Persistence of PFOA Pollution at a PTFE Production Site and Occurrence of Replacement PFASs in English Freshwaters Revealed by Sentinel Species, the Eurasian Otter (Lutra lutra).

Concentrations of 33 PFASs were determined in 20 Eurasian otters, sampled 2015-2019, along a transect away from a factory, which used PFOA in PTFE manufacture. Despite cessation of usage in 2012, PFOA concentrations remained high near the factory (>298 µg/kg ww <20 km from factory) and declined with increasing distance (<57 µg/kg ww >150 km away). Long-chain legacy PFASs dominated the Σ33PFAS profile, particularly PFOS, PFOA, PFDA, and PFNA. Replacement compounds, PFECHS, F-53B, PFBSA, PFBS, PFHpA, and 8:2 FTS, were detected in ≥19 otters, this being the first report of PFBSA and PFECHS in the species. Concentrations of replacement PFASs were generally lower than legacy compounds (max: 70.3 µg/kg ww and 4,640 µg/kg ww, respectively). Our study underscores the utility of otters as sentinels for evaluating mitigation success and highlights the value of continued monitoring to provide insights into the longevity of spatial associations with historic sources. Lower concentrations of replacement, than legacy, PFASs likely reflect their lower bioaccumulation potential, and more recent introduction. Continued PFAS use will inevitably lead to increased environmental and human exposure if not controlled. Further research is needed on fate, toxicity, and bioaccumulation of replacement compounds.

Significant Turning Point: Common Buzzard (Buteo buteo) Exposure to Second-Generation Anticoagulant Rodenticides in the United Kingdom.

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent populations, resulting in the serious secondary exposure of predators to these contaminants. In the United Kingdom (UK), professional use and purchase of SGARs were revised in the 2010s. Certain highly toxic SGARs have been authorized since then to be used outdoors around buildings as resistance-breaking chemicals under risk mitigation procedures. However, it is still uncertain whether and how these regulatory changes have influenced the secondary exposure of birds of prey to SGARs. Based on biomonitoring of the UK Common Buzzard (Buteo buteo) collected from 2001 to 2019, we assessed the temporal trend of exposure to SGARs and statistically determined potential turning points. The magnitude of difenacoum decreased over time with a seasonal fluctuation, while the magnitude and prevalence of more toxic brodifacoum, authorized to be used outdoors around buildings after the regulatory changes, increased. The summer of 2016 was statistically identified as a turning point for exposure to brodifacoum and summed SGARs that increased after this point. This time point coincided with the aforementioned regulatory changes. Our findings suggest a possible shift in SGAR use to brodifacoum from difenacoum over the decades, which may pose higher risks of impacts on wildlife.

Modelling the effects of the pyrethroid insecticide cypermethrin on the life cycle of the soil dwelling annelid Enchytraeus crypticus, an original experimental design to calibrate a DEB-TKTD model.

The Dynamic Energy Budget theory (DEB) enables ecotoxicologists to model the effects of chemical stressors on organism life cycles through the coupling of toxicokinetic-toxicodynamic (TK-TD) models. While good progress has been made in the application of DEB-TKTD models for aquatic organisms, applications for soil fauna are scarce, due to the lack of dedicated experimental designs suitable for collecting the required time series effect data. Enchytraeids (Annelida: Clitellata) are model organisms in soil ecology and ecotoxicology. They are recognised as indicators of biological activity in soil, and chemical stress in terrestrial ecosystems. Despite this, the application of DEB-TKTD models to investigate the impact of chemicals has not yet been tested on this family. Here we assessed the impact of the pyrethroid insecticide cypermethrin on the life cycle of Enchytraeus crypticus. We developed an original experimental design to collect the data required for the calibration of a DEB-TKTD model for this species. E. crypticus presented a slow initial growth phase that has been successfully simulated with the addition of a size-dependent food limitation for juveniles in the DEB model. The DEB-TKTD model simulations successfully agreed with the data for all endpoints and treatments over time. The highlighted physiological mode of action (pMoA) for cypermethrin was an increase of the growth energy cost. The threshold for effects on survival was estimated at 73.14 mg kg- 1, and the threshold for effects on energy budget (i.e., sublethal effects) at 19.21 mg kg- 1. This study demonstrates that DEB-TKTD models can be successfully applied to E. crypticus as a representative soil species, and may improve the ecological risk assessment for terrestrial ecosystems, and our mechanistic understanding of chemical effects on non-target species.

