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Presence of perfluoroalkyl substances in Mediterranean sea and North Italian lake fish addressed to Italian consumer

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International Journal of Food Science & Technology
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Maria Grazia Luca at Azienda Socio-Sanitaria Territoriale - (ASST) PAPA GIOVANNI XXIII
Maria Grazia Luca
  • Azienda Socio-Sanitaria Territoriale - (ASST) PAPA GIOVANNI XXIII
Radmila Pavlovic at University of Milan
Radmila Pavlovic
Francesco Arioli at University of Milan
Francesco Arioli
Maria Nobile at University of Milan
Maria Nobile
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Abstract and Figures

The primary source of perfluoroalkyl substances (PFASs) exposure is the diet, mainly fish. Seabass (Dicentrarchus labrax) and seabream (Sparus aurata) are among the most consumed sea fish in Italy. Fish from Northern Italy lakes like perch (Perca fluviatilis) is of particular importance in terms of consumption volume, while Mediterranean shad (Alosa agone) and European whitefish (Coregonus lavaretus) represent niche consumption. These species too could be a cause of consumer exposure to PFAS. The study investigated the presence of PFASs in the above‐mentioned fish species through LC‐HRMS analysis. Only PFBA and PFOS were found both in lake and sea fish while PFBS was found only in lake fish. The found concentrations were used to estimate intake of PFOS, the only detected molecule of the four discussed in the last EFSA report. The Tolerable Weekly Intake of 4.4 ng kg⁻¹ b.w. per week was never exceeded also for the 99th percentile consumers.
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Original article
Presence of perfluoroalkyl substances in Mediterranean sea and
North Italian lake fish addressed to Italian consumer
Luca Maria Chiesa,
1
Radmila Pavlovic,
1
Francesco Arioli,
1*
Maria Nobile,
1*
Federica Di Cesare,
1
Giacomo Mosconi,
1
Ermelinda Falletta,
2
Renato Malandra
3
& Sara Panseri
1
1 Department of Health, Animal Science and Food Safety, University of Milan, Via dell’ Universit`
a 6, Lodi 26900, Italy
2 Department of Chemistry, University of Milan, Via Golgi, 19 - Corpo A, Milan 20133, Italy
3 Director of Veterinary Unit, ATS Milano-Citt`
a metropolitana, Via Celoria 10, Milan 20133, Italy
(Received 1 September 2021; Accepted in revised form 16 December 2021)
Summary The primary source of perfluoroalkyl substances (PFASs) exposure is the diet, mainly fish. Seabass
(Dicentrarchus labrax) and seabream (Sparus aurata) are among the most consumed sea fish in Italy. Fish
from Northern Italy lakes like perch (Perca fluviatilis) is of particular importance in terms of consumption
volume, while Mediterranean shad (Alosa agone) and European whitefish (Coregonus lavaretus) represent
niche consumption. These species too could be a cause of consumer exposure to PFAS. The study investi-
gated the presence of PFASs in the above-mentioned fish species through LC-HRMS analysis. Only
PFBA and PFOS were found both in lake and sea fish while PFBS was found only in lake fish. The
found concentrations were used to estimate intake of PFOS, the only detected molecule of the four dis-
cussed in the last EFSA report. The Tolerable Weekly Intake of 4.4 ng kg
−1
b.w. per week was never
exceeded also for the 99th percentile consumers.
Keywords Food safety, HPLC-HRMS, intake evaluation, lake fish, perfluoroalkyl substances, seabass, seabream.
Introduction
Perfluoroalkyl substances (PFASs) are fluorinated com-
pounds with high chemical, biological and thermal
inertness, used for a wide range of industrial and chemi-
cal products for their non-stick and non-stain properties
(Christensen et al., 2017). The wide use of PFASs led
to their global spread and distribution in the environ-
ment and biota. At neutral pH, these substances have
anionic terminal groups, which most explain their
chemical properties and behavior. PFASs are both
hydrophilic and fat-soluble, and therefore they do not
accumulate in fatty tissues as other persistent pollutants
(EFSA, 2008; Chiesa et al., 2019a). PFASs are included
among the contaminants of emerging concern (CECs),
able to bioaccumulate and to biomagnify in higher
trophic levels of a food chain, and categorized as endo-
crine disruptors (Jensen & Leffers, 2008).
Due to their potential for carcinogenic, reproduc-
tive, and developmental toxicity, demonstrated in dif-
ferent experimental animal species, perfluorooctane
sulfonic acid (PFOS) and perfluorooctanoic acid
(PFOA) are the most known and investigated PFASs.
