Identification of polystyrene nanoplastics from natural organic matter in complex environmental matrices by pyrolysis-gas chromatography-mass spectrometry.

Due to the flux of plastic debris entering the environment, it becomes urgent to document and monitor their degradation pathways at different scales. At the colloidal scale, the systematic hetero-association of nanoplastics with the natural organic matter complexifies the ability to detect plastic signatures in the particle collected in the various environments. The current techniques used for microplastics could not discriminate the polymers at the nanoscale from the natural macromolecules, as the plastic mass in the aggregate is within the same order. Only a few methods are available concerning nanoplastics identification in complex matrices, with the coupling of pyrolysis with gas chromatography and mass spectrometry (Py-GC-MS) as one of the most promising due to its mass-based detection. However, natural organic matter in environmental samples interferes with similar pyrolysis products. These interferences are even more critical for polystyrene polymers as this plastic presents no dominant pyrolysis markers, such as polypropylene, that could be identified at trace concentrations. Here, we investigate the ability to detect and quantify polystyrene nanoplastics in a rich phase of natural organic matter proposed based on the relative ratio of pyrolyzates. The use of specific degradation products (styrene dimer and styrene trimer) and the toluene/styrene ratio (RT/S) are explored for these two axes. While the size of the polystyrene nanoplastics biased the pyrolyzates of styrene dimer and trimer, the RT/S was correlated with the nanoplastics mass fraction in the presence of natural organic matter. An empirical model is proposed to evaluate the relative quantity of polystyrene nanoplastics in relevant environmental matrices. The model was applied to real contaminated soil by plastic debris and literature data to demonstrate its potential.

Volatile organic compounds identification and specific stable isotopic analysis (δ13C) in microplastics by purge and trap gas chromatography coupled to mass spectrometry and combustion isotope ratio mass spectrometry (PT-GC-MS-C-IRMS).

Microplastics (MPs) have become one of the major global environmental issues in recent decades due to their ubiquity in the environment. Understanding MPs source origin and reactivity is urgently needed to better constrain their fate and budget. Despite improvements in analytical methods to characterize MPs, new tools are needed to help understand their sources and reactivity in a complex environment. In this work, we developed and applied an original Purge-&-Trap system coupled to a GC-MS-C-IRMS to explore the δ13C compound-specific stable isotope analysis (CSIA) of volatile organic compounds (VOC) embedded in MPs. The method consists of heating and purging MP samples, with VOCs being cryo-trapped on a Tenax sorbent, followed by GC-MS-C-IRMS analysis. The method was developed using a polystyrene plastic material showing that sample mass and heating temperature increased the sensitivity while not influencing VOC δ13C values. This robust, precise, and accurate methodology allows VOC identification and δ13C CSIA in plastic materials in the low nanogram concentration range. Results show that the monomer styrene displays a different δ13C value (- 22.2 ± 0.2‰), compared to the δ13C value of the bulk polymer sample (- 27.8 ± 0.2‰). This difference could be related to the synthesis procedure and/or diffusion processes. The analysis of complementary plastic materials such as polyethylene terephthalate, and polylactic acid displayed unique VOC δ13C patterns, with toluene showing specific δ13C values for polystyrene (- 25.9 ± 0.1‰), polyethylene terephthalate (- 28.4 ± 0.5‰), and polylactic acid (- 38.7 ± 0.5‰). These results illustrate the potential of VOC δ13C CSIA in MP research to fingerprint plastic materials, and to improve our understanding of their source cycle. Further studies in the laboratory are needed to determine the main mechanisms responsible for MPs VOC stable isotopic fractionation.

Trace metal sorption on nanoplastics: An innovative analytical approach combining surface analysis and mass spectrometry techniques.

