Aquatic macroinvertebrate community responses to pollution of perfluoroalkyl substances (PFAS): Can we define threshold body burdens?

The pollution of per- and polyfluorinated alkyl substances (PFAS) in aquatic environments is a worldwide concern of which the ecological impact is still not well understood. Especially field-based effect studies in aquatic ecosystems are generally lacking, creating a knowledge gap that goes along with monitoring and regulatory challenges. Therefore, this study examined if bioaccumulated PFAS concentrations could be related to ecological responses assessed by changes in the macroinvertebrate community structure. In addition, threshold body burdens that are protective of ecological damage were estimated. Aquatic macroinvertebrates were sampled in 30 streams across Flanders (Belgium) and 28 PFAS target analytes were measured in three resident taxa (Gammarus sp., Asellus sp. and Chironomus sp.) and translocated zebra mussels (Dreissena polymorpha). The macroinvertebrate community structure was assessed by calculating the Multimetric Macroinvertebrate Index Flanders (MMIF). Primarily long-chain perfluorinated carboxylic acids (PFCAs) were detected in both resident taxa (passive biomonitoring) and zebra mussels (active biomonitoring). Based on a 90th quantile regression model, safe threshold body burdens could be calculated for PFTeDA (7.1 ng/g ww) and ΣPFAS (2264 ng/g ww) in Gammarus sp. and for PFOA (5.5 ng/g ww), PFDoDA (1.7 ng/g ww), PFTrDA (0.51 ng/g ww), PFTeDA (2.4 ng/g ww), PFOS (644 ng/g ww) and ΣPFAS (133 ng/g ww) in zebra mussel. An additional threshold value was calculated for most compounds and species using the 95th percentile method. However, although these estimated thresholds are pertinent and indicative, regulatory applicability requires further lines of evidence and validation. Nevertheless, this study offers first-time evidence of associations between accumulated PFAS concentrations in invertebrates and a reduced ecological water quality in terms of macroinvertebrate community structure and highlights the potential of Gammarus sp. and zebra mussels to serve as reliable PFAS biomonitoring species.

Dynamic spatiotemporal changes of per- and polyfluoroalkyl substances (PFAS) in soil and eggs of private gardens at different distances from a fluorochemical plant.

Homegrown food serves as an important human exposure source of per- and polyfluoroalkyl substances (PFAS), yet little is known about their spatiotemporal distribution within and among private gardens. This knowledge is essential for more accurate site-specific risk assessment, identification of new sources and evaluating the effectiveness of regulations. The present study evaluated spatiotemporal changes of legacy and emerging PFAS in surface soil from vegetable gardens (N = 78) and chicken enclosures (N = 102), as well as in homegrown eggs (N = 134) of private gardens, across the Province of Antwerp (Belgium). Hereby, the potential influence of the wind orientation and distance towards a major fluorochemical plant was examined. The ∑short-chain PFAS and precursor concentrations were higher in vegetable garden soil (8.68 ng/g dry weight (dw)) compared to chicken enclosure soil (4.43 ng/g dw) and homegrown eggs (0.77 ng/g wet weight (ww)), while long-chain sulfonates and C11-14 carboxylates showed the opposite trend. Short-term (2018/2019-2022) changes were mostly absent in vegetable garden soil, while changes in chicken enclosure soils oriented S-SW nearby (<4 km) the fluorochemical plant were characterized by a local, high-concentration plume. Moreover, soil from chicken enclosures oriented SE and remotely from the plant site was characterized by a widespread, diffuse but relatively low-concentration plume. Long-term data (2010-2022) suggest that phaseout and regulatory measures have been effective, as PFOS concentrations nearby the fluorochemical plant in soil and eggs have declined from 25.8 to 2.86 ng/g dw and from 528 to 39.4 ng/g ww, respectively. However, PFOS and PFOA concentrations have remained largely stable within this timeframe in gardens remotely from the plant site, warranting further rapid regulation and remediation measures. Future monitoring efforts are needed to allow long-term comparison for multiple PFAS and better distinction from potential confounding variables, such as variable emission outputs and variability in wind patterns.