Recently, EFSA published a new scientific opinion on
the risks to human health related to the presence of
PFASs in food (EFSA, 2020). The CONTAM
Panel carried out the assessment for the sum of four
PFASs: PFOA, PFNA, PFHxS and PFOS.
These are the PFASs that contribute most to the
levels observed in human serum following available
occurrence data and ‘in humans, share toxicokinetic
properties, and show similar accumulation and long
half-lives’. After two studies that measured the antibody
titres for diphtheria, tetanus, and haemophilus influen-
zae type b (Hib) in children aged 1–7years,theEFSA
report considered as the most critical effect the immune
response to vaccination, therefore the immune system
was indicated as the primary target for PFASs toxic
effects (Grandjean et al., 2012; Abraham et al., 2020).
The CONTAM Panel concluded stating a group
Tolerable Weekly Intake (TWI) of 4.4 ng kg
−1
b.w.
per week for the sum of PFOA, PFNA, PFHxS and
PFOS (EFSA, 2020). Moreover, with the application
of the modern omics techniques, the toxicological
potential of short-chain PFASs is also being progres-
sively explored and, consequently, attention to the
*Correspondent: Fax: +00390250317941;
e-mail: francesco.arioli@unimi.it (F.A.) and Fax: +00390250317941;
e-mail: maria.nobile1@unimi.it (M.N.)
International Journal of Food Science and Technology 2022, 57, 1303–1316
doi:10.1111/ijfs.15532
©2021 Institute of Food, Science and Technology (IFSTTF).
1303
... The dried extract was suspended in 10 mL of purified Milli-Q water and underwent SPE extraction using the Strata PFAS (WAX/GCB), 200 mg/50 mg/6 mL, purchased by Phenomenex SRL (Torrance, CA, USA), for further purification and extraction under vacuum according to the conditions of a previously validated method [25]. At complete drying, the samples were resuspended in 100 µL of MeOH with a 100 µL mobile phase composed of 90% water with ammonium formate 20 mM and 10% of MeOH, centrifuged for 2 min at 23,500× g and transferred into vials for UPLC-HRMS. ...
... The dried extract was suspended in 10 mL of purified Milli-Q water and underwen SPE extraction using the Strata PFAS (WAX/GCB), 200 mg/50 mg/6 mL, purchased b Phenomenex SRL (Torrance, CA, USA), for further purification and extraction unde vacuum according to the conditions of a previously validated method [25]. At complet drying, the samples were resuspended in 100 µL of MeOH with a 100 µL mobile phas composed of 90% water with ammonium formate 20 mM and 10% of MeOH, centrifuge for 2 min at 23,500× g and transferred into vials for UPLC-HRMS. ...
... As reported in Section 2, the two areas differ in anthropogenic activities, including agricultural activities. As described in numerous studies, PFASs are contained in substances such as herbicides and pesticides widely used in these activities [25], so a difference in concentration in the tissues of roe deer belonging to rural and urbanized areas was expected. The mean concentrations of PFASs detected in the urbanized area deer were not significantly higher than in the rural area deer, even if, as shown in Figure 3, all compounds tended to be higher (p ≤ 0.1) in animals from the urbanized area. ...
Influence of Area, Age and Sex on Per- and Polyfluorinated Alkyl Substances Detected in Roe Deer Muscle and Liver from Selected Areas of Northern Italy
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  • Feb 2024
Due to their physicochemical properties, per- and polyfluorinated alkyl substances (PFASs) persist and bioaccumulate in living organisms, causing adverse health effects. Since exposure to xenobiotics is influenced by factors related to both the living organism and the considered compounds, biomonitoring PFASs’ presence in the environment is of crucial importance. This study aimed to detect and quantify 15 PFASs in the muscle and liver of 40 roe deer from a specific area in Northern Italy by UPLC-HRMS. In the roe deer, liver PFAS concentrations were higher than those seen in muscle (p < 0.05). Although PFAS content in animals from urbanized areas was higher than those found in deer from rural areas, this difference was not statistically significant. In female roe deer, the concentration was higher than in males (p < 0.05); moreover, older animals showed higher concentrations of PFASs in the liver than younger animals (p < 0.05). In conclusion, the amount of PFASs was higher in tissues from roe deer belonging to urbanized areas, showing that this species might serve as a good bioindicator due to its territorial behavior. PFAS content was significantly higher in female roe deer, although the reason is not fully known. Finally, PFAS concentration was higher in the liver of older animals, probably due to compromised hepatic function.
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... Studies have detected PFASs in various wild animal species, including birds, fish, and mammals [10][11][12][13]. These chemicals have been found in the blood, liver, and muscle tissues of animals, indicating that they are absorbed and distributed throughout the body [11,14]. ...