The mass and volume concentration of nanoplastics is extremely low, but incredibly high in terms of surface area; this is expected to increase their toxicity through the ab/adsorption and transport of chemical co-pollutants such as trace metals. In this context, we studied the interactions between nanoplastics model materials functionalized with carboxylated groups, with either smooth or raspberry-like surface morphologies, and copper as representative of trace metals. For this purpose, a new methodology, using two complementary surface analysis techniques: Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) was developed. In addition, inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify the total mass of sorbed metal on the nanoplastics. This innovative analytical approach from the top surface to the core of nanoplastics demonstrated not only the interactions with copper at the surface level, but also the ability of nanoplastics to absorb metal at their core. Indeed, after 24 h of exposition, the copper concentration at the nanoplastic surface remained constant due to saturation whereas the copper concentration inside the nanoplastic keeps increasing with the time. The sorption kinetic was evaluated to increase with the density of charge of the nanoplastic and the pH. This study confirmed the ability of nanoplastics to act as metal pollutant carriers by both adsorption and absorption phenomena.

NMR investigation on the thermogelation of partially hydrolysed polyacrylamide/polyethylenimine mixtures.

Since the introduction of polyethylenimine (PEI)/acrylamide-based polymer gel systems in the late 90's, the literature knowledge on the crosslinking mechanisms between the various polymers (PAM, PHPA, and PatBA) and the crosslinker (PEI) was only limited to observations on gelation times and gel strength variations compared to other gel systems. In this paper, classic proton and carbon nuclear magnetic resonance "NMR" experiments and advanced 2D DOSY and NOESY techniques were employed for studying the interactions between the amine groups of PEI and amide or carboxylate groups of partially hydrolysed polyacrylamide (PHPA). Among the many possibilities, we showed that the interaction occurring during thermogelation is mainly due to covalent bonding. The latter results from a transamidification reaction between the polymer amide groups and the primary amines of the crosslinker. The reaction, at high temperatures, was accompanied by some hydrolysis of the polymer amide groups. Consequently, the kinetics of the reaction and hydrolysis were evaluated and fitted using pseudo first-order equations where the hydrolysis kinetics was found to be three times lower than that of the reaction.

Nanoplastic Labelling with Metal Probes: Analytical Strategies for Their Sensitive Detection and Quantification by ICP Mass Spectrometry.

The detection and quantification of nanoplastics in aquatic environments is one of the major challenges in environmental and analytical research nowadays. The use of common analytical techniques for this purpose is not only hampered by the size of nanoplastics, but also because they are mainly made of carbon. In addition, the expected concentrations in environmental samples are below the detection limit of the majority of analytical techniques. In this context, the great detection capabilities of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in its Single Particle mode (SP-ICP-MS) have made of this technique a good candidate for the analysis of nanoplastics. Since the monitoring of carbon by ICP-MS faces several difficulties, the use of metal tags, taking advantage of the great potential of nanoplastics to adsorb chemical compounds, has been proposed as an alternative. In this perspectives paper, three different strategies for the analysis of polystyrene (PS) nanoplastics by SP-ICP-MS based on the use of metals species (ions, hydrophobic organometallic compound, and nanoparticles) as tags are presented and discussed. Advantages and disadvantages of each strategy, which rely on the labelling process, are highlighted. The metal nanoparticles labelling strategy is shown as a promising tool for the detection and quantification of nanoplastics in aqueous matrices by SP-ICP-MS.

Nanoplastics Identification in Complex Environmental Matrices: Strategies for Polystyrene and Polypropylene.

Identification of nanoplastics in complex environmental matrices remains a challenge. Despite the increase in nanoplastics studies, there is a lack of studies dedicated to nanoplastics detection, partially explained by their carbon-based structure, their wide variety of composition, and their low environmental concentrations compared to the natural organic matter. Here, pyrolysis coupled to a GCMS instrumental setup provided a relevant analytical response for polypropylene and polystyrene nanoplastic suspensions. Specific pyrolysis markers and their indicative fragment ions were selected and validated. Possible interferences with environmental matrices were explored by spiking nanoplastics in various organic matter suspensions (i.e., algae, soil natural organic matter, and soil humic acid) and analyzing an environmental suspension of nanoplastics. While a rapid polypropylene nanoplastics identification was validated, polystyrene nanoplastics require preliminary treatment. The strategies presented herein open new possibilities for the detection/identification of nanoplastics in environmental matrices such as soil, dust, and biota.

