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.

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.

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).

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.

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.

High separation efficiency of gold nanomaterials of different aspect ratio and size using capillary transient isotachophoresis.

Two modes of capillary electrophoresis (CE), capillary zone electrophoresis (CZE) and capillary transient isotachophoresis (ctITP), were compared for the detection and separation of spherical gold nanoparticles (AuNPs) and gold nanorods (AuNRs). The development of ctITP using two different leading ions is described. Overall, when compared to traditional capillary zone electrophoresis (CZE), ctITP resulted in improved peak shape and peak efficiency. Specifically, the number of theoretical plates for AuNR samples increased by a factor of 2-2.5 depending on the choice of leading ion. Further, using ctITP two AuNRs differing by aspect ratio were baseline resolved, whereas the same AuNRs could not be separated using CZE or other techniques like single particle inductively coupled plasma mass spectrometry (spICP-MS) and asymmetric flow field-flow fractionation (AF4). The results of this study demonstrate that ctITP is an efficient on-line technique for the improved detection and separation of gold nanomaterials in CE.

Fast quantification of nanorod geometry by DMA-spICP-MS.

A fast, quantitative method for determining the dimensions of nanorods (i.e., length and diameter) is described, based on hyphenation of differential mobility analysis (DMA) with single particle inductively coupled plasma mass spectrometry (spICP-MS). Seven gold nanorod samples with different dimensions (diameters 11.8 nm to 38.2 nm, aspect ratios 1.8 to 6.9) were used to validate the method. We demonstrate that DMA-spICP-MS can (1) achieve quantification of both length and diameter comparable with TEM analysis, (2) make statistically meaningful measurements in minutes at low concentrations (<108 mL-1) and (3) separate nanorods from spheres and quantify the geometry of each population. A robustness analysis of this method was performed to evaluate potential biases in this approach.

An assessment of retention behavior for gold nanorods in asymmetrical flow field-flow fractionation.

Applications of asymmetrical flow field-flow fractionation (AF4) continue to expand rapidly in the fields of nanotechnology and biotechnology. In particular, AF4 has proven valuable for the separation and analysis of particles, biomolecular species (e.g., proteins, bacteria) and polymers (natural and synthetic), ranging in size from a few nanometers to several micrometers. The separation of non-spheroidal structures (e.g., rods, tubes, etc.) with primary dimensions in the nanometer regime, is a particularly challenging application deserving of greater study and consideration. The goal of the present study was to advance current understanding of the mechanism of separation of rod-like nano-objects in the AF4 channel. To achieve this, we have systematically investigated a series of commercially available cetyltrimethylammonium bromide stabilized gold nanorods (AuNRs), with aspect ratios from 1.7 to 10. Results show clearly that the retention time is principally dependent on the translational diffusion coefficient of the AuNRs. Equations used to calculate translational and rotational diffusion coefficients (cylinder and prolate ellipsoid models) yield similarly good fits to experimental data. Well characterized gold nanorods (length and diameter by transmission electron microscopy) can be used as calibrants for AF4 measurements allowing one to determine the aspect ratio of nanorod samples based on their retention times. Graphical abstract ᅟ.

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.

Asymmetrical flow field flow fractionation methods to characterize submicron particles: application to carbon-based aggregates and nanoplastics.

In the last 10 years, asymmetrical flow field flow fractionation (AF4) has been one of the most promising approaches to characterize colloidal particles. Nevertheless, despite its potentialities, it is still considered a complex technique to set up, and the theory is difficult to apply for the characterization of complex samples containing submicron particles and nanoparticles. In the present work, we developed and propose a simple analytical strategy to rapidly determine the presence of several submicron populations in an unknown sample with one programmed AF4 method. To illustrate this method, we analyzed polystyrene particles and fullerene aggregates of size covering the whole colloidal size distribution. A global and fast AF4 method (method O) allowed us to screen the presence of particles with size ranging from 1 to 800 nm. By examination of the fractionating power F d, as proposed in the literature, convenient fractionation resolution was obtained for size ranging from 10 to 400 nm. The global F d values, as well as the steric inversion diameter, for the whole colloidal size distribution correspond to the predicted values obtained by model studies. On the basis of this method and without the channel components or mobile phase composition being changed, four isocratic subfraction methods were performed to achieve further high-resolution separation as a function of different size classes: 10-100 nm, 100-200 nm, 200-450 nm, and 450-800 nm in diameter. Finally, all the methods developed were applied in characterization of nanoplastics, which has received great attention in recent years. Graphical Absract Characterization of the nanoplastics by asymmetrical flow field flow fractionation within the colloidal size range.

Electrospray-Differential Mobility Hyphenated with Single Particle Inductively Coupled Plasma Mass Spectrometry for Characterization of Nanoparticles and Their Aggregates.