Are Chinese mitten crabs (Eriocheir sinensis) suitable as biomonitor or bioindicator of per- and polyfluoroalkyl substances (PFAS) pollution?

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment. In Flanders, the bioaccumulation in aquatic organisms is currently being monitored using European perch and European eel. Since both are native species, there is an ethical need to search for other suitable biomonitors. This study aims to investigate whether the invasive Chinese mitten crab could be used in biomonitoring programs by assessing PFAS accumulation in hepatopancreas, muscle tissue, and carapace. Furthermore, we correlated accumulated concentrations to those in the local abiotic environment. Concentrations in the crabs (highest average ∑PFAS concentration of 688 ± 505 ng/g ww) were often higher than those in crab species from other regions across the globe, confirming that Flanders is highly polluted with PFAS. Concentrations in the crabs did not reflect those in the abiotic environment. This implies that biomonitoring is necessary to investigate the impact of PFAS pollution on organisms in aquatic ecosystems, as important data is missing when only the abiotic environment is monitored. The accumulation profiles differed between the invasive crab and the native European perch and European eel, potentially due to a different ecology and trophic position. Since all three species provide complementary information on the PFAS pollution, a multi-species approach in biomonitoring is recommended. Overall, our results show that the crabs can be used as biomonitor, but more information is necessary to confirm their suitability as bioindicator.

Prediction of perfluoroalkyl acids (PFAAs) in homegrown eggs: Insights into abiotic and biotic factors affecting bioavailability and derivation of potential remediation measures.

Homegrown eggs from free-ranging laying hens often contain elevated concentrations of perfluoroalkyl acids (PFAAs). However, it is unclear which factors contribute to these relatively large exposure risk scenarios. Moreover, existing bioavailability and modeling concepts of conventional organic pollutants cannot be generalized to PFAAs due to their different physicochemical soil interactions. Therefore, there is an urgent need for empirical models, based on real-world data, to provide insights into how (a)biotic factors affect the bioavailability to eggs. To this end, 17 targeted analytes were analyzed in abiotic (i.e. rainwater, soil; both N = 101) matrices and homegrown eggs (N = 101), which were sampled in 101 private gardens across Flanders (Belgium) in 2019, 2021 and 2022. Various soil characteristics were measured to evaluate their role in affecting PFAA bioavailability to the eggs. Finally, PFAAs were measured in potential feed sources (i.e. homegrown vegetable and earthworm pools; respectively N = 49 and N = 34) of the laying hens to evaluate their contribution to the egg burden. Modeling suggested that soil was a major exposure source to laying hens, accounting for 16-55% of the total variation in egg concentrations for dominant PFAAs. Moreover, concentrations in vegetables and earthworms for PFBA and PFOS, respectively, were significantly positively related with corresponding egg concentrations. Predictive models based on soil concentrations, total organic carbon (TOC), pH, clay content and exchangeable cations were successfully developed for major PFAAs, providing possibilities for time- and cost-effective risk assessment of PFAAs in homegrown eggs. Among other soil characteristics, TOC and clay content were related with lower and higher egg concentrations for most PFAAs, respectively. This suggests that bioavailability of PFAAs to the eggs is driven by complex physicochemical interactions of PFAAs with TOC and clay. Finally, remediation measures were formulated that are readily applicable to lower PFAA exposure via homegrown eggs.

Growth Hormones in Broad Bean (Vicia faba L.) and Radish (Raphanus raphanistrum subsp. sativus L.) Are Associated with Accumulated Concentrations of Perfluoroalkyl Substances.

