Pyr-GC-Orbitrap-MS method for the target/untargeted analysis of microplastics in air.

Pyrolysis-gas chromatography coupled to Orbitrap-mass spectrometry is a novel technique that allows the low level and precise determination of microplastics in environmental samples. In this paper, we develop and assess the target and untargeted performance of Pyr-GC-Orbitrap-MS. The method was optimized for 10 plastic polymers: polymethyl methacrylate, nylon-6,6, polypropylene, nitrile butadiene rubber, polyvinyl chloride, polyethylene terephthalate, acrylonitrile butadiene styrene, polyethylene, polycarbonate, and polystyrene. Standards were home-made using a diamond driller to attain mean sizes within the range of 45-382 µm. A step-by-step optimization of the analytical procedure was carried out. First, accurate mass measurement of each polymer at 60,000 resolution was studied to select the 3 most intense and selective quantification and confirmation ions. Second, internal standard quantification was optimized, and good linearity, repeatability, and reproducibility were obtained. Blank contribution and instrumental detection limit were evaluated for each polymer. Finally, the combined and expanded uncertainty of the Pyr-GC-Orbitrap-MS method was calculated to determine the sources of variation, considering that home-made standards were used. To evaluate method performance, targeted and non-targeted analysis of indoor air samples collected from gyms and department stores were carried out. The Pyr-GC-Orbitrap-MS methodology herein described can be applied for the quantitative assessment of MPs and other substances in different matrices.

Microplastics: Human exposure assessment through air, water, and food.

BACKGROUND: Microplastics (MP) are plastic particles with dimension up to 5 mm. Due to their persistence, global spread across different ecosystems and potential human health effects, they have gained increasing attention during the last decade. However, the extent of human exposure to MP through different pathways and their intake have not been elucidated. OBJECTIVES: The objective of this review is to provide an overview on the pathways of exposure to MP through inhalation, ingestion, and dermal contact considering data from the open bibliography on MP in air, dust, food, water and drinks. METHODS: A bibliographic search on Scopus and PubMed was conducted using keywords on MP in outdoor and indoor air, indoor dust, food including beverages and water and human intake (n = 521). Articles were sorted by their title and abstract (n = 213), and only studies reporting MP identification and quantification techniques were further considered (n = 168). A total of 115 articles that include quality assurance and quality control (QA/QC) procedures are finally discussed in the present review. Based on MP concentration data available in literature, we estimated the potential inhaled dose (ID), dust intake (DI), the estimated daily intake (EDI) via food and beverages. Finally, the total daily intake (TDI) considering both inhalation and ingestion routes are provided for adults, infants and newborns. RESULTS: The concentrations of MP in outdoor and indoor air, dust, and in food and water are provided according to the bibliography. Human exposure to MP through dust ingestion, inhalation of air and food/drinks consumption revealed that indoor air and drinking waters were the main sources of MP. CONCLUSIONS: This study reveals that humans are constantly exposed to MP, and that the indoor environment and the food and water we ingest decisively contribute to MP intake. Additionally, we highlight that infants and newborns are exposed to high MP concentrations and further studies are needed to evaluate the presence and risk of MP in this vulnerable age-population.

Human biomonitoring of microplastics and health implications: A review.

BACKGROUND: Microplastics (MPs) are plastic particles (<5 mm) ubiquitous in water, soil, and air, indicating that humans can be exposed to MPs through ingestion of water and food, and inhalation. OBJECTIVE: This review provides an overview of the current human biomonitoring data available to evaluate human exposure and health impact of MPs. METHOD: We compiled 91 relevant studies on MPs in human matrices and MPs toxicological endpoints to provide evidence on MPs distribution in the different tissues and the implications this can have from a health perspective. RESULTS: Human exposure to MPs has been corroborated by the detection of MPs in different human biological samples including blood, urine, stool, lung tissue, breast milk, semen and placenta. Although humans have clearance mechanisms protecting them from potentially harmful substances, health risks associated to MPs exposure include the onset of inflammation, oxidative stress, and DNA damage, potentially leading to cardiovascular and respiratory diseases, as well as cancer, as suggested by in vitro and in vivo studies. CONCLUSION: Based on compiled data, MPs have been recurrently identified in different human tissues and fluids, suggesting that humans are exposed to MPs through inhalation and ingestion. Despite differences in MPs concentrations appear in exposed and non-exposed people, accumulation and distribution pathways and potential human health hazards is still at an infant stage. Human biomonitoring data enables the assessment of human exposure to MPs and associated risks, and this information can contribute to draw management actions and guidelines to minimize MP release to the environment, and thus, reduce human uptake.

Migration of Microplastics and Phthalates from Face Masks to Water.