Anthropogenic Drivers of Variation in Concentrations of Perfluoroalkyl Substances in Otters (Lutra lutra) from England and Wales.

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous environmental contaminants that have been linked to adverse health effects in wildlife and humans. Here, we report the presence of PFASs in Eurasian otters (Lutra lutra) in England and Wales and their association with anthropogenic sources. The following 15 compounds were analyzed: 10 perfluoroalkyl carboxylic acids (PFCAs), 4 perfluoroalkyl sulfonic acids (PFSAs), and perfluorooctane sulfonamide, in livers of 50 otters which died between 2007 and 2009. PFASs were detected in all otters analyzed, with 12/15 compounds detected in ≥80% of otters. Perfluorooctane sulfonate (PFOS) accounted for 75% of the ΣPFAS profile, with a maximum concentration of 6800 µg/kg wet weight (ww). Long-chain (≥C8) PFCAs accounted for 99.9% of the ΣPFCA profile, with perfluorodecanoic acid and perfluorononanoic acid having the highest maxima (369 µg/kg ww and 170 µg/kg ww, respectively). Perfluorooctanoic acid (PFOA) concentrations were negatively associated with the distance from a factory that used PFOA in polytetrafluoroethylene manufacture. Most PFAS concentrations in otters were positively associated with load entering wastewater treatment works (WWTW) and with arable land, suggesting that WWTW effluent and sewage sludge-amended soils are significant pathways of PFASs into freshwaters. Our results reveal the widespread pollution of British freshwaters with PFASs and demonstrate the utility of otters as effective sentinels for spatial variation in PFAS concentrations.

Laboratory-Based Comparison for the Effects of Environmental Stressors Supports Field Evidence for the Relative Importance of Pollution on Life History and Behavior of the Pond Snail, Lymnaea stagnalis.

Biodiversity is declining at an alarming rate globally, with freshwater ecosystems particularly threatened. Field-based correlational studies have "ranked" stressors according to their relative effects on freshwater biota, however, supporting cause-effect data from laboratory exposures are lacking. Here, we designed exposures to elicit chronic effects over equivalent exposure ranges for three ubiquitous stressors (temperature: 22-28 °C; pollution [14 component mixture]: 0.05-50 µg/L; invasive predator cue [signal crayfish, Pacifasticus leniusculus]: 25-100% cue) and investigated effects on physiological end points in the pond snail (Lymnaeastagnalis). All stressors reduced posthatch survival at their highest exposure levels, however, highly divergent effects were observed at lower test levels. Temperature stimulated hatching, growth, and reproduction, whereas pollution delayed hatching, decreased growth, reduced egg number/embryo viability, and induced avoidance behavior. The invasive predator cue stimulated growth and reduced embryo viability. In agreement with field-based ranking of stressors, pollution was identified as having the most severe effects in our test system. We demonstrate here the utility of laboratory studies to effectively determine hierarchy of stressors according to their likelihood of causing harm in the field, which has importance for conservation. Finally, we report negative impacts on life-history traits central to population stability (survival/reproduction) at the lowest pollution level tested (0.05 µg/L).

Off-Target Stoichiometric Binding Identified from Toxicogenomics Explains Why Some Species Are More Sensitive than Others to a Widely Used Neonicotinoid.

