Platinum vaporization-deposition coated polycarbonate membranes for comprehensive, multimodal, and correlative microscopic analysis of micro-and nanoplastics and other environmental particles.

Anthropogenic particles, including microplastics, are receiving ever-increasing concern due to their potential environmental impact. Surveys and monitoring require sampling from many environmental and biological matrices, including natural water, drinking water, sediment, and air. However, there are no standard methods for sampling particles in the environment; thereby, many different approaches are used for both single particle and ensemble distribution or bulk chemical analyses. In the microplastics field, particles are often analyzed on membranes using automated analysis with spectroscopic techniques such as Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy. For automated analysis, the filters' properties are crucial. We coated polycarbonate (PC) membranes with 100 nm platinum (Pt) on both side using a e-beam evaporator and evaluated their suitability for filtrating and analysis of environmental samples. The PC membranes have a defined and practical pore size, available in many pore sizes and with circular diameter of 47 mm and 25 mm. Our Pt coated membranes can handle large volumes of fresh and marine waters, high pressure, and various treatment solutions. Moreover, they have good optical properties for imaging with light microscopy (LM) and Scanning Electron Microscopy (SEM), and no disturbing background signal for Raman or FTIR spectroscopy analysis.

Unraveling the Marine Microplastic Cycle: The First Simultaneous Data Set for Air, Sea Surface Microlayer, and Underlying Water.

Microplastics (MP) including tire wear particles (TWP) are ubiquitous. However, their mass loads, transport, and vertical behavior in water bodies and overlying air are never studied simultaneously before. Particularly, the sea surface microlayer (SML), a ubiquitous, predominantly organic, and gelatinous film (<1 mm), is interesting since it may favor MP enrichment. In this study, a remote-controlled research catamaran simultaneously sampled air, SML, and underlying water (ULW) in Swedish fjords of variable anthropogenic impacts (urban, industrial, and rural) to fill these knowledge gaps in the marine-atmospheric MP cycle. Polymer clusters and TWP were identified and quantified with pyrolysis-gas chromatography-mass spectrometry. Air samples contained clusters of polyethylene terephthalate, polycarbonate, and polystyrene (max 50 ng MP m-3). In water samples (max. 10.8 µg MP L-1), mainly TWP and clusters of poly(methyl methacrylate) and polyethylene terephthalate occurred. Here, TWP prevailed in the SML, while the poly(methyl methacrylate) cluster dominated the ULW. However, no general MP enrichment was observed in the SML. Elevated anthropogenic influences in urban and industrial compared to the rural fjord areas were reflected by enhanced MP levels in these areas. Vertical MP movement behavior and distribution were not only linked to polymer characteristics but also to polymer sources and environmental conditions.

Comparison of pre-treatment methods and heavy density liquids to optimize microplastic extraction from natural marine sediments.

The ubiquitous occurrence of anthropogenic particles, including microplastics in the marine environment, has, over the last years, gained worldwide attention. As a result, many methods have been developed to estimate the amount and type of microplastics in the marine environment. However, there are still no standardized protocols for how different marine matrices should be sampled or how to extract and identify these particles, making meaningful data comparison hard. Buoyant microplastics are influenced by winds and currents, and concentrations could hence be expected to be highly variable over time. However, since both high density and most of the initially buoyant microplastics are known to eventually sink and settle on the seafloor, marine sediments are proposed as a suitable matrix for microplastics monitoring. Several principles, apparatuses, and protocols for extracting microplastics from marine sediments have been presented, but extensive comparison of the different steps in the protocols using real environmental samples is lacking. Thus, in this study, different pre-treatment and subsequent density separation protocols for extraction of microplastics from replicate samples of marine sediment were compared. Two pre-treatment methods, one using inorganic chemicals (NaClO + KOH + Na4P2O7) and one using porcine pancreatic enzymes, as well as one with no pre-treatment of the sediment, were compared in combination with two commonly used high-density saline solutions used for density separation, sodium chloride (NaCl) and zinc chloride (ZnCl2). Both pre-treatment methods effectively removed organic matter, and both saline solutions extracted lighter plastic particles such as polyethylene (PE) and polypropylene (PP). The most efficient combination, chemical pre-treatment and density separation with ZnCl2, was found to extract > 15 times more particles (≥ 100 µm) from the sediment than other treatment combinations, which could largely be explained by the high presence and efficient extraction of PVC particles.

Ecotoxicological effects of silver nanoparticles in marine mussels.