Nanoplastics are neither microplastics nor engineered nanoparticles.

Increasing concern and research on the subject of plastic pollution has engaged the community of scientists working on the environmental health and safety of nanomaterials. While many of the methods developed in nano environment, health and safety work have general applicability to the study of particulate plastics, the nanometric size range has important consequences for both the analytical challenges of studying nanoscale plastics and the environmental implications of these incidental nanomaterials. Related to their size, nanoplastics are distinguished from microplastics with respect to their transport properties, interactions with light and natural colloids, a high fraction of particle molecules on the surface, bioavailability and diffusion times for the release of plastic additives. Moreover, they are distinguished from engineered nanomaterials because of their high particle heterogeneity and their potential for rapid further fragmentation in the environment. These characteristics impact environmental fate, potential effects on biota and human health, sampling and analysis. Like microplastics, incidentally produced nanoplastics exhibit a diversity of compositions and morphologies and a heterogeneity that is typically absent from engineered nanomaterials. Therefore, nanoscale plastics must be considered as distinct from both microplastics and engineered nanomaterials.

Environmental Fate Modeling of Nanoplastics in a Salinity Gradient Using a Lab-on-a-Chip: Where Does the Nanoscale Fraction of Plastic Debris Accumulate?

The aim of this study is to demonstrate how the flow and diffusion of nanoplastics through a salinity gradient (SG), as observed in mangrove swamps (MSPs), influence their aggregation pathways. These two parameters have never yet been used to evaluate the fate and behavior of colloids in the environment, since they cannot be incorporated into classical experimental setups. Land-sea continuums, such as estuaries and MSP systems, are known to be environmentally reactive interfaces that influence the colloidal distribution of pollutants. Using a microfluidic approach to reproduce the SG and its dynamics, the results show that nanoplastics arriving in a MSP are fractionated. First, a substantial fraction rapidly aggregates to reach the microscale, principally governed by an orthokinetic aggregation process and diffusiophoresis drift. These large nanoplastic aggregates eventually float near the water's surface or settle into the sediment at the bottom of the MSP, depending on their density. The second, smaller fraction remains stable and is transported toward the saline environment. This distribution results from the combined action of the spatial salt concentration gradient and orthokinetic aggregation, which is largely underestimated in the literature. Due to nanoplastics' reactive behavior, the present work demonstrates that mangrove and estuarine systems need to be better examined regarding plastic pollution.

Chemicals sorbed to environmental microplastics are toxic to early life stages of aquatic organisms.

Microplastics are ubiquitous in aquatic ecosystems, but little information is currently available on the dangers and risks to living organisms. In order to assess the ecotoxicity of environmental microplastics (MPs), samples were collected from the beaches of two islands in the Guadeloupe archipelago, Petit-Bourg (PB) located on the main island of Guadeloupe and Marie-Galante (MG) on the second island of the archipelago. These samples have a similar polymer composition with mainly polyethylene (PE) and polypropylene (PP). However, these two samples are very dissimilar with regard to their contamination profile and their toxicity. MPs from MG contain more lead, cadmium and organochlorine compounds while those from PB have higher levels of copper, zinc and hydrocarbons. The leachates of these two samples of MPs induced sublethal effects on the growth of sea urchins and on the pulsation frequency of jellyfish ephyrae but not on the development of zebrafish embryos. The toxic effects are much more marked for samples from the PB site than those from the MG site. This work demonstrates that MPs can contain high levels of potentially bioavailable toxic substances that may represent a significant ecotoxicological risk, particularly for the early life stages of aquatic animals.

Fate of nanoplastics in the environment: Implication of the cigarette butts.