... Targeted analyses aim to quantify the occurrence of known PFASs by means of HPLC-HRMS in the pg/g range [10,11]. Non-targeted analyses aim to characterise PFASs more comprehensively, including PFASs that are unexpected or unknown, also by means of HPLC-HRMS but with the subsequent retrospective data processing performed with some of the available metabolomics software [22]. ...
... The map illustrates the intensities of each identified compound (Figure 3), with compounds showing significantly higher abundance depicted in red and those with lower abundance appearing in green. The compounds 2 (1,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-7-pentadecene), 9 (1-((3-(Dimethylamino)propyl)amino)- 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,13,13,13-icosafluoro-12-(trifluoromethyl)tridecan-1-ol), 11 (1-(Difluoromethoxy)-1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethane), and 38 (6-(1,1,1,3,3,3-Hexafluoro-2-hydroxypropan-2-yl)-3,5,5-trimethylcyclohex-2-en-1-ol) were exclusively detected in the muscle, while 46 (N-dihydroxyethyl amino propyl-perfluorodecane amide), 52 (Perfluoroheptanesulphonyl fluoride), and 56 (Perfluoropropyl formate) were present only in the liver matrix. A few individual samples demonstrated peculiarly high concentrations of some PFASs. ...
High-Resolution Mass Spectrometry Non-Targeted Detection of Per- and Polyfluoroalkyl Substances in Roe Deer (Capreolus capreolus)
Article
Full-text available
  • Jan 2024
  • MOLECULES
Among wildlife species, roe deer stands out as a valuable indicator of environmental pollution due to its ecological significance and role as a game animal. The assessment of poly- and perfluoro substances (PFASs) bioaccumulation is of the utmost importance, relying on the liver and muscles as the main organs of interest. The study concerned the identification of 60 PFAS through a non-target workflow analysis based on HPLC Q-Exactive Orbitrap High-Resolution Mass Spectrometry in a homogeneous group of 18 female roe deer species. The developed strategy allowed us to individuate the 60 PFAS compounds with different levels of confirmation. Apart from seven PFASs identified via analytical standards, the remaining fifty-three features were identified with CL 2 or 3. Moreover, by applying a differential statistic approach, it was possible to distinguish the bioaccumulation patterns in the liver and muscle, identifying 12 PFAS upregulated in the muscle and 20 in the liver. The analysis reveals that specific PFAS compounds present exclusively in either the muscle or in the liver. The study emphasises the specificity of the liver and muscle as significant bioaccumulation sites for PFAS, raising questions about the underlying mechanisms of this process. In conclusion, the presented non-targeted PFAS analysis workflow evidenced promising and reliable results, successfully demonstrating its feasibility in the field of environmental research.
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... The extraction protocol was carried out following the procedure of our previous work [24]. Briefly, 5 g of homogenized sample were spiked with internal standards at 5 ng g −1 , extracted with 10 mL of acetonitrile, vortexed, sonicated, and centrifuged (2500× g, 4 • C, 10 min). ...
... Furthermore, in order to retard PFASs already present in the system, a small Megabond WR C18 column (5 cm, 4.6 mm, i.d. 10 mm) was introduced before the injector. The chromatographic conditions and HRMS parameters are reported in our previous work [24]. The software used was Xcalibur TM 4.5 (Thermo Fisher Scientific, Waltham, MA, USA). ...
... Nowadays, for drinking water, the most recent Italian Legislative Decree n.18/2023, which has taken reaction from March 2023, established maximum limits of 0.5 and 0.1 µg L −1 for the "Total PFASs" (obtained considering the total sum of the detected PFASs) and "PFAS Sum" (obtained only considering the PFASs of greatest concern), respectively. Meanwhile, for other matrices of different food chains, Chiesa et al., 2022 [24] investigated the presence of PFASs in several fish species from the Mediterranean Sea and North Italian Lake, detecting the presence of PFBA, PFBS, and PFOS in the ranges of <LOQ − 26.48, <LOQ − 8.27, and <LOQ − 24.41 ng g −1 , for lake fish respectively, and <LOQ − 17.99, <LOQ − 0.67 ng g −1 for PFBA and PFOS in sea fish, respectively. Furthermore, Barbarossa et al., 2014 [37] investigated the presence of PFASs in Italian cow milk, detecting PFOS and PFOA with maximum concentrations of 0.97 and 0.32 ng L −1 , respectively. ...
