Weathering Plastics as a Planetary Boundary Threat: Exposure, Fate, and Hazards.

We described in 2017 how weathering plastic litter in the marine environment fulfils two of three criteria to impose a planetary boundary threat related to "chemical pollution and the release of novel entities": (1) planetary-scale exposure, which (2) is not readily reversible. Whether marine plastics meet the third criterion, (3) eliciting a disruptive impact on vital earth system processes, was uncertain. Since then, several important discoveries have been made to motivate a re-evaluation. A key issue is if weathering macroplastics, microplastics, nanoplastics, and their leachates have an inherently higher potential to elicit adverse effects than natural particles of the same size. We summarize novel findings related to weathering plastic in the context of the planetary boundary threat criteria that demonstrate (1) increasing exposure, (2) fate processes leading to poorly reversible pollution, and (3) (eco)toxicological hazards and their thresholds. We provide evidence that the third criterion could be fulfilled for weathering plastics in sensitive environments and therefore conclude that weathering plastics pose a planetary boundary threat. We suggest future research priorities to better understand (eco)toxicological hazards modulated by increasing exposure and continuous weathering processes, to better parametrize the planetary boundary threshold for plastic pollution.

Chemometers: an integrative tool for chemical assessment in multimedia environments.

We propose novel chemometers - passive equilibrium samplers of, e.g., silicone - as an integrative tool for the assessment of hydrophobic organic compounds in multimedia environments. The traditional way of assessing levels of organic pollutants across different environmental compartments is to compare the chemical concentration normalized to the major sorptive phase in two or more media. These sorptive phases for hydrophobic organic compounds differ between compartments, e.g., lipids in biota and organic carbon in sediments. Hence, comparability across media can suffer due to differences in sorptive capacities, but also extraction protocols and bioavailability. Chemometers overcome these drawbacks; they are a common, universal and well-defined polymer reference phase for sampling of a large range of nonpolar organic pollutants in different matrices like biota, sediment and water. When bringing the chemometer into direct contact with the sample, the chemicals partition between the sample and the polymer until thermodynamic equilibrium partitioning is established. At equilibrium, the chemical concentrations in the chemometers can be determined and directly compared between media, e.g., between organisms of different trophic levels or inhabiting different areas, between organs within an organism or between biotic and abiotic compartments, amongst others. Chemometers hence allow expressing the data on a common basis, as the equilibrium partitioning concentrations in the polymer, circumventing normalizations. The approach is based on chemical activity rather than total concentrations, and as such, gives a measure of the "effective concentration" of a compound or a mixture. Furthermore, chemical activity is the main driver for partitioning, biouptake and toxicity. As an additional benefit, the extracts of the chemometers only require limited cleanup efforts, avoiding introduction of a bias between chemicals of different persistence, and can be submitted to both chemical analysis and/or bioanalytical profiling.

Characterizing the marine mammal exposome by iceberg modeling, linking chemical analysis and in vitro bioassays.

The present study complements work on mixture effects measured with in vitro bioassays of passive equilibrium sampling extracts using the silicone polydimethylsiloxane (PDMS) in organs from marine mammals with chemical profiling. Blubber, liver, kidney and brain tissues of harbor porpoise (Phocoena phocoena), harbor seal (Phoca vitulina), ringed seal (Phoca hispida) and orca (Orcinus orca) from the North and Baltic Seas were investigated. We analyzed 117 chemicals including legacy and emerging contaminants using gas chromatography-high resolution mass spectrometry and quantified 70 of those chemicals in at least one sample. No systematic differences between the organs were found. Only for single compounds a clear distribution pattern was observed. For example, 4,4'-dichlorodiphenyltrichloroethane, enzacamene and etofenprox were mainly detected in blubber, whereas tonalide and the hexachlorocyclohexanes were more often found in liver. Furthermore, we compared the chemical profiling with the bioanalytical results using an iceberg mixture model, evaluating how much of the biological effect could be explained by the analyzed chemicals. The mixture effect predicted from the quantified chemical concentrations explained 0.014-83% of the aryl hydrocarbon receptor activating effect (AhR-CALUX), but less than 0.13% for the activation of the oxidative stress response (AREc32) and peroxisome-proliferator activated receptor (PPARγ). The quantified chemicals also explained between 0.044-45% of the cytotoxic effect measured with the AhR-CALUX. The largest fraction of the observed effect was explained for the orca, which was the individuum with the highest chemical burden. This study underlines that chemical analysis and bioassays are complementary to comprehensively characterize the mixture exposome of marine mammals.