In this study, we grew radish (Raphanus raphanistrum subsp. sativus L.) and broad beans (Vicia faba L.) in a greenhouse on soils spiked with a mixture of 15 per- and polyfluoroalkyl substances (PFASs) and investigated the association between accumulated ∑PFAS concentrations, growth, and hormone levels. Short-chained PFASs dominated aboveground tissues, whereas long-chained PFASs were most abundant in the plant roots. Our results showed that the presence or absence of exodermal Casparian strips, as well as the hydrophobicity and anion exchange capacities of PFASs, could explain the translocation of PFASs within plants. Significant associations found between accumulated PFAS concentrations and levels of gibberellins (GA1 and GA15), methionine, and indole-3-acetic acid (IAA) imply potential effects of PFASs on plant development and growth. This study provides the first evidence of associations between PFAS accumulation in plants and growth hormone levels, possibly leading to growth reduction of the apical dome and effects on the cell cycle in pericycle cells and methionine metabolism in plants.

Assessment of poly- and perfluoroalkyl substances (PFAS) in commercially available drinking straws using targeted and suspect screening approaches.

Many food contact materials (FCMs) and reusable plastics in the food industry contain poly- and perfluoroalkyl substances (PFAS), a group of synthetic pollutants that are known to be potentially harmful for wildlife, humans, and the environment. PFAS may migrate from FCMs to food consumed by humans. As a replacement for plastics, often paper and other plant-based materials are used in commercial settings. This also applies to drinking straws, where plant-based and other presumably eco-friendly straws are increasingly used to reduce plastic pollution. In order to make these materials water-repellent, PFAS are added during manufacturing but can also already be present early in the supply chain due to the use of contaminated raw materials. In the present study, we examined the PFAS concentrations in 39 different brands of straws, made from five materials (i.e. paper, bamboo, glass, stainless steel, and plastic) commercially available on the Belgian market. We combined both targeted and suspect-screening approaches to evaluate a wide range of PFAS. PFAS were found to be present in almost all types of straws, except for those made of stainless steel. PFAS were more frequently detected in plant-based materials, such as paper and bamboo. We did not observe many differences between the types of materials, or the continents of origin. The presence of PFAS in plant-based straws shows that they are not necessarily biodegradable and that the use of such straws potentially contributes to human and environmental exposure of PFAS.

Associations between PFAS concentrations and the oxidative status in a free-living songbird (Parus major) near a fluorochemical facility.

For the past 7 decades, PFAS have been used in many different products and applications, which has led to a widespread contamination of these compounds. Nevertheless at present, little is known about the effects of these compounds on avian wildlife. Therefore, this study investigated associations between PFAS concentrations in the plasma and the oxidative status (i.e. non-enzymatic antioxidants and biomarkers of oxidative stress) in great tits at two sites near a fluorochemical manufacturing facility. Different PFAS were detected in the blood plasma with a mean ΣPFAS of 16062 pg/µL at the site closest to the facility. The PFAS profile in the plasma consisted mainly of PFOS, PFOA, PFDA and PFDoDA, where concentrations were higher for these compounds at the site closest to the plant. Our results show a clear link between PFAS and the antioxidant status of the birds; total antioxidant capacity and peroxidase activity were higher near the plant site, while the glutaredoxin activity was higher further away. Additionally, positive associations were found between PFDoDA and glutathione-S-transferase activity, between PFOS and glutathione-S-transferase activity, between PFDA and peroxidase activity, and between PFOS and peroxidase activity. Lastly, a negative association was found between plasma PFDA concentrations and the total polyphenol content. Interestingly, malondialdehyde levels did not differ between sites, suggesting lipid peroxidation was not affected. Although our results suggest that great tits with elevated PFAS concentrations did not suffer oxidative damage, the antioxidant defence responses were significantly triggered by PFAS exposure. This implies that the great tits have managed to defend themselves against the possible oxidative damage coming from PFAS contamination, although the upregulated antioxidant defences may have fitness costs. Further, experiments are needed to investigate the specific mechanisms by which PFAS induce oxidative stress in avian species.

Accumulation and effects of perfluoroalkyl substances in Arabidopsis thaliana in a temperature-dependent manner: an in vitro study.