As the production of silver nanoparticles (AgNPs) is becoming more prevalent, it is becoming increasingly necessary to understand the toxicological effects they can have on different ecosystems. In the marine bioindicator species M. galloprovincialis Lam we predicted toxicity and bioaccumulation of 5 nm alkane-coated and 50 nm uncoated silver nanoparticles (AgNPs) along with silver nitrate as a function of the actual dose level. We generated a time persistence model of silver in seawater and used the Area Under the Curve (AUC) as independent variable in the hazard assessment. This approach allowed us to evaluate unbiased ecotoxicological endpoints for acute (survival) and chronic toxicity (byssal adhesion). Logistic regression analysis rendered an overall LC5096h values of 0.81 ± 0.07 mg h L-1 irrespectively of the silver form. By contrast, for byssal adhesion regression analysis revealed a much higher toxicological potential of silver nitrate vs AgNPs with EC5024h values respectively of 0.0024 ± 0.0009 vs 0.053 ± 0.016 and 0.063 (no computable error for 50 nm AgNP) mg h L-1, undoubtedly confirming a prevalence of ionic silver effects over AgNPs. Bioaccumulation was more efficient for silver nitrate >5 nm AgNP >50 nm AgNP reflecting a parallel with the preferential uptake route / target organ. Finally, we derived Risk Quotient (RQs) for acute and chronic effects of nanosilver in shellfish and showed that the RQs are far from the Level of Concern (LoC) at current estimated environmental concentrations (EECs). This information can ultimately help researchers, policy makers, and industry professionals decide how to safely regulate and/or dispose of AgNPs.

Outside the Safe Operating Space of the Planetary Boundary for Novel Entities.

We submit that the safe operating space of the planetary boundary of novel entities is exceeded since annual production and releases are increasing at a pace that outstrips the global capacity for assessment and monitoring. The novel entities boundary in the planetary boundaries framework refers to entities that are novel in a geological sense and that could have large-scale impacts that threaten the integrity of Earth system processes. We review the scientific literature relevant to quantifying the boundary for novel entities and highlight plastic pollution as a particular aspect of high concern. An impact pathway from production of novel entities to impacts on Earth system processes is presented. We define and apply three criteria for assessment of the suitability of control variables for the boundary: feasibility, relevance, and comprehensiveness. We propose several complementary control variables to capture the complexity of this boundary, while acknowledging major data limitations. We conclude that humanity is currently operating outside the planetary boundary based on the weight-of-evidence for several of these control variables. The increasing rate of production and releases of larger volumes and higher numbers of novel entities with diverse risk potentials exceed societies' ability to conduct safety related assessments and monitoring. We recommend taking urgent action to reduce the harm associated with exceeding the boundary by reducing the production and releases of novel entities, noting that even so, the persistence of many novel entities and/or their associated effects will continue to pose a threat.

Deep Learning for Reconstructing Low-Quality FTIR and Raman Spectra─A Case Study in Microplastic Analyses.

Herein we report on a deep-learning method for the removal of instrumental noise and unwanted spectral artifacts in Fourier transform infrared (FTIR) or Raman spectra, especially in automated applications in which a large number of spectra have to be acquired within limited time. Automated batch workflows allowing only a few seconds per measurement, without the possibility of manually optimizing measurement parameters, often result in challenging and heterogeneous datasets. A prominent example of this problem is the automated spectroscopic measurement of particles in environmental samples regarding their content of microplastic (MP) particles. Effective spectral identification is hampered by low signal-to-noise ratios and baseline artifacts as, again, spectral post-processing and analysis must be performed in automated measurements, without adjusting specific parameters for each spectrum. We demonstrate the application of a simple autoencoding neural net for reconstruction of complex spectral distortions, such as high levels of noise, baseline bending, interferences, or distorted bands. Once trained on appropriate data, the network is able to remove all unwanted artifacts in a single pass without the need for tuning spectra-specific parameters and with high computational efficiency. Thus, it offers great potential for monitoring applications with a large number of spectra and limited analysis time with availability of representative data from already completed experiments.

Summer sea ice melt and wastewater are important local sources of microlitter to Svalbard waters.

