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Homegrown crops can present a significant exposure source of per- and polyfluoroalkyl substances (PFAS) to humans. Field studies studying PFAS accumulation in multiple vegetable food categories and examining the potential influence of soil characteristics on vegetable bioavailability under realistic exposure conditions are very scarce. Crop PFAS accumulation depends on a complex combination of factors. The physicochemical differences among the numerous PFAS makes risk assessment very challenging. Thus, simplification of this complexity into key factors that govern crop PFAS accumulation is critical. This study analyzed 29 targeted legacy, precursor and emerging PFAS in the vertical soil profile (0-45 cm depth), rainwater and edible crop parts of 88 private gardens, at different distances from a major fluorochemical plant. Gardens closer to the plant site showed higher soil concentrations which could be linked with historical and recent industrial emissions. Most compounds showed little variation along the soil depth profile, regardless of the distance from the plant site, which could be due to gardening practices. Annual crops consistently accumulated higher sum PFAS concentrations than perennials. Highest concentrations were observed in vegetables, followed by fruits and walnuts. Single soil-crop relationships were weak, which indicated that other factors (e.g., porewater) may be better measures of bioavailability in homegrown crop accumulation. Regression models, which additionally considered soil characteristics showed limited predictive power (all R2 ≤ 35%), possibly due to low variability in crop concentrations. Human intake estimations revealed that the PFAS exposure risk via crop consumption was similar nearby and remotely from the plant site, although the contribution to the overall dietary exposure can be relatively large. The tolerable weekly intake was frequently exceeded with respect to fruit and vegetable consumption, thus potential health risks cannot be ruled out.

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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.

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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.

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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.

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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.

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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.

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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.

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Although long chained PFASs have been phased-out in several countries, their persistence in the environment and bioaccumulative potential cause the environmental and biotic concentrations to remain high, highlighting the need to further monitor these pollutants. Currently several methods are used for the quantification of perfluoroalkyl substances (PFASs) in biological matrices including different ways to correct for recovery losses, each with its specific pros and contras. With this paper we aim to re-evaluate current methodologies and to create an updated new analytical guideline that is applicable for both abiotic and biotic matrices. The developed LC/MS/MS method was validated and shown to be specific, selective, linear, robust and sensitive. Reliable results could still be obtained 6 days after extraction. The recoveries varied, depending on the matrix, between 1% and 100%, but nevertheless, a high accuracy was obtained even at the lowest recoveries. A reduction of sample mass could significantly increase method recoveries and therefore it is highly recommended to take less matrix. We confirmed that using the ISTD closest in terms of functional group and carbon chain length is a suitable method for the quantification of PFASs that lack a corresponding ISTD. The newly described method was, depending on the matrix, similar in terms of sensitivity and reliability compared to a frequently used method and could be used simultaneously in future monitoring studies. Therefore, we recommend to select the purification method based on the target analytes as well as the sample matrix. CAPSULE: The newly described method was similar in terms of sensitivity and reliability compared to a frequently used method and a selection of purification methods should be based on the target analyte and sample matrix.

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The ubiquity of perfluoroalkyl acids (PFAAs) contrasts with the limited information about their effects. We report here PFAA plasma concentrations in wild populations of great tits ( Parus major) settled at and in the vicinity of a fluorochemical plant in Antwerp (Belgium). Using two generations we obtained novel results on some poorly known issues such as differences between sexes, maternal transfer of the compounds and potential associations with the oxidative status. For five out of the 11 detected PFAAs, the concentrations were the highest ever reported in birds' plasma, which confirms that Antwerp is one of the main hotspots for PFAAs pollution. Contrary to other studies conducted in birds, we found that females presented higher mean concentrations and detection frequencies for two compounds (perfluorooctanesulfonic acid (PFOS) and perfluoroundecanoic acid (PFUnDA)) than males. Maternal transfer and the dietary intake appear to be the main route of exposure for nestlings to PFOS but not to other compounds. Finally, PFAA concentrations tended to correlate positively with protein damage in adult birds while in nestlings they positively correlated with higher activity of antioxidant enzymes (glutathione peroxidase and catalase). Experimental work is needed to confirm oxidative stress as a pathway for the pernicious effects of PFAAs.

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Over the past decades, there has been growing scientific attention and public concern towards perfluoroalkyl acids (PFAAs), due to their widespread presence in the environment and associations with adverse effects on various organisms. Bird eggs have often been used as less-invasive biomonitoring tools for toxicological risk assessments of persistent organic pollutants, including some PFAAs. Hereby, it is typically assumed that one random egg is representative for the PFAA concentrations of the whole clutch. However, variation of PFAA concentrations within clutches due to laying sequence influences can have important implications for the egg collection strategy and may impede interpretations of the quantified concentrations. Therefore, the main objective of this paper was to study variation patterns and possible laying sequence associations with PFAA concentrations in eggs of the great tit (Parus major). Eight whole clutches (4-8 eggs) were collected at a location in the Antwerp region, situated about 11 km from a known PFAA point source. The ∑ PFAA concentrations ranged from 8.9 to 75.1 ng g-1 ww. PFOS concentrations ranged from 6.7 to 55.1 ng g-1 ww and this compound was the dominant contributor to the total PFAA profile (74%), followed by PFDoA (7%), PFOA (7%), PFDA (5%), PFTrA (4%) and PFNA (3%). The within-clutch variation (70.7%) of the ∑ PFAA concentrations was much larger than the among-clutch variation (29.3%) and concentrations decreased significantly for some PFAA compounds throughout the laying sequence. Nevertheless, PFAA concentrations were positively and significantly correlated between some egg pairs within the same clutch, especially between egg 1 and egg 3. For future PFAA biomonitoring studies, we recommend to consistently collect the same egg along the laying sequence, preferably the first or third egg if maximizing egg exposure metrics is the main objective.

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Although bird eggs have been used in biomonitoring studies on perfluoroalkyl acids (PFAAs), effects of environmental concentrations on reproduction remain largely unknown in wild birds. In the present study we examined the associations between the concentrations of 4 perfluoroalkyl sulfonic acids (PFSAs) and 11 perfluoroalkyl carboxylic acids (PFCAs) in the eggs of great tits (Parus major), collected along a distance gradient from a pollution source, and multiple reproductive parameters (including the start of egg laying, clutch size, hatching success, fledging success and total breeding success) along with egg shell thickness and body condition of the nestlings. The PFAA concentrations measured at the plant site were among the highest ever reported in wild bird eggs. PFAA concentrations decreased sharply with increasing distance (0-11 km) from the plant, but remained relatively elevated in the adjacent sites. PFAAs were grouped into principal components (PCs) to prevent collinearity. High concentrations of PFOS, PFDS, PFDoDA, PFTrDA and PFTeDA (grouped as PC1) were associated with a reduced hatching success of nests where at least one egg hatched, thinner egg shells and increased survival of the hatched chicks. High concentrations of PFDA (PC2) were associated with a reduced hatching success, especially in nests where no eggs hatched, an earlier start of egg laying and a reduction of total breeding success, mainly caused by the failure in hatching. Although the major manufacturer of PFAAs phased out the production of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and related products in 2002, concentrations appear to have increased since previous measurements. Surprisingly, despite the very high concentrations close to the fluorochemical plant, there was no clear evidence for reproductive impairment as the observed associations between PFAA concentrations and reproductive parameters were rather limited compared to previous studies in songbirds. These findings also suggest potential differences in sensitivity between species. CAPSULE: Despite the very high PFAA concentrations at the perfluorochemical hotspot, correlations with reproductive parameters were limited.

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