The replacement of long-chained per- and polyfluoroalkyl substances (PFAS) with their short-chained homologues may have an impact on the accumulation in plants. The extent to which PFAS are absorbed by plants may differ among species and may depend on environmental factors, including temperature. The effect of an increased temperature on root uptake and translocation of PFAS in plants has been poorly studied. In addition, very few studies have examined toxicity of environmentally realistic PFAS concentrations to plants. Here, we investigated the bioaccumulation and tissue-distribution of fifteen PFAS in Arabidopsis thaliana L. grown in vitro at two different temperatures. Additionally, we examined the combined effects of temperature and PFAS accumulation on plant growth. Short-chained PFAS mainly accumulated in the leaves. The perfluorocarboxylic acid (PFCA) concentrations in roots and leaves, and the relative contribution of PFCAs to the ΣPFAS concentrations increased with carbon chain length regardless of temperature, with the exception of perfluorobutanoic acid (PFBA). An increased uptake of PFAS in leaves and roots at higher temperatures was observed for PFAS containing either eight or nine carbon atoms and could hence potentially result in higher risks for human intake. Leaf:root ratios of PFCAs followed a U-shaped pattern with carbon chain length, which is attributed to both hydrophobicity and anion exchange. Overall, no combined effects of realistic PFAS concentrations and temperature on the growth of A. thaliana were observed. PFAS exposure positively affected early root growth rates and root hair lengths, indicating a potential effect on factors involved in root hair morphogenesis. However, this effect on root growth rate became negligible later on in the exposure, and solely a temperature effect was observed after 6 days. Temperature also affected the leaf surface area. The underlying mechanisms on how PFAS stimulates root hair growth require further examination.

Temporal trends in PFAS concentrations in livers of a terrestrial raptor (common buzzard; Buteo buteo) collected in Belgium during the period 2000-2005 and in 2021.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals that have been globally distributed. Biological time series data suggest variation in temporal PFAS concentrations due to regulations and the phase-out of multiple PFAS analytes. Nonetheless, biomonitoring temporal trends of PFAS concentrations in raptors has only been done sporadically in Europe at a national scale. In the present study, we examined the concentrations of 28 PFAS in livers of common buzzard (Buteo buteo) collected in Belgium in the period 2000-2005 and in 2021. Despite the regulations and phase-out, the ΣPFAS concentrations remained similar in the livers over the past 20 years. However, over time the abundance of perfluorooctane sulfonate (PFOS), dominant in livers collected in 2000-2005, to the ΣPFAS concentration decreased from 46% to 27%, whereas the abundance of perfluorotetradecanoic acid (PFTeDA), dominant in 2021, increased from 19% to 43%. The PFOS concentrations in the present study did not exceed the Toxicity Reference Values (TRVs), which were determined in liver on the characteristics of an avian top predator. The absence of temporal changes in PFAS concentrations is hypothesized to be due to a lagged response in environmental concentrations compared to atmospheric concentrations.

PFAS accumulation in several terrestrial plant and invertebrate species reveals species-specific differences.

Despite the known persistence and bioaccumulation potential of perfluoroalkyl substances (PFAS), much uncertainty exists regarding their bioavailability in the terrestrial environment. Therefore, this study investigated the influence of soil characteristics and PFAS concentrations on the adsorption of PFAS to soil and their influence on the PFAS bioavailability to terrestrial plants and invertebrates. PFAS concentrations and profile were compared among different invertebrate and plant species and differences between leaves and fruits/nuts of the plant species were assessed. Soil concentrations were primarily affected by organic carbon content. The PFAS accumulation in biota was, except for PFOA concentrations in nettles, unrelated to the soil concentrations, as well as to the soil characteristics. The PFAS profiles in soil and invertebrates were mainly dominated by PFOA and PFOS, whereas short-chained PFAS were more abundant in plant tissues. Our results show that different invertebrate taxa accumulate different PFAS, likely due to dietary differences. Both long-chained and, to lesser extent, short-chained PFAS were observed in herbivorous invertebrate taxa, whereas the carnivorous invertebrates only accumulated long-chained PFAS. Correlations were observed between PFOA concentrations in herbivorous invertebrates and in the leaves of some plant species, whereas such relationships were absent for the carnivorous spiders. It is essential to continuously monitor PFAS exposure in terrestrial organisms, taking into account differences in bioaccumulation, and subsequent potential toxicity, among taxa, in order to protect the terrestrial ecosystem.