Human activities leave traces of marine litter around the globe. The Arctic is, despite its remoteness, emerging as an area of no exception to this environmental issue. Arctic sea ice has previously been found to constitute a temporal sink of microplastics, but the potential release and subsequent fate of microplastics in the marine environment are yet unknown. Furthermore, the relative importance of local sources of microplastics in the Arctic marine environment is under discussion. In this study, the concentration and distribution of anthropogenic microparticles (AMPs, <5 mm, including microplastics) have been investigated in marine waters and sea ice of Svalbard. Seawater samples throughout the water column and floating sea ice samples were collected along a transect originating in Rijpfjorden, reaching northwards to the sea ice-edge. Seawater samples were also collected along a transect extending westwards from head to mouth of Kongsfjorden. Samples were collected throughout the water column with stations positioned to enable detection of potential AMP emissions from the wastewater outlet in Ny-Ålesund. Along both transects, environmental parameters were measured to explore potential correlations with AMP distribution. High concentrations of AMPs were detected in sea ice (158 ±â€¯155 AMPs L-1). Based on both AMP concentrations and characteristics, AMPs identified in seawater of the marginal ice zone are to a large extent likely released during the melting of sea ice. The release of AMPs during summer melting of sea ice was concomitantly taking place with the ice-edge bloom, suggesting increased bioavailability to Arctic marine biota. Concentrations of AMPs were up to an order of magnitude higher in Kongsfjorden (up to 48.0 AMPs L-1) than in Rijpfjorden (up to 7.4 AMPs L-1). The distribution and composition of AMPs in Kongsfjorden suggest the wastewater outlet in Ny-Ålesund to be a likely source. Our results emphasize the importance of local point- and diffuse sources of AMPs in the Arctic and stress the urgency of considering their associated environmental impact. Implementation of regulatory policy is of importance, particularly since human activities and environmental pressures are increasing in the Arctic.

Comparison between manta trawl and in situ pump filtration methods, and guidance for visual identification of microplastics in surface waters.

Owing to the development and adoption of a variety of methods for sampling and identifying microplastics, there is now data showing the presence of microplastics in surface waters from all over the world. The difference between the methods, however, hampers comparisons, and to date, most studies are qualitative rather than quantitative. In order to allow for a quantitative comparison of microplastics abundance, it is crucial to understand the differences between sampling methods. Therefore, a manta trawl and an in situ filtering pump were compared during realistic, but controlled, field tests. Identical microplastic analyses of all replicates allowed the differences between the methods with respect to (1) precision, (2) concentrations, and (3) composition to be assessed. The results show that the pump gave higher accuracy with respect to volume than the trawl. The trawl, however, sampled higher concentrations, which appeared to be due to a more efficient sampling of particles on the sea surface microlayer, such as expanded polystyrene and air-filled microspheres. The trawl also sampled a higher volume, which decreased statistical counting uncertainties. A key finding in this study was that, regardless of sampling method, it is critical that a sufficiently high volume is sampled to provide enough particles for statistical evaluation. Due to the patchiness of this type of contaminant, our data indicate that a minimum of 26 particles per sample should be recorded to allow for concentration comparisons and to avoid false null values. The necessary amount of replicates to detect temporal or spatial differences is also discussed. For compositional differences and size distributions, even higher particle counts would be necessary. Quantitative measurements and comparisons would also require an unbiased approach towards both visual and spectroscopic identification. To facilitate the development of such methods, a visual protocol that can be further developed to fit different needs is introduced and discussed. Some of the challenges encountered while using FTIR microspectroscopic particle identification are also critically discussed in relation to specific compositions found.

An efficient and gentle enzymatic digestion protocol for the extraction of microplastics from bivalve tissue.

Standardized methods for the digestion of biota for microplastic analysis are currently lacking. Chemical methods can be effective, but can also cause damage to some polymers. Enzymatic methods are known to be gentler, but often laborious, expensive and time consuming. A novel tissue digestion method with pancreatic enzymes and a pH buffer (Tris) is here presented in a comparison to a commonly applied digestion protocol with potassium hydroxide. The novel protocol demonstrates a highly efficient removal of bivalve tissue (97.7 ±â€¯0.2% dry weight loss) already over-night. Furthermore, it induces no impairment in terms of ability to correctly identify four pre-weathered plastic polymers and six textile fiber polymers by Fourier transform infrared spectroscopy after exposure. The high-throughput protocol requires minimal handling, is of low cost and does not pose risk to the performer or the environment. It is therefore suggested as a candidate for a standardized digestion protocol, enabling successful analysis of microplastics ingested by bivalves.

Are We Speaking the Same Language? Recommendations for a Definition and Categorization Framework for Plastic Debris.