Neonicotinoids are currently licensed for use in 120 countries, making accurate nontarget species sensitivity predictions critical. Unfortunately, such predictions are fraught with uncertainty, as sensitivity is extrapolated from only a few test species and neonicotinoid sensitivities can differ greatly between closely related taxa. Combining classical toxicology with de novo toxicogenomics could greatly improve sensitivity predictions and identify unexpectedly susceptible species. We show that there is a >30-fold differential species sensitivity (DSS) for the neonicotinoid imidacloprid between five earthworm species, a critical nontarget taxon. This variation could not be explained by differential toxicokinetics. Furthermore, comparing key motif expression in subunit genes of the classical nicotinic acetylcholine receptor (nAChR) target predicts only minor differences in the ligand binding domains (LBDs). In contrast, predicted dissimilarities in LBDs do occur in the highly expressed but nonclassical targets, acetylcholine binding proteins (AChBPs). Critically, the predicted AChBP divergence is capable of explaining DSS. We propose that high expression levels of putative nonsynaptic AChBPs with high imidacloprid affinities reduce imidacloprid binding to critical nAChRs involved in vital synaptic neurotransmission. This study provides a clear example of how pragmatic interrogation of key motif expression in complex multisubunit receptors can predict observed DSS, thereby informing sensitivity predictions for essential nontarget species.

Interactions between Environmental Contaminants and Gastrointestinal Parasites: Novel Insights from an Integrative Approach in a Marine Predator.

Environmental contaminants and parasites are ubiquitous stressors that can affect animal physiology and derive from similar dietary sources (co-exposure). To unravel their interactions in wildlife, it is thus essential to quantify their concurring drivers. Here, the relationship between blood contaminant residues (11 trace elements and 17 perfluoroalkyl substances) and nonlethally quantified gastrointestinal parasite loads was tested while accounting for intrinsic (sex, age, and mass) and extrinsic factors (trophic ecology inferred from stable isotope analyses and biologging) in European shags Phalacrocorax aristotelis. Shags had high mercury (range 0.65-3.21 µg g-1 wet weight, ww) and extremely high perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) residues (3.46-53 and 4.48-44 ng g-1 ww, respectively). Males had higher concentrations of arsenic, mercury, PFOA, and PFNA than females, while the opposite was true for selenium, perfluorododecanoic acid (PFDoA), and perfluooctane sulfonic acid (PFOS). Individual parasite loads (Contracaecum rudolphii) were higher in males than in females. Females targeted pelagic-feeding prey, while males relied on both pelagic- and benthic-feeding organisms. Parasite loads were not related to trophic ecology in either sex, suggesting no substantial dietary co-exposure with contaminants. In females, parasite loads increased strongly with decreasing selenium:mercury molar ratios. Females may be more susceptible to the interactive effects of contaminants and parasites on physiology, with potential fitness consequences.

Accumulation of polybrominated diphenyl ethers and microbiome response in the great pond snail Lymnaea stagnalis with exposure to nylon (polyamide) microplastics.

Microplastics attract widespread attention, including for their potential to transport toxic chemicals in the form of plasticisers and associated hydrophobic organic chemicals, such as polybrominated diphenyl ethers (PBDEs). The aims of this study were to investigate how nylon (polyamide) microplastics may affect PBDE accumulation in snails, and the acute effects of nylon particles and PBDEs on survival, weight change and inherent microbiome diversity and community composition of the pond snail Lymnaea stagnalis. Snails were exposed for 96 h to BDEs-47, 99, 100 and 153 in the presence and absence of 1% w/w nylon microplastics in quartz sand sediment. No mortality was observed over the exposure period. Snails not exposed to microplastics lost significantly more weight compared to those exposed to microplastics. Increasing PBDE concentration in the sediment resulted in an increased PBDE body burden in the snails, however microplastics did not significantly influence total PBDE uptake. Based on individual congeners, uptake of BDE 47 by snails was significantly reduced in the presence of microplastics. The diversity and composition of the snail microbiome was not significantly altered by the presence of PBDEs nor by the microplastics, singly or combined. Significant effects on a few individual operational taxonomic units (OTUs) occurred when comparing the highest PBDE concentration with the control treatment, but in the absence of microplastics only. Overall within these acute experiments, only subtle effects on weight loss and slight microbiome alterations occurred. These results therefore highlight that L. stagnalis are resilient to acute exposures to microplastics and PBDEs, and that microplastics are unlikely to influence HOC accumulation or the microbiome of this species over short timescales.