Home-produced eggs: An important human exposure pathway of perfluoroalkylated substances (PFAS).

Humans are generally exposed to per- and polyfluoroalkyl substances (PFAS) through their diet. Whilst plenty of data are available on commercial food products, little information exists on the contribution of self-cultivated food, such as home-produced eggs (HPE), to the dietary PFAS intake in humans. The prevalence of 17 legacy and emerging PFAS in HPE (N = 70) from free-ranging laying hens was examined at 35 private gardens, situated within a 10 km radius from a fluorochemical plant in Antwerp (Belgium). Potential influences from housing conditions (feed type and number of individuals) and age of the chickens on the egg concentrations was examined, and possible human health risks were evaluated. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were detected in all samples. PFOS was the dominant compound and concentrations (range: 0.13-241 ng/g wet weight) steeply decreased with distance from the fluorochemical plant, while there was no clear distance trend for other PFAS. Laying hens receiving an obligate diet of kitchen leftovers, exhibited higher PFOS and PFOA concentrations in their eggs than hens feeding only on commercial food, suggesting that garden produce may be a relevant exposure pathway to both chickens and humans. The age of laying hens affected egg PFAS concentrations, with younger hens exhibiting significantly higher egg PFOA concentrations. Based on a modest human consumption scenario of two eggs per week, the European health guideline was exceeded in ≥67% of the locations for all age classes, both nearby and further away (till 10 km) from the plant site. These results indicate that PFAS exposure via HPE causes potential human health risks. Extensive analysis in other self-cultivated food items on a larger spatial scale is highly recommended, taking into account potential factors that may affect PFAS bioavailability to garden produce.

Perfluoroalkylated compounds in the eggs and feathers of resident and migratory seabirds from the Antarctic Peninsula.

In this study, we investigated factors that influence the differences in exposure of perfluoroalkyl acids (PFAAs) from eight species of Antarctic seabirds, including Pygoscelis penguins, Stercorarius maccormicki, and Macronectes giganteus. We analyzed the relationship between foraging ecology (based on δ13C, δ15N, and δ34S values) and PFAAs accumulated in eggs and breast feathers. Ten out of 15 targeted PFAAs were detected in eggs compared to eight in feathers. Mean ∑PFAA concentrations in feathers ranged from 0.47 in P. antarcticus to 17.4 ng/g dry weight (dw) in S. maccormicki. In eggs, ∑PFAA concentrations ranged from 3.51 in P. adeliae to 117 ng/g dw in S. maccormicki. The highest concentrations of most PFAAs were found in trans-equatorial migrators such as S. maccormicki, probably due their high trophic position and higher concentrations of PFAAs in the Northern Hemisphere compared to the Southern Hemisphere. Based on stable isotopes correlations, our results suggest that the trophic position (δ15N) and the foraging area (δ13C and δ34S) influence PFAAs concentrations in Antarctic seabirds. Our results point to the possibility that long-distance migratory birds may have as bio-vectors in the transport of pollutants, including PFCAs, in Antarctic environments, although this must be further confirmed in future studies using a mass balanced approach, such as extractable organofluorine (EOF).

Distribution of metals in water, sediment and fish tissue. Consequences for human health risks due to fish consumption in Lake Hawassa, Ethiopia.