The novel hyphenation of electrospray-differential mobility analysis with single particle inductively coupled plasma mass spectrometry (ES-DMA-spICPMS) was demonstrated with the capacity for real-time size, mass, and concentration measurement of nanoparticles (NPs) on a particle-to-particle basis. In this proof-of-concept study, the feasibility of this technique was validated through both concentration and mass calibration using NIST gold NP reference materials. A detection limit of 10(5) NPs mL(-1) was determined under current experimental conditions, which is about 4 orders of magnitude lower in comparison to that of a traditional ES-DMA setup using a condensation particle counter as detector. Furthermore, independent and simultaneous quantification of both size and mass of NPs provides information regarding NP aggregation states. Two demonstrative applications include gold NP mixtures with a broad size range (30-100 nm), and aggregated gold NPs with a primary size of 40 nm. Finally, this technique was shown to be potentially useful for real-world samples with high ionic background due to its ability to remove dissolved ions yielding a cleaner background. Overall, we demonstrate the capacity of this new hyphenated technique for (1) clearly resolving NP populations from a mixture containing a broad size range; (2) accurately measuring a linear relationship, which should inherently exist between mobility size and one-third power of ICPMS mass for spherical NPs; (3) quantifying the early stage propagation of NP aggregation with well-characterized oligomers; and (4) differentiating aggregated NPs and nonaggregated states based on the "apparent density" derived from both DMA size and spICPMS mass.

Impact of and correction for instrument sensitivity drift on nanoparticle size measurements by single-particle ICP-MS.

The effect of ICP-MS instrument sensitivity drift on the accuracy of nanoparticle (NP) size measurements using single particle (sp)ICP-MS is investigated. Theoretical modeling and experimental measurements of the impact of instrument sensitivity drift are in agreement and indicate that drift can impact the measured size of spherical NPs by up to 25 %. Given this substantial bias in the measured size, a method was developed using an internal standard to correct for the impact of drift and was shown to accurately correct for a decrease in instrument sensitivity of up to 50 % for 30 and 60 nm gold nanoparticles. Graphical Abstract Correction of nanoparticle size measurement by spICP-MS using an internal standard.

Asymmetric flow-field flow fractionation-multidetection coupling for assessing colloidal copper in drain waters from a Bordeaux wine-growing area.

The objective of this study was to show that on-line asymmetric flow-field flow fractionation (AFFFF)-multidetection coupling is useful for studying environmental colloids in a qualitative and quantitative way. The utility of the technique was illustrated by assessing the colloidal fraction of the copper that was extracted from the soil, transferred to an aqueous phase and then transported by drain waters in a wine-growing area. To determine the size and composition of the colloids, AFFFF was coupled to UV, multi-angle light scattering and inductively coupled plasma mass spectrometry detectors. Colloidal copper represents between 20 and 60% of the total copper in the sub 450 nm of drain waters. Copper is mainly associated with organic-rich colloids with a size below 10 nm. It is also found in organo-mineral populations (as clay or (oxy)hydroxides), with sizes ranging between 10 and 450 nm.

Optimization of flow field-flow fractionation for the characterization of natural colloids.

The methodological approach used to robustly optimize the characterization of the polydisperse colloidal phase of drain water samples is presented. The approach is based on asymmetric flow field-flow fractionation coupled to online ultraviolet/visible spectrophotometry, multi-angle light scattering, and inductively coupled plasma mass spectrometry. Operating factors such as the amount of sample injected and the ratio between main-flow and cross-flow rates were considered. The evaluation of the injection and fractionation steps was performed considering the polydispersity index and the contribution to the polydispersity of the plate height, the recovery, the retention ratio and the size range of the fractionated colloids. This approach allows the polydispersity of natural colloid samples to be taken into consideration to achieve the most efficient and representative fractionation. In addition to the size characterization, elemental analysis was also evaluated using the recovery, precision, and limits of detection and quantification relative to a trace element of interest (copper) in drain water. To complete this investigation, the potential application of the methodology was assessed using several independent drain water samples from different soils. The contribution of the polydispersity to the plate height ranges from 4.8 to 8.9 cm with a mean precision of 6%. The mean colloidal recovery was 81 ± 3 %, and the mean retention ratio was 0.043-0.062. The limits of detection and quantification for copper were 0.6 and 1.8 µg L(-1), respectively.

Assessment of diffuse contamination of agricultural soil by copper in Aquitaine region by using French national databases.

A long-term application of copper-based fungicides to fight against downy mildew has led to soil contamination by copper particularly in Aquitaine region where viticulture is important. This work aims to statistically validate the origin of diffuse contamination of Aquitaine agricultural soils and show that contamination is closely related to wine-growing in this region. For this purpose, several national databases have been used. From the French National Soil Monitoring Network (Réseau de Mesures de la Qualité des sols RMQS) data, an Exploratory Data Analysis (EDA) was performed to bring out the copper contamination. The French test soil database (Base de Données des Analyses de Terre BDAT) and the national census of agriculture (Recensement Général Agricole RGA) have been crossed. A statistical approach has been used to determine the relationship between the median concentration of copper extracted by Ethylene Diamine Tetra-acetic Acid (EDTA) referred to as CuEDTA in cultivated topsoils of the Aquitaine region and the ratio between winegrowing area (Svine) and the Used Agricultural Area (UAA) expressed as the form Svine/UAA. The results revealed a strongly significant exponential correlation between these two variables. They allow concluding that at cantonal scale, when vines cover more than 80% of the UAA, an overexposure of soils to the diffuse contamination by copper can occur.