The accumulation of plastic litter in natural environments is a global issue. Concerns over potential negative impacts on the economy, wildlife, and human health provide strong incentives for improving the sustainable use of plastics. Despite the many voices raised on the issue, we lack a consensus on how to define and categorize plastic debris. This is evident for microplastics, where inconsistent size classes are used and where the materials to be included are under debate. While this is inherent in an emerging research field, an ambiguous terminology results in confusion and miscommunication that may compromise progress in research and mitigation measures. Therefore, we need to be explicit on what exactly we consider plastic debris. Thus, we critically discuss the advantages and disadvantages of a unified terminology, propose a definition and categorization framework, and highlight areas of uncertainty. Going beyond size classes, our framework includes physicochemical properties (polymer composition, solid state, solubility) as defining criteria and size, shape, color, and origin as classifiers for categorization. Acknowledging the rapid evolution of our knowledge on plastic pollution, our framework will promote consensus building within the scientific and regulatory community based on a solid scientific foundation.

Influence of thermooxidative degradation on the in situ fate of polyethylene in temperate coastal waters.

Polyethylene is a commonly used polymer in plastic products and is often found as marine litter. Nevertheless there is limited knowledge about what happens to the material when it ends up in the sea. Polyethylene films were therefore thermally oxidised to four different levels of degradation. The films were then placed in stainless-steel cages in the sea off the Swedish west coast for 12 summer weeks. Subsamples were analysed with respect to biofouling, degradation and buoyancy. All levels showed a continued oxidation in the field. The pre-degraded films started fragmenting and the non-degraded films showed a decrease in tensile strain. All levels showed increased biofouling with higher presence of filamentous algae and bryozoans on pre-degraded materials. The density (kg·m-3) of the films was seen to increase slightly, and the apparent density for the pre-degraded films (density of the films with biofilm) showed a strong increase, which resulted in sinking.

Microplastics in sub-surface waters of the Arctic Central Basin.

Polar oceans, though remote in location, are not immune to the accumulation of plastic debris. The present study, investigated for the first time, the abundance, distribution and composition of microplastics in sub-surface waters of the Arctic Central Basin. Microplastic sampling was carried out using the bow water system of icebreaker Oden (single depth: 8.5 m) and CTD rosette sampler (multiple depths: 8-4369 m). Potential microplastics were isolated and analysed using Fourier Transform Infrared Spectroscopy (FT-IR). Bow water sampling revealed that the median microplastic abundance in near surface waters of the Polar Mixed Layer (PML) was 0.7 particles m-3. Regarding the vertical distribution of microplastics in the ACB, microplastic abundance (particles m-3) in the different water masses was as follows: Polar Mixed Layer (0-375) > Deep and bottom waters (0-104) > Atlantic water (0-95) > Halocline i.e. Atlantic or Pacific (0-83).

The unaccountability case of plastic pellet pollution.

Plastic preproduction pellets are found in environmental samples all over the world and their presence is often linked to spills during production and transportation. To better understand how these pellets end up in the environment we assessed the release of plastic pellets from a polyethylene production site in a case study area on the Swedish west coast. The case study encompasses; field measurements to evaluate the level of pollution and pathways, models and drifters to investigate the potential spread and a revision of the legal framework and the company permits. This case study show that millions of pellets are released from the production site annually but also that there are national and international legal frameworks that if implemented could help prevent these spills. Bearing in mind the negative effects observed by plastic pollution there is an urgent need to increase the responsibility and accountability of these spills.

Screening for microplastics in sediment, water, marine invertebrates and fish: Method development and microplastic accumulation.

Measurements of microplastics in biota and abiotic matrices are key elements of exposure and risk assessments for this emerging environmental pollutant. We investigated the abundance of microplastics in field-collected biota, sediment and water. An improved sediment extraction method, based on density separation was developed. For analysis of microplastics in biota we found that an adapted enzymatic digestion protocol using proteinase K performed best, with a 97% recovery of spiked plastic particles and no observed degradation effects on the plastics in subsequent Raman analysis. Field analysis revealed that 8 of 9 tested invertebrate species from the North Sea and 68% of analyzed individuals of brown trout (Salmo trutta) from the Swedish West Coast had microplastics in them. Based on the number of plastic particles per kg d.w. the microplastic concentrations found in mussels were approximately a thousand-fold higher compared to those in sediment and surface water samples from the same location.

Influence of organic molecules on the aggregation of TiO2 nanoparticles in acidic conditions.