Water pollution may be a serious environmental problem for Lake Hawassa, an important fishing and recreational site as well as a drinking-water source in Ethiopia. The present study aims at determining the distribution of metals and metalloids in the lake's water, sediment and fish tissues and assessing the resulting human health and ecological risks. Metals were detected in both abiotic and biotic samples. In water, only the Hg concentration was significantly different among sampling sites. The average concentration of As, Cd, Cr, Cu, Ni, Pb, and Zn in water were below the environmental quality thresholds, thus not having potentially adverse effect on aquatic life. In sediment, significant differences in metals concentration among sites were found for As, Cd, Pb, Co, Zn and Hg (p < 0.05). Exceedances of As, Cr, Cu, Hg, Ni and Zn were found in sediment, with Cr, Ni and Zn above the probable effect concentration and being potentially toxic to aquatic life. Fish stored more metals in their liver than in their muscle. The concentration of metals in carnivorous fish (Barbus intermedius) was not higher in muscle and liver than those in herbivores fish (Oreochromis niloticus). The Bioaccumulation Factor of Cr in all fish species muscle was >1. The Biota-Sediment Accumulation Factor of all metals in all fish species muscle were <1. Positive correlations among metals in water and correlations among metals in sediment were found, indicating a potential common pollution source. Positive correlation of total organic carbon with Cd, Co and Se and clay content with Pb, As and Hg was found and may imply that metals are easily adsorbed by the organic matter and fine sediment. With respect to the measured metals no potential health risk due to consumption of fish from Lake Hawassa was observed.

Distribution of perfluoroalkyl substances (PFASs) in water, sediment, and fish tissue, and the potential human health risks due to fish consumption in Lake Hawassa, Ethiopia.

Due to their global distribution, persistence, bioaccumulative potential and toxicity, perfluoroalkyl substances (PFASs) are considered as hazardous chemicals. Although many studies on PFASs pollution in aquatic environments have been done in the Northern hemisphere, less is known on PFASs pollution in African aquatic ecosystems and the risks they pose to humans through consumption of contaminated biota. The objective of this study was to determine the spatial distribution of PFASs in water, sediment, and fish tissue in Lake Hawassa, Ethiopia, and to investigate possible human health risks due to fish consumption. Among the PFASs detected in water and sediment, perfluorooctanoic acid (PFOA) was the most abundant with mean concentrations of 6.93 ng/L and 0.23 ng/g dw respectively. Long-chained PFASs dominated the PFAS accumulation profiles in fish tissues, with higher concentrations measured in liver compared to muscle tissue. The detected concentrations of PFASs were, however, often similar to those reported in other African aquatic ecosystems. This study showed no potential health risk due to consumption of contaminated fish based on mean concentrations and fish consumption. However, it is expected that peoples who consume more fish (fishermen and local peoples living close to Lake Hawassa) may suffer health risks due to PFASs contamination.

Perfluoroalkylated acids (PFAAs) accumulate in field-exposed snails (Cepaea sp.) and affect their oxidative status.

Perfluoroalkyl acids (PFAAs) are a group of synthetic persistent chemicals with distinctive properties, such as a high thermal and chemical stability, that make them suitable for a wide range of applications. They have been produced since the 1950s, resulting in a global contamination of the environment and wildlife. They are resistant to biodegradation and have the tendency to bio-accumulate in organisms and bio-magnify in the food chain. However, little is known about the bioaccumulation of PFAAs in terrestrial invertebrates, including how they affect the physiology and particularly oxidative status. Therefore, we studied the bioaccumulation of PFAAs in snails that were exposed for 3 and 6 weeks along a distance gradient radiating from a well-known fluorochemical hotspot (3M). In addition, we examined the potential effects of PFAAs on the oxidative status of these snails. Finally, we tested for relationships between the concentrations of PFAAs in snails with those in soil and nettles they were feeding on and the influence of soil physicochemical properties on these relationships. Our results showed higher concentrations of PFOA and/or PFOS in almost every matrix at the 3M site, but no concentration gradient along the distance gradient. The PFOS concentrations in snails were related to those in the nettles and soil, and were affected by multiple soil properties. For PFOA, we observed no relationships between soil and biota concentrations. Short-chained PFAAs were dominant in nettles, whereas in soil and snails long-chained PFAAs were dominant. We found a significant positive correlation between peroxidase, catalase and peroxiredoxins and PFAA concentrations, suggesting that snails, in terms of oxidative stress (OS) response, are possibly susceptible to PFAAs pollution. CAPSULE: We observed a positive correlation between the levels of PFAAs and the antioxidants peroxidase, catalase and peroxiredoxins in snails, exposed on nettles grown at contaminated sites.

