Assessment of contaminants of emerging concern in European apex predators and their prey by LC-QToF MS wide-scope target analysis.

Apex predators are good indicators of environmental pollution since they are relatively long-lived and their high trophic position and spatiotemporal exposure to chemicals provides insights into the persistent, bioaccumulative and toxic (PBT) properties of chemicals. Although monitoring data from apex predators can considerably support chemicals' management, there is a lack of pan-European studies, and longer-term monitoring of chemicals in organisms from higher trophic levels. The present study investigated the occurrence of contaminants of emerging concern (CECs) in 67 freshwater, marine and terrestrial apex predators and in freshwater and marine prey, gathered from four European countries. Generic sample preparation protocols for the extraction of CECs with a broad range of physicochemical properties and the purification of the extracts were used. The analysis was performed utilizing liquid (LC) chromatography coupled to high resolution mass spectrometry (HRMS), while the acquired chromatograms were screened for the presence of more than 2,200 CECs through wide-scope target analysis. In total, 145 CECs were determined in the apex predator and their prey samples belonging in different categories, such as pharmaceuticals, plant protection products, per- and polyfluoroalkyl substances, their metabolites and transformation products. Higher concentration levels were measured in predators compared to prey, suggesting that biomagnification of chemicals through the food chain occurs. The compounds were prioritized for further regulatory risk assessment based on their frequency of detection and their concentration levels. The majority of the prioritized CECs were lipophilic, although the presence of more polar contaminants should not be neglected. This indicates that holistic analytical approaches are required to fully characterize the chemical universe of biota samples. Therefore, the present survey is an attempt to systematically investigate the presence of thousands of chemicals at a European level, aiming to use these data for better chemicals management and contribute to EU Zero Pollution Ambition.

Determination of 56 per- and polyfluoroalkyl substances in top predators and their prey from Northern Europe by LC-MS/MS.

Per- and polyfluoroalkyl substances (PFAS) are a group of emerging substances that have proved to be persistent and highly bioaccumulative. They are broadly used in various applications and are known for their long-distance migration and toxicity. In this study, 65 recent specimens of a terrestrial apex predator (Common buzzard), freshwater and marine apex predators (Eurasian otter, harbour porpoise, grey seal, harbour seal) and their potential prey (bream, roach, herring, eelpout) from northern Europe (United Kingdom, Germany, the Netherlands and Sweden) were analyzed for the presence of legacy and emerging PFAS, employing a highly sensitive liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) method. 56 compounds from 14 classes were measured; 13 perfluoroalkyl carboxylic acids (PFCAs), 7 perfluoroalkyl sulphonic acids (PFSAs), 3 perfluorooctane sulfonamides (FOSAs), 4 perfluoroalkylphosphonic acids (PFAPAs), 3 perfluoroalkylphosphinic acids (PFPi's), 5 telomer alcohols (FTOHs), 2 mono-substituted polyfluorinated phosphate esters (PAPs), 2 di-substituted polyfluorinated phosphate esters (diPAPs), 6 saturated fluorotelomer acids (FTAS), 3 unsaturated fluorotelomer acids (FTUAs), 2 N-Alkyl perfluorooctane sulfonamidoethanols (FOSEs), 3 fluorotelomer sulphonic acids (FTSAs), 2 perfluoroether carboxylic acids (PFECAs) and 1 chlorinated perfluoroether sulphonic acid (Cl-PFESA). All samples were lyophilized before analysis, in order to enhance extraction efficiency, improve the precision and achieve lower detection limits. The analytes were extracted from the dry matrices through generic methods of extraction, using an accelerated solvent extraction (ASE), followed by clean-up through solid phase extraction (SPE). Method detection limits and method quantification limits ranged from 0.02 to 1.25 ng/g wet weight (ww) and from 0.05 to 3.79 ng/g (ww), respectively. Recovery ranged from 40 to 137%. Method precision ranged from 3 to 20 %RSD. The sum of PFAS concentration in apex predators livers ranged from 0.2 to 20.2 µg/g (ww), whereas in the fish species muscle tissues it ranged from 16 to 325 ng/g (ww). All analyzed specimens were primarily contaminated with PFOS, while the three PFPi's included in this study exhibited frequency of appearance (FoA) 100 %. C9 to C13 PFCAs were found at high concentrations in apex predator livers, while the overall PFAS levels in fish fillets also exceeded ecotoxicological thresholds. The findings of our study show a clear association between the PFAS concentrations in apex predators and the geographical origin of the specimens, with samples that were collected in urban and agricultural zones being highly contaminated compared to samples from pristine or semi-pristine areas. The high variety of PFAS and the different PFAS composition in the apex predators and their prey (AP&P) samples is alarming and strengthens the importance of PFAS monitoring across the food chain.