Biological Traits and the Transfer of Persistent Organic Pollutants through River Food Webs.

Freshwater organisms remain at risk from bioaccumulation and biomagnification of persistent organic pollutants (POPs), but factors affecting their transfer through food webs are poorly understood. Here, we investigate transfer pathways of polychlorinated biphenyls, polybrominated diphenyl ethers, and organochlorine through a river food web, assessing the distribution and flux between basal resources (n = 3), macroinvertebrates (n = 22), and fish (n = 1). We investigate the effects of biological traits on the observed patterns and use trait-based models to predict POP bioaccumulation. Transfer pathways differed among POPs and traits such as habitat affinity, feeding behavior, and body size explained some variation in POP burdens between organisms. Trait-based models indicated that relationships between POPs, trophic transfers, and traits were relatively well conserved across a wider array of river food webs. Although providing more consistent predictions of POP bioaccumulation than steady-state models, variability in bioaccumulation across food webs limited the accuracy of trait-model predictions. As some of the first data to illustrate how ecological processes alter the flux of pollutants through river food webs, these results reveal important links between POPs and contrasting energetic pathways. These data also show the utility of trait-based methods in the assessment of persistent contaminants, but further field validations are required.

Temporal and Spatial Distribution of Mercury in Gulls Eggs from the Iberian Peninsula.

We examined how coastal mercury contamination varied spatially and temporally across the Iberian Peninsula by measuring mercury concentrations in the eggs of the sentinel biomonitor yellow-legged gull (Larus michahellis). Samples were collected from eight colonies that ranged from the Atlantic across the south and northern areas of the Mediterranean. We also measured Hg residues in eggs of the one of the most endangered gull species in the world, the Audouin's gull (Larus audouinii) from the Ebro Delta, where colonies of yellow-legged and Audouin's gull co-occur. Fresh eggs were collected in 2009 and 2016 and samples were pooled from each colony for analysis. Mercury concentrations in yellow-legged gulls ranged between 0.4 and 2.8 mg/kg dry weight (dw); although there were no significant differences in concentrations between sampling periods, significant differences were found between colonies. Higher concentrations were associated with northern Mediterranean colonies (Columbretes and Ebro Delta), likely due to proximity to emission sources, circulatory marine currents and diet composition. Mercury concentrations in yellow-legged gull eggs were lower than those reported to result in impaired hatching. Residues in Audouin's gull eggs from the Ebro Delta were significantly higher (4.0-5.6 mg/kg dw) than those in yellow-legged gull from the same location, probably associated with dietary differences. Mercury levels in Audouin's gull were ten times above the benchmark suggested to reduce nest success by 10%. Overall, these results raise concern for adverse health impacts in this protected seabird species and further investigation in Audouin's gull eggs from the Ebro Delta is recommended.

Levels of Organochlorine Pesticides Are Associated with Amyloid Aggregation in Apex Avian Brains.

Organochlorine (OC) pesticides pose a significant environmental risk to wildlife and humans and have been associated with Alzheimer's disease (AD). This study aims to spectroscopically analyze brains from free-flying birds and link the results to OC exposure and consequent amyloid aggregation. As long-lived apex predators, predatory birds represent a sentinel species similar to humans. Therefore, the results have implications for both species and may also add to our understanding of the role OC pesticides play in the development of AD. Brains of wild Sparrowhawks were analyzed using ATR-FTIR and Raman spectroscopy and Congo red staining; results were correlated with OC pesticide concentrations in livers. Effects of OC exposure were sex- and age-dependent and associated alterations were seen in lipids and protein secondary structure. A shift from α-helix to ß-sheet conformation of proteins indicated that concentrations of OC pesticides >7.18 µg/g may lead to cerebral amyloid aggregation.