Fate, transport and accumulation of nanoplastics have attracted considerable attention in the past few years. While actual researches have been focused on nanoplastics dispersed or aggregated in different environmental system, no study have been focused on the possibility that nanoplastics are co-transported with other natural or anthropogenic materials. Therefore, the large quantity of debris released in the environment, such as cigarette butts (CGB), could be part of the nanoplastics fate and behavior. Here we show the considerable sorption capacities of cigarette filters for nanoplastics. To address this topic, we chose polystyrene-based nanoplastics with similar state of charge (according to the physico-chemical characteristic of the zeta potential -45 to -40 mV) but with different sizes (50-800 nm) and morphologies. A kinetic approach to sorption in fresh water (pH = 8.05; 179.5 µS cm-1) at room temperature was carried out by means of the flow field flow analysis method (AF4) to determine the partition coefficients and water sampling rates between nanoplastics and cigarette butts. Using different models of, more or less environmentally relevant, nanoplastics (NPTs) and adequate analytical strategies, we found partition coefficients between the NPTs and CGBs ranged from 102 to 104 in freshwater conditions. We demonstrated that the physical features of the NPTs (size and morphology) have an influence on the sorption behaviour. Asymmetrical shaped NPTs with broader size distribution seems to be mostly retained in the CGBs after longer equilibration time. This result shows the importance of the NPTs features on the mechanisms governing their transfer and fate in the environment through environmental matrices, especially when other materials are involved. We anticipate our work to be a starting point for investigating the co-transport of NPTs with other materials present in the environment (natural and anthropogenic).

Nanoplastic occurrence in a soil amended with plastic debris.

While several studies have investigated the potential impact of nanoplastics, proof of their occurrence in our global environment has not yet been demonstrated. In the present work, by developing an innovative analytical strategy, the presence of nanoplastics in soil was identified for the first time. Our results demonstrate the presence of nanoplastics with a size ranging from 20 to 150 nm and covering three of the most common plastic families: polyethylene, polystyrene and polyvinyl chloride. Given the amount of organic matter in the soil matrix, the discrimination and identification of large nanoplastic aggregates are challenging. However, we provided an innovative methodology to circumvent the organic matter impact on nanoplastic detection by coupling size fractionation to molecular analysis of plastics. While photodegradation has been considered the principal formation pathway of nanoplastics in the environment, this study provides evidence, for the first time, that plastic degradation and nanoplastic production can, however, occur in the soil matrix. Moreover, by providing an innovative and simple extraction/analysis method, this study paves the way to further studies, notably regarding nanoplastic environmental fate and impacts.

Trace element distribution in marine microplastics using laser ablation-ICP-MS.

Due to the dramatic quantity of plastic debris released into our environment, one of the biggest challenges of the next decades is to trace and quantify microplastics (MPs) in our environments, especially to better evaluate their capacity to transport other contaminants such as trace metals. In this study, trace elements (Fe, Cu, Zn, As, Cd, Sn, Sb, Pb, and U) were analyzed in the microplastic subsurface (200 µm) using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Microplastics subjected to the marine environment were collected on beaches (Guadeloupe) exposed to the north Atlantic gyre. We established a strategy to discriminate sorbed contaminants from additives based on the metal concentration profiles in MP subsurface using qualitative and quantitative approaches. A spatiotemporal correlation of the sorption pattern was proposed to compare MPs in terms of relative exposure time and time-weighted average concentrations in the exposure media.