A dataset of organic pollutants identified and quantified in recycled polyethylene pellets.

Plastics are produced with a staggering array of chemical compounds, with many being known to possess hazardous properties, and others lacking comprehensive hazard data. Furthermore, non-intentionally added substances can contaminate plastics at various stages of their lifecycle, resulting in recycled materials containing an unknown number of chemical compounds at unknown concentrations. While some national and regional regulations exist for permissible concentrations of hazardous chemicals in specific plastic products, less than 1 % of plastics chemicals are subject to international regulation [1]. There are currently no policies mandating transparent reporting of chemicals throughout the plastics value chain or comprehensive monitoring of chemicals in recycled materials. The dataset presented here provides the chemical analysis of 28 samples of recycled High-Density Polyethylene (HDPE) pellets obtained from various regions of the Global South, along with a reference sample of virgin HDPE. The analysis comprises both Target and Non-Targeted Screening approaches, employing Liquid Chromatography-High-Resolution Mass Spectrometry (LC-HRMS) and Gas Chromatography-High-Resolution Mass Spectrometry (GC-HRMS). In total, 491 organic compounds were detected and quantified, with an additional 170 compounds tentatively annotated. These compounds span various classes, including pesticides, pharmaceuticals, industrial chemicals, plastic additives. The results highlight the prevalence of certain chemicals, such as N-ethyl-o-Toluesulfonamide, commonly used in HDPE processing, found in high concentrations. The paper provides a dataset advancing knowledge of the complex chemical composition associated with recycled plastics.

Exploring the partitioning of hydrophobic organic compounds between water, suspended particulate matter and diverse fish species in a German river ecosystem.

Background: Bioaccumulation of hydrophobic organic compounds (HOCs) along freshwater food chains is a major environmental concern as top predators in food webs are relevant for human consumption. To characterize and manage the associated risks, considerable numbers of organisms are sampled regularly for monitoring purposes. However, ethical and financial issues call for an alternative, more generic and more robust approach for assessing the internal exposure of fish that circumvents large variability in biota sampling due to interindividual differences. Passive sampling devices (PSDs) offer a fugacity-based approach for pollutant enrichment from different abiotic environmental compartments with a subsequent estimation of bioaccumulation in fish which we explored and compared to HOC concentrations in fish as determined using traditional approaches. Results: In this study, concentrations in silicone-based PSDs applied to the water phase and suspended particulate matter (SPM) of a river polluted with HOCs were used to estimate the concentration in model lipids at thermodynamic equilibrium with either environmental compartment. For comparison, muscle tissue of seven fish species (trophic level 1.8 to 2.8) was extracted using traditional exhaustive solvent extraction, and the lipid-normalized concentrations of HOCs were determined. The PSD-based data from SPM proved to be a more conservative estimator for HOCs accumulated in fish than those from water. Body length of the fish was found to be more suitable to describe increasing accumulation of HOCs than their trophic level as derived from stable isotope analysis and might offer a suitable alternative for future studies. Conclusions: By combining fugacity-based sampling in the abiotic environment, translation into corresponding concentrations in model lipids and body length as an indicator for increasing bioaccumulation in fish, we present a suggestion for a robust approach that may be a meaningful addition to conventional monitoring methods. This approach potentially increases the efficiency of existing monitoring programs without the need to regularly sacrifice vertebrate species. Supplementary Information: The online version contains supplementary material available at 10.1186/s12302-022-00644-w.