Feather corticosterone content in predatory birds in relation to body condition and hepatic metal concentration.

This study investigated the feasibility of measuring corticosterone in feathers from cryo-archived raptor specimens, in order to provide a retrospective assessment of the activity of the stress axis in relation to contaminant burden. Feather samples were taken from sparrowhawk Accipiter nisus, kestrel Falco tinnunculus, buzzard Buteo buteo, barn owl Tyto alba, and tawny owl Strix aluco and the variation in feather CORT concentrations with respect to species, age, sex, feather position, and body condition was assessed. In sparrowhawks only, variation in feather CORT content was compared with hepatic metal concentrations. For individuals, CORT concentration (pgmm(-1)) in adjacent primary flight feathers (P5 and P6), and left and right wing primaries (P5), was statistically indistinguishable. The lowest concentrations of CORT were found in sparrowhawk feathers and CORT concentrations did not vary systematically with age or sex for any species. Significant relationships between feather CORT content and condition were observed in only tawny owl and kestrel. In sparrowhawks, feather CORT concentration was found to be positively related to the hepatic concentrations of five metals (Cd, Mn, Co, Cu, Mo) and the metalloid As. There was also a negative relationship between measures of condition and total hepatic metal concentration in males. The results suggest that some factors affecting CORT uptake by feathers remain to be resolved but feather CORT content from archived specimens has the potential to provide a simple effects biomarker for exposure to environmental contaminants.

Mid-infrared spectroscopic assessment of nanotoxicity in gram-negative vs. gram-positive bacteria.

Nanoparticles appear to induce toxic effects through a variety of mechanisms including generation of reactive oxygen species (ROS), physical contact with the cell membrane and indirect catalysis due to remnants from manufacture. The development and subsequent increasing usage of nanomaterials has highlighted a growing need to characterize and assess the toxicity of nanoparticles, particularly those that may have detrimental health effects such as carbon-based nanomaterials (CBNs). Due to interactions of nanoparticles with some reagents, many traditional toxicity tests are unsuitable for use with CBNs. Infrared (IR) spectroscopy is a non-destructive, high throughput technique, which is unhindered by such problems. We explored the application of IR spectroscopy to investigate the effects of CBNs on Gram-negative (Pseudomonas fluorescens) and Gram-positive (Mycobacterium vanbaalenii PYR-1) bacteria. Two types of IR spectroscopy were compared: attenuated total reflection Fourier-transform infrared (ATR-FTIR) and synchrotron radiation-based FTIR (SR-FTIR) spectroscopy. This showed that Gram-positive and Gram-negative bacteria exhibit differing alterations when exposed to CBNs. Gram-positive bacteria appear more resistant to these agents and this may be due to the protection afforded by their more sturdy cell wall. Markers of exposure also vary according to Gram status; Amide II was consistently altered in Gram-negative bacteria and carbohydrate altered in Gram-positive bacteria. ATR-FTIR and SR-FTIR spectroscopy could both be applied to extract biochemical alterations induced by each CBN that were consistent across the two bacterial species; these may represent potential biomarkers of nanoparticle-induced alterations. Vibrational spectroscopy approaches may provide a novel means of fingerprinting the effects of CBNs in target cells.

Relationship between the concentrations of dissolved organic matter and polycyclic aromatic hydrocarbons in a typical U.K. upland stream.