A Novel Strategy for the Detection and Quantification of Nanoplastics by Single Particle Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

A method for the detection and quantification of nanoplastics (NPTs) at environmentally relevant concentrations was developed. It is based on conjugating nanoplastics with functionalized metal (Au)-containing nanoparticles (NPs), thus making them detectable by highly sensitive inductively coupled plasma mass spectrometry (ICP-MS) operated in single particle (SP) mode. The selectivity of the method was achieved by the coupling of negatively charged carboxylate groups present at the surface of nanoplastics with a positively charged gelatin attached to the custom-synthesized AuNPs. The adsorbed Au produced a SP-ICP-MS signal allowing the counting of individual nanoplastic particles, and hence their accurate quantification (<5% error). Polystyrene (PS) particle models with controlled surface functionalization mimicking the nanoplastics formed during natural degradation of plastic debris were used for the method development. The nanoplastic number concentration quantification limit was calculated at 8.4 × 105 NPTs L-1 and the calibration graph was linear up to 3.5 × 108 NPTs L-1. The method was applied to the analysis of nanoplastics of up to 1 µm in drinking, tap, and river water. The minimum detectable and quantifiable size depended on the degree of functionalization and the surface available for labeling. For a fully functionalized nanoplastic, the lower size detectable by this strategy is reported as 135 nm. In this study, authors use the recommendation for the definition of nanoplastics as plastic particles with sizes ranging between 1 nm and 1 µm, although it has not been accepted by a dedicated organization.

Deposition of environmentally relevant nanoplastic models in sand during transport experiments.

Nanoplastics (NPTs) are defined as colloids that originated from the unintentional degradation of plastic debris. To understand the possible risks caused by NPTs, it is crucial to determine how they are transported and where they may finally accumulate. Unfortunately, although most sources of plastic are land-based, risk assessments concerning NPTs in the terrestrial environmental system (soils, aquifers, freshwater sediments, etc.) have been largely lacking compared to studies concerning NPTs in the marine system. Furthermore, an important limitation of environmental fate studies is that the NPT models used are questionable in terms of their environmental representativeness. This study describes the fate of different NPT models in a porous media under unfavorable (repulsive) conditions, according to their physical and chemical properties: average hydrodynamic diameters (200-460 nm), composition (polystyrene with additives or primary polystyrene) and shape (spherical or polymorphic). NPTs that more closely mimic environmental NPTs present an inhomogeneous shape (i.e., deviating from a sphere) and are more deposited in a sand column by an order of magnitude. This deposition was attributed in part to physical retention, as confirmed by the straining that occurred for the larger size fractions. Additionally, different Derjaguin-Landau-Verwey-Overbeek (DLVO) models -the extended DLVO (XDLVO) and a DLVO modified by surface element integration (SEI) method-suggest that the environmentally relevant NPT models may alter its orientation to diminish repulsion from the sand surface and may find enough kinetic energy to deposit in the primary energetic minimum. These results point to the importance of choosing environmentally relevant NPT models.

Advanced nanomedicine characterization by DLS and AF4-UV-MALS: Application to a HIV nanovaccine.

Nanoformulations are complex systems where physicochemical properties determine their therapeutic efficacy and safety. In the case of nanovaccines, particle size and shape play a crucial role on the immune response generated. Furthermore, the antigen's integrity is also a key aspect to control when producing a nanovaccine. The determination of all those physicochemical properties is still an analytical challenge and the lack of well-established methods hinders the access of new therapeutics to the market. In this work, robust methods for the characterization of a novel HIV nanoparticle-based vaccine produced in good manufacturing practice (GMPs)-like environment were developed. With slightly polydisperse particles (< 0.2) close to 180 nm of size, batch-mode Dynamic Light Scattering (DLS) was validated to be used as a quality control technique in the pilot production plant. In addition, a high size resolution method using Asymmetrical Flow Field Flow Fractionation (AF4) demonstrated its ability to determine not only size and size distribution but also shape modification across the size and accurate quantification of the free active ingredient. Results showed a monomodal distribution of particles from 60 to 700 nm, most of them (> 90%) with size lower than 250 nm, consistent with more traditional techniques, and revealed a slight change in the structure of the particles induced by the presence of the antigen. Finally, a batch to batch variability lower than 20% was obtained by both DLS and AF4 methods indicating that preparation method was highly reproducible.

Synthesis and Viscosimetric Behavior of Poly(acrylamide-co-2-acrylamido-2-methylpropanesulfonate) Obtained by Conventional and Adiabatic Gel Process via RAFT/MADIX Polymerization.

