Co-occurrence of macroplastics, microplastics, and legacy and emerging plasticisers in UK soils.

Despite a theoretical link between plastic and plasticiser occurrence in the terrestrial environment, there are few empirical studies of the relationship between these contaminants in soils. We carried out a field study to assess the co-occurrence of plastic waste, and legacy and emerging plasticisers in UK soils (n = 19) from various land uses (woodlands, urban roadsides, urban parklands, landfill-associated). Surface plastics and soil microplastics were quantified and characterised using ATR-FTIR and µ-FTIR. Eight legacy (phthalate) and three emerging (adipate, citrate, trimellitate) plasticisers were quantified using GC-MS. Surface plastics were found at higher prevalence at landfill-associated and urban roadside sites, with levels significantly (2 orders of magnitude) greater than in woodlands. Microplastics were detected in landfill-associated (mean 12.3 particles g-1 dw), urban roadside (17.3 particles g-1 dw) and urban parkland (15.7 particles g-1 dw) soils, but not in woodland soils. The most commonly detected polymers were polyethene, polypropene and polystyrene. Mean ∑plasticiser concentration in urban roadside soils (3111 ng g-1 dw) was significantly higher than in woodlands (134 ng g-1 dw). No significant difference was found between landfill-associated (318 ng g-1 dw) and urban parkland (193 ng g-1 dw) soils and woodlands. Di-n-butyl phthalate (94.7% detection frequency) and the emerging plasticiser trioctyl trimellitate (89.5%) were the most commonly detected plasticisers, with diethylhexyl phthalate (493 ng g-1 dw) and di-iso-decyl phthalate (96.7 ng g-1 dw) present at the highest concentrations. ∑plasticiser concentrations were significantly correlated with surface plastic (R2 = 0.23), but not with soil microplastic concentrations. Whilst plastic litter seems a fundamental source of plasticisers in soils, mechanisms such as airborne transport from source areas may be as important. Based on the data from this study, phthalates remain the dominant plasticisers in soils, but emerging plasticisers are already widespread, as reflected by their presence in all land uses studied.

Reproducibility of methods required to identify and characterize nanoforms of substances.

Nanoforms (NFs) of a substance may be distinguished from one another through differences in their physicochemical properties. When registering nanoforms of a substance for assessment under the EU REACH framework, five basic descriptors are required for their identification: composition, surface chemistry, size, specific surface area and shape. To make the risk assessment of similar NFs efficient, a number of grouping frameworks have been proposed, which often require assessment of similarity on individual physicochemical properties as part of the group justification. Similarity assessment requires an understanding of the achievable accuracy of the available methods. It must be demonstrated that measured differences between NFs are greater than the achievable accuracy of the method, to have confidence that the measured differences are indeed real. To estimate the achievable accuracy of a method, we assess the reproducibility of six analytical techniques routinely used to measure these five basic descriptors of nanoforms: inductively coupled plasma mass spectrometry (ICP-MS), Thermogravimetric analysis (TGA), Electrophoretic light scattering (ELS), Brunauer-Emmett-Teller (BET) specific surface area and transmission and scanning electron microscopy (TEM and SEM). Assessment was performed on representative test materials to evaluate the reproducibility of methods on single NFs of substances. The achievable accuracy was defined as the relative standard deviation of reproducibility (RSDR) for each method. Well established methods such as ICP-MS quantification of metal impurities, BET measurements of specific surface area, TEM and SEM for size and shape and ELS for surface potential and isoelectric point, all performed well, with low RSDR, generally between 5 and 20%, with maximal fold differences usually <1.5 fold between laboratories. Applications of technologies such as TGA for measuring water content and putative organic impurities, additives or surface treatments (through loss on ignition), which have a lower technology readiness level, demonstrated poorer reproducibility, but still within 5-fold differences. The expected achievable accuracy of ICP-MS may be estimated for untested analytes using established relationships between concentration and reproducibility, but this is not yet the case for TGA measurements of loss on ignition or water content. The results here demonstrate an approach to estimate the achievable accuracy of a method that should be employed when interpreting differences between NFs on individual physicochemical properties.

Refinement of the selection of physicochemical properties for grouping and read-across of nanoforms.

Before placing a new nanoform (NF) on the market, its potential adverse effects must be evaluated. This may e.g. be done via hazard and risk assessment. Grouping and read-across of NFs is a possible strategy to reduce resource consumption, maximising the use of existing data for assessment of NFs. The GRACIOUS project provides a framework in which possible grouping and read-across for NFs is mainly based on an evaluation of their similarity. The impact of NFs on human health and the environment depends strongly on the concentration of the NF and its physicochemical properties, such as chemical composition, size distribution, shape, etc. Hence, knowledge of the most relevant physicochemical properties is essential information for comparing similarity. The presented work aims to refine existing proposals for sets of descriptors (descriptor array) that are needed to describe distinct NFs of a material to identify the most relevant ones for grouping and read-across. The selection criteria for refining this descriptor array are explained and demonstrated. Relevant protocols and methods are proposed for each physicochemical property. The required and achievable measurement accuracies of the refined descriptor array are reviewed, as this information is necessary for similarity assessment of NFs based on individual physicochemical properties.