Removing Disturbing Matrix Constituents from Biota Extracts from Total Extraction and Silicone-Based Passive Sampling.

Contaminant analysis in biota extracts can be hampered by matrix interferences caused by, for example, co-extracted lipids that compromise the quality of the analytical data and require frequent maintenance of the analytical instruments. In the present study, using gas chromatography coupled to high resolution mass spectrometry (GC-HRMS), we aimed to develop and validate a straightforward, robust, and reproducible cleanup method with acceptable recoveries for diverse compound classes with a wide range of physicochemical properties representative of pollutant screening in biota extracts. We compared Oasis PRiME HLB cartridges, Agilent Captiva EMR-Lipid cartridges, and "Freeze-Out" with salmon lipids spiked with 113 target chemicals. The EMR-Lipid cartridges provided extracts with low matrix effects at reproducible recoveries of the multi-class target analytes (93 ± 9% and 95 ± 7% for low and high lipid amounts, respectively). The EMR-Lipid cartridges were further tested with spiked pork lipids submitted to total extraction or silicone-based passive sampling. Reproducible recoveries were achieved and matrix residuals were largely removed as demonstrated gravimetrically for both types of extracts. Ion suppression of halogenated compounds was not as efficiently removed by the cleanup of total and silicone-based extracts of pork lipids as for the salmon lipids. However, the samples with clean up provided better instrument robustness than those without cleanup. Hence, EMR-Lipid cartridges were shown to be efficient as a cleanup method in multi-class monitoring of biota samples and open up new possibilities as a suitable cleanup method for silicone extracts in biota passive sampling studies using GC-HRMS analysis. Environ Toxicol Chem 2021;40:2693-2704. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Passive equilibrium sampling of hydrophobic organic compounds in homogenised fish tissues of low lipid content.

Passive equilibrium sampling using polymer samplers in lean tissue is one of the current challenges in assessing bioaccumulation and biomagnification due to the long time needed to reach equilibrium. Despite recent progress achieved by rolling pieces of intact fish fillet with sheets of silicone, there is still a need for a passive sampling method for homogenates that achieves equilibrium before tissue decay starts. In this work, a new approach for relocation of silicone passive samplers in homogenates of lean fish was established for three homogenates with lipid contents varying from 1.2% to 6.1%. Results showed that for 20 model hydrophobic organic compounds with log KOW between 3.9 and 7.8, equilibrium between the silicone and the tissue was achieved in less than 3 days at 4 °C. The concentrations in lipids obtained using passive equilibrium sampling and those from traditional total solvent extraction agreed well, within a factor of 1.3. This new procedure extends the use of passive samplers to homogenised fish tissues of low lipid content, which is highly relevant for environmental studies focused on bioaccumulation of contaminants.

Using stable isotope analysis to assess trophic relationships between Atlantic bluefin tuna (Thunnus thynnus) and striped dolphin (Stenella coeruleoalba) in the Strait of Gibraltar.

Stable isotope analysis (δ13C and δ15N from liver and muscle) was used to assess trophic relationships between Atlantic bluefin tuna (ABFT) (Thunnus thynnus) and striped dolphin (SC) (Stenella coeruleoalba) in the Strait of Gibraltar (SoG). δ15N values from ABFT muscle and liver tissues were significantly different from those of dolphin samples, but no for δ13C values. Diet estimation by MixSIAR models from muscle and liver revealed that ABFT fed mainly on squids (Todaropsis eblanae and Illex coindetii). The shrimp Pasiphaea sp. was estimated to be the most important prey-species in the diet of SC. Trophic positions estimated from muscle and liver isotopic data suggested that ABFT occupy a higher trophic level than SC. Estimations of isotopic niche, as measured by the standard ellipse area, indicated that ABFT show a broader trophic niche than SC; furthermore, SEAc did not show trophic overlap between both predators. The results of this study suggest that resource partitioning occurs between ABFT and SC in the SoG ecosystem.