Correction to: Progress on bringing together raptor collections in Europe for contaminant research and monitoring in relation to chemicals regulation.

The correct affiliation of Sabrina Lo Brutto is shown in this paper.

Sampling designs for contaminant temporal trend analyses using sedentary species exemplified by the snails Bellamya aeruginosa and Viviparus viviparus.

Environmental monitoring typically assumes samples and sampling activities to be representative of the population being studied. Given a limited budget, an appropriate sampling strategy is essential to support detecting temporal trends of contaminants. In the present study, based on real chemical analysis data on polybrominated diphenyl ethers in snails collected from five subsites in Tianmu Lake, computer simulation is performed to evaluate three sampling strategies by the estimation of required sample size, to reach a detection of an annual change of 5% with a statistical power of 80% and 90% with a significant level of 5%. The results showed that sampling from an arbitrarily selected sampling spot is the worst strategy, requiring much more individual analyses to achieve the above mentioned criteria compared with the other two approaches. A fixed sampling site requires the lowest sample size but may not be representative for the intended study object e.g. a lake and is also sensitive to changes of that particular sampling site. In contrast, sampling at multiple sites along the shore each year, and using pooled samples when the cost to collect and prepare individual specimens are much lower than the cost for chemical analysis, would be the most robust and cost efficient strategy in the long run. Using statistical power as criterion, the results demonstrated quantitatively the consequences of various sampling strategies, and could guide users with respect of required sample sizes depending on sampling design for long term monitoring programs.

Temporal Trends and Geographical Differences of Perfluoroalkyl Acids in Baltic Sea Herring and White-Tailed Sea Eagle Eggs in Sweden.

Temporal and spatial trends of perfluoroalkyl acids (PFAAs) were investigated in Baltic Sea herring liver (Clupea harengus) from three sites, and white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two freshwater and two marine areas in Sweden. Trends of most quantifiable PFAAs increased over the monitored period (1980-2014 in herring, 1960s/1980s-2010 in WTSE). No significant decreasing trends were observed for the most recent ten years for any substances, except perfluorooctane sulfonamide (FOSA). Concentrations of perfluorooctanesulfonic acids (PFOS) in herring showed a distinct decreasing spatial trend moving from the more southern site toward the more northern site, indicating main input of PFOS into the southern Baltic Sea. For WTSE, PFOS concentration was higher in the marine compared to the freshwater environment, explained by the cumulative historic contamination of the Baltic Sea. Similarly, concentrations in WTSE were lower in the northern part of the Baltic Sea compared to further south. Concentrations of PFUnDA, representing long-chain perfluoroalkyl carboxylic acids (PFCAs), showed a more homogeneous spatial distribution compared to PFOS for both herring and WTSE, indicating that atmospheric inputs (via precursors) of the long-chain PFCAs are important contributors in the study areas.

Temporal and spatial trends of PCBs, DDTs, HCHs, and HCB in Swedish marine biota 1969-2012.