A rapid method for the detection and quantification of legacy and emerging per- and polyfluoroalkyl substances (PFAS) in bird feathers using UPLC-MS/MS.

The bioaccumulation and toxicity of per- and polyfluoroalkyl substances (PFAS) have raised scientific and public concern in recent decades, leading to regulatory measures for some PFAS (e.g. perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA)). In addition, the discovery of new PFAS alternatives in the environment has led to growing concern about the presence of numerous other PFAS that are used unrestricted. Feathers have been successfully applied as non-destructive indicators for various contaminants, mostly metals and persistent organic pollutants (POPs), whereas their suitability as an indicator for PFAS is still discussed. Previous studies on PFAS in feathers have focused primarily on perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs); analytical methods for other groups of PFAS or PFAS alternatives in feathers are still lacking. Hence, this study aimed to develop a rapid, sensitive and reliable analytical method for determining a broad range of PFAS (N = 32) in feathers, using liquid chromatography-tandem mass spectrometry (LC-MS/MS). An extraction duration of 24 h was found to be sufficient to extract the majority of PFAS from the feathers. The extraction recovery of the internal standards ranged on average from 68% (PFBA) to 97% (PFOS). The spike recovery was within an acceptable range of at least 70% for most of the target analytes and the precision was often > 80%. A further extract clean-up using weak anion exchange (WAX) solid phase extraction (SPE), was proven unnecessary, as it resulted in a similar or lower spike recovery, and, as a consequence, a lower precision and higher quantification limit. The analytical method allows detection of low PFAS concentrations in a low quantity of matrix (i.e. small feathers). The developed LC-MS/MS method was validated and shown to be a fast, sensitive and reliable method for determining a broad range of legacy and emerging PFAS in feathers.

Risks posed by per- and polyfluoroalkyl substances (PFAS) on the African continent, emphasizing aquatic ecosystems.

Per- and polyfluoroalkyl substances (PFAS) are organic pollutants that may have adverse effects on the ecosystem. Despite the global presence of PFAS, knowledge of PFAS on the African continent is limited because monitoring of PFAS is challenging and often not feasible owing to the lack of analytical capacity and high cost. However, it is necessary to understand the environmental risks posed by these chemicals in developing countries, because increasing urbanization will likely increase PFAS contamination in the environment. Although, as far as is known, PFAS concentrations in the African aquatic environment are generally lower than in more developed countries, exceedances of ecological quality standards (EQS) were reported in a few cases, providing evidence of potential ecological risks to these ecosystems. However, the number of ecosystems at risk will likely increase as urbanization and modernization increase in African countries. Therefore, environmental regulations should be updated and implemented to reduce further contamination of the aquatic environment with these chemicals. In addition, analytical laboratories in Africa should develop their capacity to detect PFAS and related compounds regularly and routinely. Local hot spots need to be identified, the influence of these hot spots on the PFAS burden in the environment should be investigated, and environmental regulations should be implemented for these hot spots to reduce their environmental impact. Therefore, we recommend a more routine monitoring of PFAS, including new PFAS that are currently used as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) alternatives, which are not regulated and environmentally concerning. Integr Environ Assess Manag 2021;17:726-732. © 2021 SETAC.

Preliminary study on the distribution of metals and persistent organic pollutants (POPs), including perfluoroalkylated acids (PFAS), in the aquatic environment near Morogoro, Tanzania, and the potential health risks for humans.

Metals and persistent organic pollutants (POPs), including perfluoroalkylated acids (PFAS), are chemicals with a bioaccumulative potential that are detected in wildlife around the world. Although multiple studies reported the pollution of the aquatic environment with these chemicals, only limited data is present on the environmental pollution of Tanzania's aquatic environment and the possible risks for human health through consumption of contaminated fish or invertebrates. In the present study, we examined the distribution of metals and POPs in fish, invertebrates, sediment and water, collected at two different years at multiple important water reservoirs for domestic and industrial purposes, in the aquatic environment near Morogoro, Tanzania. Furthermore, we assessed the possible risks for human health through consumption of contaminated fish and shrimp. Metal concentrations in the water, sediment, invertebrates and fish appeared to increase in sites downstream from Morogoro city, likely caused by the presence of the city as pollution source. Significant differences in accumulated concentrations of metals and POPs were observed between species, which was hypothesized to be caused by dietary differences. Concentrations of multiple metals exceeded water and sediment quality guidelines values. Only Cu (2.8-17 µg/L) and Zn (

Perfluoroalkyl acid (PFAA) profile and concentrations in two co-occurring tit species: distinct differences indicate non-generalizable results across passerines.

