high-resolution mass spectrometry with an atmospheric pressure photoionisation source by negative ionisation conditions (LC(APC)-APPI(-)-HRMS). The identification of NPL/MPLs polymers has been based on increasing confirmation level, including the monomers characterisation by the Kendrick Mass Defect and confirmation and quantification when standards were available. In parallel, the identification of main additives in NPL/MPLs composition, as well organic contaminants adsorbed onto the plastic particles were carried out by analysis of the extracts by LC(C18)-APPI (+/-)-HRMS. To assess the impact of plastic pollution it is necessary to assess the composition in terms of polymers but also the additives. This screening approach has been employed to study composition of NPL/MPLs in the Ebro Delta. Two sampling campaigns including freshwater and seawater samples have been investigated to assess plastic composition in the top 5 cm. Polystyrene (PS), polyethylene (PE), polyisoprene (PI), polybutadiene (PBD), polypropylene (PP) and polysiloxanes were the most detected polymers and PP and PE, sizing between < 1000 and 2000 Da, were found at concentrations reaching up to 7000 ng/L in some areas. The pentadecanoic acid, 1,2,3-benzotriazoles, 2-ethylhexanoic acid (2-EHA), and phthalates such as dimethyl phthalate, mono(2-ethylhexyl) phthalate (MEHP) and the phthalimide were more frequently detected plastic additives. Finally, series of organic contaminants were as well detected in the particulate fraction. These organic contaminants cannot be associated to plastic compositions but can be associated to their adsorption to the particulate matter, in particular to NPL/MPLs, due to their non-polar character. Among these organic contaminants, the more frequently detected were pharmaceutical compounds, food additives and pesticides.

Adsorption and Desorption Behaviour of Polychlorinated Biphenyls onto Microplastics' Surfaces in Water/Sediment Systems.

The potential of microplastics (MPLs) in marine ecosystems to adsorb and transport other micropollutants to biota, contributing to their entry in the food chain, is a primary cause of concern. However, these interactions remain poorly understood. Here, we have evaluated the adsorption/desorption behaviour of marker polychlorinated biphenyls (PCBs), onto MPL surfaces of three widely used polymers-polystyrene (PS), polyethylene (PE), and polyethylene terephthalate (PET). The range of MPL sizes ranged from 1 to 600 µm. The adsorption/desorption was evaluated in sediment/water systems in marine microcosms emulating realistic environmental conditions for 21 days. The adsorption percentages ranged from 20 to 60%. PCBs with a lower degree of chlorination showed higher adsorption percentages because of conformational impediments of PCBs with high-degree chlorination, and also by their affinity to be adsorbed in sediments. Glassy plastic polymers as PET and PS showed a superior affinity for PCBs than rubbery polymers, such as PE. The polymers that can bond PCBs by π-π interactions, rather than van der Waals forces showed better adsorption percentages, as expected. Finally, the adsorption/desorption behaviour of selected PCBs onto MPLs was fitted to a Freundlich isotherm model, with correlations higher than 0.8 in most of the cases.