In the 1960s, the Baltic Sea was severely polluted by organic contaminants such as PCBs, HCHs, HCB, and DDTs. Elevated concentrations caused severe adverse effects in Baltic biota. Since then, these substances have been monitored temporally and spatially in Baltic biota, primarily in herring (Clupea harengus) and in guillemot (Uria aalge) egg, but also in cod (Gadus morhua), perch (Perca fluviatilis), eelpout (Zoarces viviparous), and blue mussel (Mytilus edulis). These chemicals were banned in Sweden in the late 1970s/early 1980s. Since the start of monitoring, overall significant decreases of about 70-90 % have been observed. However, concentrations are still higher in the Baltic Sea than in, for example, the North Sea. CB-118 and DDE exceed the suggested target concentrations (24 µg kg(-1) lipid weight and 5 µg kg(-1) wet weight, respectively) at certain sites in some of the monitored species, showing that concentrations may still be too high to protect the most sensitive organisms.

Spatio-temporal trends of PCBs in the Swedish freshwater environment 1981-2012.

Polychlorinated biphenyls (PCBs) have been monitored in perch (Perca fluviatilis), pike (Esox lucius), and Arctic char (Salvelinus alpinus) in reference lakes since the late 1960s. Temporal trends and spatial patterns are currently monitored in nine and 32 lakes, respectively. Overall, PCB concentrations are decreasing. However, this is not consistent for all congeners across all lakes and species. Perch has comparatively low PCB concentrations relative to suggested target levels, but individual congener concentrations in some lakes are concerningly high. No temporal trend is seen for CB-118 and CB-153 in perch, but significant decreasing trends exist for Arctic char and pike, for which monitoring started earlier than for perch. The lower/higher chlorinated congener ratio decreased over time in most lakes, indicating fewer new emissions. CB-118 and CB-153 concentrations in perch show spatial gradients across Sweden, with higher concentrations found near urban/industrial areas.

Comparing temporal trends of organochlorines in guillemot eggs and Baltic herring: advantages and disadvantage for selecting sentinel species for environmental monitoring.

Within Europe, the Marine Strategy Framework Directive (MSFD) is aimed at addressing the chemical status and quality of the marine environment. One of the main goals is to achieve Good Environmental Status (GES) in the marine environment. Environmental monitoring of biota e.g., Baltic herring and guillemot eggs, is conducted annually in Sweden to follow temporal changes in environmental contaminants. To determine the suitability of guillemot eggs as a sentinel species for investigating GES, we compared temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in these two species from single sampling sites within Sweden. Lipid content from guillemot eggs was consistently high and stable (yearly mean for >40 years, ∼12%) compared to that of herring (yearly mean for >20 years, ∼3%). A significant decreasing trend of ΣPCDD/F in TEQ WHO1998 was observed in guillemot eggs, but no trend was seen in herring. CB118 significantly decreased in both species, but in the last 10 years this decrease was not significant in herring. A number of advantages, such as high lipid content in the egg and a low coefficient of variation make guillemot suitable as a sentinel species. The advantages and disadvantages of using either guillemot eggs or Baltic herring are compared.

Consequences of using pooled versus individual samples for designing environmental monitoring sampling strategies.

Choosing an appropriate sampling strategy for chemical analysis within environmental monitoring includes the important decision of whether to sample and store individual or pooled samples. This choice impacts on future analyses from Environmental Specimen Bank samples. A number of advantages exist to support using either individual or pooled samples for temporal trend studies. However, it is important to know the total and analytical variance to be able to design the best sampling strategy. Statistical power in temporal or spatial studies is determined by the random/unexplained sample variation. The relationship between chemical analytical error and other sources of variation, as well as the cost for collection, preparation of samples and chemical analysis, will determine the number of individuals in each pool, and the number of pools that should be analysed to achieve high cost efficiency and good statistical power. Various scenarios of different numbers of individual samples, different numbers of pooled samples containing various numbers of individual specimens, the relationships between chemical analytical error and other sources of sample variance, have been compared by simulating random sampling from computer generated populations using realistic measures of variation from ongoing monitoring activities. These results offer guidance in the design of a cost-efficient, statistically sound sampling strategy.