Since the outbreak of COVID-19, face masks have been introduced in the complex strategy of infection prevention and control. Face masks consist of plastic polymers and additives such as phthalates. The aim of this study was to evaluate the migration of microplastics (MP) and phthalates from face masks to water. Four types of masks including FFP2 masks and surgical were studied. Masks were first characterized to determine the different layers and the material used for their fabrication. Then, masks were cut into 20 pieces of 0.5 cm2, including all their layers, placed in water, and the migration of MP and phthalates was evaluated according to the conditions stated in EU Regulation No 10/2011 on plastic materials and articles intended to come into contact with food. For MP, the morphological analysis (shape, dimension, particle count) was performed using a stereomicroscope, while the identification of both masks and MP released was conducted using µ-Fourier-transform infrared spectroscopy (µ-FT-IR). Migration of phthalates was assessed by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometer (UPLC-MS/MS). Face masks analyzed in the present study were made of atactic polypropylene (PP) as stated by the manufacturer. The µ-FT-IR confirmed that PP and polyamide (PA) were released as fragments, while both PP and polyester (PES) were released as fibers. In addition, 4 phthalates were identified at concentrations between 2.34 and 21.0 µg/mask. This study shows that the migration study can be applied to evaluate the potential release of MP and phthalates from face masks to water and could give a hint for the potential impact of their incorrect disposal on the aquatic resources.

Placental transport of parabens studied using an ex-vivo human perfusion model.

INTRODUCTION: Parabens are a group of chemicals widely used as preservatives in daily consumer products such as cosmetics, food items, pharmaceuticals and household commodities. They have been broadly detected in human samples indicating a general human exposure, and concerns arose from their potential endocrine disrupting effect. Especially the exposure to parabens during pregnancy is concerning, as the time of fetal development is a particularly vulnerable period. The aim of this study was to investigate the transport and metabolism of four commonly used parabens: methyl-, ethyl-, propyl- and butylparaben (MeP, EtP, PrP and BuP) and the metabolite para-hydroxybenzoic acid (PHBA) across the human placenta. METHODS: An ex-vivo human placental perfusion model was used. The test compounds were added in the maternal compartment (with initial concentrations of 1 mM or 0.1 mM). Placental transport was evaluated by fetal-maternal concentration ratios (FM-ratio), transport index (TI) and indicative permeability (IP). RESULTS: Information about parabens kinetics was taken from 10 perfusions and PHBA from 7 perfusions. Paraben metabolism was not detected. The placental transport of MeP, EtP, PrP, BuP and PHBA revealed a transfer from maternal to fetal circulations with FM120 of 0.86 ± 0.27 (MeP), 0.98 ± 0.28 (EtP), 1.00 ± 0.28 (PrP), 1.12 ± 0.59 (BuP) and 0.82 ± 0.37 (PHBA). The test substances accumulated in the perfused tissue in some degree. The average kinetic parameters FM-ratio, TI and IP were not different between chemicals. DISCUSSION: The present study shows that the placenta barrier is permeable to all four parabens and the metabolite, which implies potential fetal exposure.

Assembly of symmetrical and unsymmetrical platinum(II) rollover complexes with bidentate phosphine ligands.

The reaction of the cyclometalated rollover complex [Pt(bpy-H)(Me)(DMSO)] (bpy-H = cyclometalated 2,2'-bipyridine) with two diphosphines, dppm (1,1-bis(diphenylphosphino)methane) and dppe (1,2-bis(diphenylphosphino)ethane), was investigated. According to the reaction conditions, dppm behaves as a monodentate, bridging or chelated ligand, whereas dppe gave only chelated species. Some aspects of the reactivity of the isolated species were studied, including protonation with [H3O·18-crown-6][BF4] and coordination reactions of mononuclear complexes, obtaining, inter alia, rare examples of unsymmetrical organometallic species with bridging dppm.

Modelling of human transplacental transport as performed in Copenhagen, Denmark.

Placenta perfusion models are very effective when studying the placental mechanisms in order to extrapolate to real-life situations. The models are most often used to investigate the transport of substances between mother and foetus, including the potential metabolism of these. We have studied the relationships between maternal and foetal exposures to various compounds including pollutants such as polychlorinated biphenyls, polybrominated flame retardants, nanoparticles as well as recombinant human antibodies. The compounds have been studied in the human placenta perfusion model and to some extent in vitro with an established human monolayer trophoblast cell culture model. Results from our studies distinguish placental transport of substances by physicochemical properties, adsorption to placental tissue, binding to transport and receptor proteins and metabolism. We have collected data from different classes of chemicals and nanoparticles for comparisons across chemical structures as well as different test systems. Our test systems are based on human material to bypass the extrapolation from animal data. By combining data from our two test systems, we are able to rank and compare the transport of different classes of substances according to their transport ability. Ultimately, human data including measurements in cord blood contribute to the study of placental transport.

A proposed study on the transplacental transport of parabens in the human placental perfusion model.

Human exposure to parabens as a preservative used in personal care products is of increasing concern, as there is evidence from in vivo and in vitro studies of hormone disruption in association with exposure to parabens. Transport across the placenta could be critical for risk assessment, but the available data are sparse. The aim is to develop a method for estimating fetal exposure, via the placenta, to the most commonly-used parabens, by using a human placental perfusion model. The use of human tissue is vital for determining human fetal exposure, because animal studies are of little relevance, since the placenta exhibits significant interspecies variation. An HPLC model is currently being established to simultaneously quantify four different parabens, namely, methylparaben, ethylparaben, propylparaben and butylparaben, and their main metabolite, p-hydroxybenzoic acid. With this model, we aim to determine the transport kinetics of these parabens across the human placenta, and to investigate placental metabolism, including differences in transport due to molecular characteristics. This will facilitate assessment of the risks associated with the use of paraben-containing products during pregnancy.