High molar masses homopolymers of both acrylamide (AM) and 2-acrylamido-2-methylpropanesulfonate (AMPS) as well as poly(AM-stat-AMPS) exhibiting a large range copolymer composition has been obtained via the optimization of a purely adiabatic gel process. Monomer concentrations ranging from 2.0 to 3.47 M have been successfully tested while keeping the control of the molar masses up to 5 × 106 g mol-1. The products have been characterized in terms of molecular mass and viscosimetric properties.

Rheological behaviour and adsorption phenomenon of a polymer-particle composite based on hydrolysed polyacrylamide/functionalized poly(styrene-acrylic acid) microspheres.

The properties in aqueous solution of polymer-particle composites (PPC) depend on the size and the concentration of both the particles and the polymers as well as the interactions between them. In this work, rheological behaviour was studied in a semi-diluted regime of partially hydrolysed polyacrylamide (HPAM) with 2Rg/d a particle diameter/polymer gyration radius (Rg) ratio and a confinement parameter (pc) that were both greater than 1. Rg is the polymer gyration radius and d the particle diameter. pc characterizes the inter-particle distance (ID) with respect to the polymer size (pc = ID/2Rg) and depends on the concentration and size of the particles. We highlighted the PPC thickening effects as a function of the number of carboxylic functions on the surface of the polystyrene particles (PSL) obtained by free soap free emulsion polymerization (0.16-1.2 mmol g-1 of COOH). Thickening increases linearly with surface functionality for a pc of less than 10. This behaviour has been correlated to the polymer-particle interactions, which was demonstrated by adsorption measurements in dilute solution (12-22 mg g-1 of HPAM on PSL). Adsorption was quantified by zero-shear capillary viscosity measurements in a microfluidic device. In contrast, a thinning effect was observed for a pc greater than 10, which is also related to the salt effect studies (6-12 g L-1 in NaCl).

Are nanoplastics able to bind significant amount of metals? The lead example.

The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log Kadsfreundlich=8.36 against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

Current opinion: What is a nanoplastic?

With the large amount of attention being given to microplastics in the environment, several researchers have begun to consider the fragmentation of plastics down to lower scales (i.e., the sub-micrometer scale). The term "nanoplastics" is still under debate, and different studies have set the upper size limit at either 1000 nm or 100 nm. The aim of the present work is to propose a definition of nanoplastics, based on our recently published and unpublished research definition of nanoplastics. We define nanoplastics as particles unintentionally produced (i.e. from the degradation and the manufacturing of the plastic objects) and presenting a colloidal behavior, within the size range from 1 to 1000 nm.

Nano-litter from cigarette butts: Environmental implications and urgent consideration.

Cigarette butts (CGB) are equivalent to plastic litter in terms of number of pieces released directly into the environment. Due to their small size and social use, CGB are commonly found in natural systems, and several questions have been raised concerning the contaminants that are released with CGB, including metals, organic species, and nanoparticles. The aim of the present study is to investigate the release of nanoscale particles from CGB by leaching with rainwater. After seven days of passive stirring of both smoked and unsmoked CGB in synthetic rainwater, the solutions were treated and analyzed by specific nano-analytical methods. Our results demonstrate the release of 4.12 ± 0.24% (w/CGB) organic carbon in the range of 10 nm up to 400 nm and with a z-average diameter of 202.4 ± 74.1 nm. The fractal dimension (Df) of the nanoscale particles ranges from 1.14 to 1.52 and suggests a soot (carbon)-based composition. The analysis of some metallic species (As, Pb, Cd, Cu, Ni, Cr, Co, Al, Mn, Zn, and Fe) shows that these species are essentially attached to the nanoscale particles per gram of carbon released. By considering the diffusion of the nanomaterials into different environmental compartments, our results suggest a new emerging and global contamination of the environment by cigarette butts, comparable to plastic litter, which urgently needs to be considered.