Eggs of terrestrial bird species have often been used to biomonitor both legacy and emerging anthropogenic contaminants, such as perfluoroalkyl acids (PFAAs). However, few, if any, studies have examined whether results obtained in a given model species can be generalized across bird species. Therefore, we compared potential differences in egg PFAA profile and concentrations between two widely studied passerine species, great tit (Parus major) and blue tit (Cyanistes caeruleus), which are similar in many aspects of their ecology and life history. Whole clutches of both species were collected from the same breeding season and at the same place (Antwerp, Belgium), enabling us to study laying order effects. Additionally, we evaluated how egg PFAA concentrations for both species changed along a distance gradient from a PFAA point source. Although the sum PFAA concentrations did not significantly differ between great tits and blue tits, large differences in PFAA profile and laying order effects were observed. Great tits showed a more diverse PFAA detection profile, including perfluorooctane sulfonic acid (PFOS) and various long-chain perfluorocarboxylic acids (PFCAs) but no short-chain compounds. Contrarily, short-chain PFCAs (perfluorobutanoic acid (PFBA) and perfluorohexanoic acid (PFHxA)) were only detected in blue tit eggs. The variation of perfluorooctanoic acid (PFOA) concentrations within clutches was large in both species, although laying order effects on PFOA concentrations were only found in blue tits. Although egg PFOA concentrations of both species decreased similarly from the fluorochemical point source onwards, more variation in egg PFOA concentrations could be explained by distance from the fluorochemical plant in great tits (60%) than in blue tits (15%). Results showed that both species markedly differed in terms of egg PFAA profile and concentrations, most likely reflecting differences in diet, foraging habits and egg protein composition. Finally, biomonitoring results of PFAAs in eggs are likely not generalizable across bird species.

Are Feathers of a Songbird Model Species (The Great Tit, Parus major) Suitable for Monitoring Perfluoroalkyl Acids (PFAAs) in Blood Plasma?

Feathers have been shown to be useful in the biomonitoring of environmental contaminants, such as metals and persistent organic pollutants. However, little is known regarding the levels of perfluoroalkyl acids (PFAAs) in feathers and the applicability of these structures for the biomonitoring of these compounds. In the present study, we report the extent to which feathers are suitable for monitoring PFAA concentrations in the blood plasma of an insectivorous songbird model species, the great tit (Parus major), settled at and in the vicinity of a fluorochemical plant in Antwerp, Belgium. For most of the target analytes (out of the 15 investigated), the feather PFAA concentrations near the plant are the highest ever reported in free-living birds. As PFAA concentrations did not differ in the adjacent sites, no pollution gradient with distance from the plant was observed. In addition, the PFAA concentrations were not associated with the age and sex of the birds. Perfluorooctanoic acid (PFOA) concentrations were significantly higher in P. major feathers than in blood plasma, but for most other PFAAs, these differences were not observed. The concentrations of perfluorooctanesulfonate (PFOS) and PFOA in P. major feathers and plasma were significantly and positively correlated when combining data from all sites but often not at individual sites. This result was likely caused by lower sample sizes at the individual sites and the use of matrices that represent different time periods. Our results suggest that P. major feathers cannot be used to estimate PFOA and PFOS concentrations in blood plasma, except when there is a great deal of variation in pollutant concentrations among sites/individual birds. Both matrices represent different time frames, providing complementary information on environmental PFAA concentrations, as illustrated by the observation that more PFAA compounds could be detected in P. major feathers than in blood plasma.