Concentrations of total and freely dissolved polycyclic aromatic hydrocarbons (PAHs) and dissolved organic carbon (DOC) were measured in water collected during four sampling events at five sites from the River Wyre. The sites are typical of streams draining upland organically rich soils in northwest U.K. Freely dissolved PAHs were separated from those associated with DOC using a flocculation method. The sum of concentrations of the total and freely dissolved PAHs analyzed ranged from 2.71 to 18.9 ng/L and 2.61 to 16.8 ng/L, respectively. PAH concentrations and PAH fluxes derived from concentrations and water flow rates generally increased downstream, the trend in the latter being more pronounced. The concentration of individual PAHs containing five or more aromatic rings was found to be strongly correlated to the DOC concentration (p < 0.0001), suggesting common terrestrial sources and hydrological pathways. In contrast, no significant relationships were observed between concentrations of PAHs with four or fewer rings and DOC. Concentrations of PAHs with more than four rings showed similar seasonal variation as DOC concentration (peaking in the late summer), while variation in two or three ring PAHs was out of phase with DOC (peaking in the winter). As the PAH-DOC relationship appeared partly dependent on the molecular weight of the PAHs, a linear regression function that included an interaction between this variable and DOC concentration was used to model PAH concentrations over a 2 year period to estimate annual fluxes. The relationship identified between PAH concentrations and DOC should help to enhance interpretation of PAH monitoring data that are currently sparse both spatially and temporally and, thus, enable more robust assessments of the potential risks of these environmental pollutants to sensitive aquatic organisms and human water supplies.

Fate and behaviour of Microplastics (> 25µm) within the water distribution network, from water treatment works to service reservoirs and customer taps.

Water treatment works have previously shown high efficiency in removing microplastics > 25 µm from raw source water. However, what is less well known is the extent to which microplastics of this size class are generated or lost within the water distribution network, particularly whether there is a greater presence in the customer tap than in the water treatment works outlet. This study focused on the presence of 21 different types of synthetic polymer particles with sizes larger than 25 µm examined through multiple rounds of sampling at outlets of water treatment works (WTW), service reservoirs (SR), and customer taps (CT) managed by seven different water companies in Britain. Nineteen different types of polymers were detected; their signature and concentration varied based on the round of sampling, the location within the water supply network, and the water company responsible for managing the supply. Among the polymers examined, polyamide (PA), polyethene terephthalate (PET), polypropylene (PP), and polystyrene (PS) were the most commonly found. Apart from PET having its highest concentration of 0.0189 microplastic per litre (MP/L) in the SR, the concentrations of the other three most frequent polymers (PS = 0.017 MP/L, PA = 0.0752 MP/L, PP= 0.1513 MP/L) were highest in the CT. The overall prevalence of this size of microplastics in the network is low, but there was a high variability of polymer types and occurrences. These spatial and temporal variations suggested that the MP in the distribution network may exist as a series of pulses. Given the presence and polymer types, the potential for some of the microplastics to originate from materials used in the water network and domestic plumbing systems cannot be ruled out. As found before, the absolute number of microplastics in the water distribution network remained extremely low.

Co-located ecological data for exploring top- and subsoil carbon dynamics across grassland-woodland contrasts.

Soil organic carbon (SOC) is a soil health indicator and understanding dynamics changing SOC stocks will help achieving net zero goals. Here we present four datasets featuring 11,750 data points covering co-located aboveground and below-ground metrics for exploring ecosystem SOC dynamics. Five sites across England with an established land use contrast, grassland and woodland next to each other, were rigorously sampled for aboveground (n = 109), surface (n = 33 soil water release curves), topsoil, and subsoil metrics. Commonly measured soil metrics were analysed in five soil increments for 0-1 metre (n = 4550). Less commonly measured soil metrics which were assumed to change across the soil profile were measured on a subset of samples only (n = 3762). Additionally, we developed a simple method for soil organic matter fractionation using density fractionation which is part of the less common metrics. Finally, soil metrics which may impact SOC dynamics, but with less confidence as to their importance across the soil profile were only measured on topsoil (~5-15 cm = mineral soil) and subsoil (below 50 cm) samples (n = 2567).