Engineered nanoparticles released into the environment may interact with natural organic matter (NOM). Surface complexation affects the surface potential, which in turn may lead to aggregation of the particles. Aggregation of synthetic TiO2 (anatase) nanoparticles in aqueous suspension was investigated at pH 2.8 as a function of time in the presence of various organic molecules and Suwannee River fulvic acid (SRFA), using dynamic light scattering (DLS) and high-resolution transmission electron microscopy (TEM). Results showed that the average hydrodynamic diameter and ζ-potential were dependent on both concentration and molecular structure of the organic molecule. Results were also compared with those of quantitative batch adsorption experiments. Further, a time study of the aggregation of TiO2 nanoparticles in the presence of 2,3-dihydroxybenzoic acid (2,3-DHBA) and SRFA, respectively, was performed in order to observe changes in ζ-potential and particle size over a time period of 9 months. In the 2,3-DHBA-TiO2 system, ζ-potentials decreased with time resulting in charge neutralization and/or inversion depending on ligand concentration. Aggregate sizes increased initially to the micrometer size range, followed by disaggregation after several months. No or very little interaction between SRFA and TiO2 occurred at the lowest concentrations tested. However, at the higher concentrations of SRFA, there was an increase in both aggregate size and the amount of SRFA adsorbed to the TiO2 surface. This was in correlation with the ζ-potential that decreased with increased SRFA concentration, leading to destabilization of the system. These results stress the importance of performing studies over both short and long time periods to better understand and predict the long-term effects of nanoparticles in the environment.

Effects of silver nanoparticles on the freshwater snail Physa acuta: The role of test media and snails' life cycle stage.

Silver nanoparticles (AgNPs) are widely used worldwide, most likely leading to their release into the environment and a subsequent increase of environmental concentrations. Studies of their deleterious effects on organisms is crucial to understand their environmental impacts. The freshwater snail Physa acuta was chosen to evaluate the potential deleterious effects of AgNPs and their counterpart AgNO3 , through water-only exposures. The toxicity of AgNPs is greatly influenced by medium composition. Thus, 2 media were tested: artificial pond water (APW) and modified APW (adapted by removing calcium chloride). Acute tests (96 h) were performed with juvenile and adult snails in both media to assess lethality, and egg mass chronic tests were conducted with APW medium only to assess embryo viability and mortality, carried out until 90% hatching success was reached in the control. Acute toxicity increased with decreasing shell length for both silver forms (ion and nanoparticle); that is, juveniles were more sensitive than adults. Different test media led to dissimilar median lethal concentrations, with chloride playing an important role in toxicity, most likely by complexation with silver ions, which would reduce the bioavailability, uptake, and toxicity of silver. Chronic tests showed that hatching success was more sensitive to silver in the ionic form than in the particulate form. Different forms of silver, exposure media, and life cycle stages led to different patterns of toxicity, highlighting an impairment in the snails' life cycle. Environ Toxicol Chem 2017;36:243-253. © 2016 SETAC.

Effects of alginate on stability and ecotoxicity of nano-TiO2 in artificial seawater.

The large-scale use of titanium dioxide nanoparticles (nano-TiO2) in consumer and industrial applications raised environmental health and safety concerns. Potentially impacted ecosystems include estuarine and coastal organisms. Results from ecotoxicological studies with nano-TiO2 dispersed in salt exposure media are difficult to interpret due to fast flocculation and sedimentation phenomena affecting the dispersion stability. The goal of this study was to investigate the stabilisation effect of alginate on uncoated nano-Ti22 in artificial seawater dispersions used in ecotoxicity bioassays. The most effective stabilisation was obtained at alginate concentration of 0.45 g/L after sonicating dispersions for 20 min (100 W). The size distribution remained constant after re-suspension, indicating that no agglomeration occurred after deposition. Ecotoxicity tests on Artemia franciscana and Phaeodactylum tricornutum did not show any adverse effects related to the presence of alginate in the exposure media, and provided evidence on possible reduced bioavailability of nano-TiO2. The suitable concentration of alginate is recommended to occur on a case-by-case basis.

Common strategies and technologies for the ecosafety assessment and design of nanomaterials entering the marine environment.

The widespread use of engineered nanomaterials (ENMs) in a variety of technologies and consumer products inevitably causes their release into aquatic environments and final deposition into the oceans. In addition, a growing number of ENM products are being developed specifically for marine applications, such as antifouling coatings and environmental remediation systems, thus increasing the need to address any potential risks for marine organisms and ecosystems. To safeguard the marine environment, major scientific gaps related to assessing and designing ecosafe ENMs need to be filled. In this Nano Focus, we examine key issues related to the state-of-the-art models and analytical tools being developed to understand ecological risks and to design safeguards for marine organisms.