Assessing trace elements in striped dolphins from the Strait of Gibraltar: Clues to link the bioaccumulation in the westernmost Mediterranean Sea area and nearest Atlantic Ocean.

Dolphins are considered sentinel species in the marine environment. The Strait of Gibraltar is the only passage between the Mediterranean Sea and the Atlantic Ocean, being the transitional region which connects these two basins and one of the most important routes of cetacean migration worldwide. In this work, eight trace elements (TE) were studied in 45 samples of liver, kidney and muscle, from 15 specimens stranded in this study area. The preliminary results show, among others, the patterns of distribution of the TE in the target organs studied, the influence of sex, length and developmental stage in these TE concentrations and the Se/Hg ratio. Subsequently, the results of TE concentrations in liver have being compared to previous data on S. coeruleoalba from the westernmost Mediterranean Sea and the nearest Atlantic Ocean. For some elements (e.g. for As), concentrations are similar to those obtained from Atlantic samples, despite in other cases (e.g. for Cd) results are lined up with those observed in Mediterranean studies. In addition, in the case of some TE (e.g. Se and Zn) the results are in the middle of those reported for both basins, reinforcing the idea of the Strait of Gibraltar being a transitional zone. Present study is the first research regarding this issue in this outstanding region, aiming to give insights of how this matchless area can help to link TE concentrations observed in these Atlantic and Mediterranean threatened species.

Estimating baseline toxicity of PAHs from marine chronically polluted sediments and bioaccumulation in target organs of fish hypothetically exposed to them: a new tool in risk assessment.

In soils and sediments contaminated by Hydrophobic Organic Compounds (HOCs), the total concentrations are less indicative of potential exposure and distribution than the associated freely dissolved concentrations (Cfree) or chemical activity. Therefore, these two parameters are increasingly used to assess sediment contamination with regard to their (1) partitioning into the water column, (2) bioaccumulation and (3) baseline toxic potential. In this work, sediments from a chronically polluted coastal area, with similar total PAH concentrations, were studied using PDMS coated glass jars (obtaining Cfree(SW) and chemical activity) to predict baseline toxicity and potential bioaccumulation from these sediments. The results indicate that, on the one hand, the chemical activity of the sediments differed by up to one order of magnitude and was below the level at which lethal baseline toxicity is expected, but is still a cause for concern due to the presence of other pollutants and different mechanisms of action. On the other hand, the combination of Cfree measurements and Biota to Sediment Accumulation Factors (BSAFs) allowed concentrations in different target organs of benthic flatfish, hypothetically exposed to these chronically polluted sediments, to be estimated. This new approach allows us to predict the concentration in biological tissues under the study of Cfree(SW) in sediments, as a useful tool in risk assessment.

Sources, transport and fate of PAHs in sediments and superficial water of a chronically polluted semi-enclosed body of seawater: linking of compartments.

This paper describes a study of the occurrence, levels and temporal evolution of PAHs in a bay characterized by persistent chronic impacts. A total of 40 samples, 20 of sediment and 20 of water, were taken at each of five different stations, in four sampling campaigns. Analyses of pollutants have been made using GC-MS. Results indicate that in a coastal environment subjected to chronic pollution by pyrolytic PAHs, episodes of petrogenic pollution, like oil-spills, can be identified by the combination of different source ratios. Results also indicate that, in the study area, PAHs are transported from superficial water to sediment. This conclusion is based on the degree of coincidence found in the presence/absence of individual PAHs in both compartments and in their petrogenic/pyrolytic nature, the positive sedimentation rate in the study area, together with the performance of the analyses of unfiltered water and the distribution of sources of PAHs found.