Eurasian dipper eggs indicate elevated organohalogenated contaminants in urban rivers.

Many urban European streams are recovering from industrial, mining, and sewage pollution during the 20th century. However, associated recolonization by clean water organisms can potentially result in exposure to legacy or novel toxic pollutants that persist in the environment. Between 2008 and 2010, we sampled eggs of a river passerine, the Eurasian dipper (Cinclus cinclus), from 33 rivers in South Wales and the English borders (UK) which varied in catchment land use from rural to highly urbanized. Dipper egg δ(15)N and δ(13)C stable isotopes were enriched from urban rivers while δ(34)S was strongly depleted, effectively discriminating their urban or rural origins at thresholds of 10% urban land cover or 1000 people/km(2). Concentrations of total polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs) were positively related to urban land cover and human population density while legacy organochlorine pesticides such as p,p'-DDE, lindane, and hexachlorobenzene were found in higher concentrations at rural sites. Levels of PBDEs in urban dipper eggs (range of 136-9299 ng/g lw) were among the highest ever reported in passerines, and some egg contaminants were at or approaching levels sufficient for adverse effects on avian development. With the exception of dieldrin, our data shows PCBs and other organochlorine pesticides have remained stable or increased in the past 20 years in dipper eggs, despite discontinued use.

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.

Long-term rise in riverine dissolved organic carbon concentration is predicted by electrolyte solubility theory.

The riverine dissolved organic carbon (DOC) flux is of similar magnitude to the terrestrial sink for atmospheric CO2, but the factors controlling it remain poorly determined and are largely absent from Earth system models (ESMs). Here, we show, for a range of European headwater catchments, that electrolyte solubility theory explains how declining precipitation ionic strength (IS) has increased the dissolution of thermally moderated pools of soluble soil organic matter (OM), while hydrological conditions govern the proportion of this OM entering the aquatic system. Solubility will continue to rise exponentially with declining IS until pollutant ion deposition fully flattens out under clean air policies. Future DOC export will increasingly depend on rates of warming and any directional changes to the intensity and seasonality of precipitation and marine ion deposition. Our findings provide a firm foundation for incorporating the processes dominating change in this component of the global carbon cycle in ESMs.

The importance of in-year seasonal fluctuations for biomonitoring of apex predators: A case study of 14 essential and non-essential elements in the liver of the common buzzard (Buteobuteo) in the United Kingdom.

Trace elements are chemical contaminants spread in the environment by anthropogenic activities and threaten wildlife and human health. Many studies have investigated this contamination in apex raptors as sentinel birds. However, there is limited data for long-term biomonitoring of multiple trace elements in raptors. In the present study, we measured the concentrations of 14 essential and non-essential trace elements in the livers of the common buzzard (Buteo buteo) collected in the United Kingdom from 2001 to 2019 and investigated whether concentrations have changed during this period. In addition, we estimated the importance of selected variables for modelling element accumulations in tissues. Except for cadmium, hepatic concentrations of harmful elements in most buzzards were lower than the biological significance level of each element. Hepatic concentrations of certain elements, including lead, cadmium, and arsenic, varied markedly seasonally within years. Their peak was in late winter and trough in late summer, except copper which showed an opposite seasonal pattern. In addition, lead in the liver consistently increased over time, whereas strontium showed a decreasing trend. Hepatic concentrations of cadmium, mercury, and chromium increased with age, whereas selenium and chromium were influenced by sex. Hepatic concentrations of arsenic and chromium also differed between different regions. Overall, our samples showed a low risk of harmful effects of most elements compared to the thresholds reported in the literature. Seasonal fluctuation was an important descriptor of exposure, which might be related to the diet of the buzzard, the ecology of their prey, and human activities such as the use of lead shot for hunting. However, elucidating reasons for these observed trends needs further examination, and biomonitoring studies exploring the effects of variables such as age, sex, and seasonality are required.