Similarity assessment of metallic nanoparticles within a risk assessment framework: A case study on metallic nanoparticles and lettuce.

Similarity assessment is one of the means of optimally using scarcely available experimental data on the fate and hazards of nanoforms (NFs) for regulatory purposes. For a set of NFs that are shown to be similar it is allowed in a regulatory context to apply the information available on any of the NFs within the group to the whole set of NFs. Obviously, a proper justification for such a similarity assessment is to be provided. Within the context of exemplifying such a justification, a case study was performed aimed at assessing the similarity of a set of spherical metallic NFs that different with regard to chemical composition (three metals) and particle size (three different sizes). The endpoints of assessment were root elongation and biomass increase of lettuce (Lactuca sativa L.) seedlings and exposure assessment was performed in order to express the actual exposure concentration in terms of time-weighted average particle concentrations. The results of the study show that for the specific endpoints assessed, chemical composition is driving NF toxicity and this is mostly due to impacts on the fate of the NFs. On the other hand, particle size of Cu NFs had a negligible impact on the dose-response relationships for the specific endpoints assessed. It is thus concluded that hazard data available on spherical Cu NF tested in our case can be used to inform on the hazards of any spherical Cu NF within the size range of 25-100 nm, but only applies for the certain endpoints. Also, toxicity data for the Cu2+-ion are suited for such a similarity assessment.

Semi-automated analysis of microplastics in complex wastewater samples.

In order to assess risks to the natural environment from microplastics, it is necessary to have reliable information on all potential inputs and discharges. This relies on stringent quality control measures to ensure accurate reporting. Here we focus on wastewater treatment works (WwTWs) and the complex sample matrices these provide. Composite samples of both influent and effluent were collected over a 24 h period on two separate occasions from eight different WwTWs across the UK. Sludge samples were taken on five occasions from five WwTWs. The WwTW treatments included activated sludge, trickling filter and biological aerated flooded filter with or without tertiary treatment. Using micro-FTIR analysis, microplastics ≥25 µm were identified and quantified. Procedural blanks were used to derive limits of detection (LOD) and limits of quantification (LOQ). Where values were above the LOQ, microplastics in the influent ranged from 955 to 17,214 microplastic particles/L and in the effluent from 2 to 54 microplastic particles/L, giving an average removal rate of 99.8%. Microplastics could be quantified in sludge at concentrations of 301-10,380 microplastics/g dry weight, this analytical method therefore revealing higher concentrations than reported in previous studies. The most common polymers present overall were polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET). We also report on critical considerations for blank corrections and quality control measures to ensure reliable microplastic analysis across different sample types.

Toward the Systematic Identification of Microplastics in the Environment: Evaluation of a New Independent Software Tool (siMPle) for Spectroscopic Analysis.

Microplastics (MP) are ubiquitous within the environment, but the approaches to analysis of this contaminant are currently quite diverse, with a number of analytical methods available. The comparability of results is hindered as even for a single analytical method such as Fourier transform infrared spectroscopy (FT-IR) the different instruments currently available do not allow a harmonized analysis. To overcome this limitation, a new free of charge software tool, allowing the systematic identification of MP in the environment (siMPle) was developed. This software tool allows a rapid and harmonized analysis of MP across FT-IR systems from different manufacturers (Bruker Hyperion 3000, Agilent Cary 620/670, PerkinElmer Spotlight 400, and Thermo Fischer Scientific Nicolet iN10). Using the same database and the automated analysis pipeline in siMPle, MP were identified in samples that were analyzed with instruments with different detector systems as well as optical resolutions and the results discussed.

The fate of cerium oxide nanoparticles in sediments and their routes of uptake in a freshwater worm.

The relative importance of ingestion and transdermal uptake of nanomaterials is poorly understood, particularly in sediment dwelling organisms, where diet has the potential to contribute significantly to particle accumulation. In aquatic sediments, nanoparticles may partition to bind with the solid fraction of sediment, be freely mobile in the pore water or, for certain metal/metal oxides, undergo dissolution, each of which could influence the route of nanoparticle uptake. Here, we used the freshwater worm Lumbriculus variegatus as a model species. We took advantage of its unique feeding and non-feeding life-stages to assess the contribution of dietary and transdermal uptake in the bioaccumulation of cerium oxide nanoparticles (CeO2 NP) and soluble Ce(III)NO3. Distribution of cerium between the solid, colloidal and soluble fractions in the sediments was determined through sediment separations using micro and ultrafiltration techniques. We assessed particles of differing sizes (10, 28 and 615 nm CeO2) and stabilizing surfactants (10 nm electrostatic Citrate-CeO2 and steric stabilized PEG-CeO2). Soluble Ce(III)NO3, was found to accumulate readily across the skin of the worms whilst nanoparticles were not. Sediments reduced the uptake of CeIII by limiting the presence of dissolved species of cerium in the pore waters. Neither particle size nor the coatings studied altered the distribution of nanoparticles between solid and colloidal fractions of the sediment, with ∼99% associated to the solid phase. Any uptake of CeO2 nanoparticles into worms was only through ingestion. Stabilized 10 nm particles were retained even after gut clearance, indicating that these particles may translocate across the gut wall.