Incidence of Perfluoroalkyl Substances in Commercial Eggs and Their Impact on Consumer’s Safety
Article
Full-text available
  • Oct 2023
Eggs play an important role in a balanced diet; however, the European Food Safety Authority (EFSA) recognizes eggs as a major source of poly and per-fluoroalkyl substances (PFASs). In this study, the presence of PFASs was analysed in eggs produced by hens from Northern Italian regions, a PFASs-contaminated area. Sixty-five samples were analysed by high-performance liquid chromatography coupled with high-resolution mass spectrometry. The greatest presence of PFASs was found in eggs from Veneto and Emilia Romagna, and the most detected PFASs were perfluorobutanoic acid (PFBA) and perfluorooctanesulfonic acid (PFOS) (mean concentrations 0.30 ± 0.15 and 0.05 ± 0.00 ng g−1). Considering the most recent updates for the sum of the main four PFASs, the highest concentration found in the analysed samples was 0.05 ng g−1, well below the maximum limit set by the European Union. The PFAS intake evaluation confirmed that egg consumption does not represent a risk for Italian consumers.
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... In the end, the extract was reconstituted by adding 100 μl of MeOH and 100 μl of the mobile phase (90% water with 20 mM ammonium formate and 10% MeOH), vortexed, and transferred into vials for UPLC-HRMS. For the extraction of PFASs from muscle and liver samples, a method already validated by the authors in other biological matrices was used (39,48,49). The instrumental method, based on the recent study by Draghi et al. (49), used a Vanquish system equipped with a binary pump, auto-sampler, and a thermostatted compartment for two columns (Thermo Fisher Scientific, Waltham, MA, USA), coupled to a Thermo Q Exactive Orbitrap™ (Thermo Fisher Scientific, Waltham, MA, USA) with a heated electrospray ionization source. ...
Comparative analysis of PFASs concentrations in fur, muscle, and liver of wild roe deer as biomonitoring matrices
Article
Full-text available
  • Dec 2024
Background Recently, environmental pollution has become a significant concern for human, animal, and environmental health, fitting within the “One Health” framework. Among the various environmental contaminants, per- and polyfluoroalkyl substances (PFASs) have gathered substantial attention due to their persistence, bioaccumulation, and adverse health effects. This study aimed to compare the levels of 12 PFASs in the fur, liver, and muscle of wild roe deer to evaluate the feasibility of using fur as a non-invasive biomonitoring matrix. Methods A total of 20 male and 20 female roe deer aged between 12 and 24 months were randomly sampled from a hunting area in Northern Italy. Samples of fur, muscle, and liver were collected post-mortem, and PFAS concentrations were measured using a validated UHPLC-HRMS method. Results and discussion The results indicated significant differences in PFAS concentrations among the three matrices. Fur, although easier to sample and store, showed highly variable PFAS levels, with different detection frequencies compared to the muscle and liver. PFASs such as PFHxA were more frequently detected in fur than in the liver and muscle, while compounds such as PFBA, PFPeA, PFHpA, PFDA, PFHxS, 6-2 FTS, and 8-2 FTS were less frequently detected in fur. In conclusion, while fur presents many practical advantages for biomonitoring, such as non-invasive sampling and stability, its use is complicated by varying detection frequencies and concentration levels. These aspects, together with the use of a single sampling technique, can be considered a limitation of the study. Notably, compounds such as PFOA, PFNA, and PFOS showed partially similar detection frequencies across the matrices, suggesting potential interest for further research. This study offers new perspectives on the use of fur for environmental monitoring, highlighting the need for more extensive research to understand the relationship between PFAS concentrations in fur and other biological matrices. Future studies should focus on methodological improvements in extraction and quantification techniques for PFASs in fur to enhance their reliability as a biomonitoring tool.
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... Regarding European perch, Squadrone et al. quantified PFOS in the muscle of specimens caught in Varese Lake, with a mean of 9.6 µg kg −1 (from 5.4 to 17 µg kg −1 ), while the PFOA level was <LOQ [28]. Valsecchi [27]. The PFAS levels reported in the present study are much lower than those in samples from different European basins. ...
Exploring Perfluoroalkyl Substances (PFASs) in Aquatic Fauna of Lake Trasimeno (Italy): Insights from a Low-Anthropized Area
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  • Mar 2024
This study investigated the concentrations and profiles of 19 perfluoroalkyl substances (PFASs) in the muscle and liver of four freshwater species from Lake Trasimeno (Italy): Anguilla anguilla (European eel), Carassius auratus (goldfish), Perca fluviatilis (European perch), and Procambarus clarkii (red swamp crayfish). In livers, the amount of PFASs ranged from 3.1 to 10 µg kg⁻¹, significantly higher than that in muscle (0.032–1.7 µg kg⁻¹). The predominant PFASs were perfluorooctane sulfonic acid (PFOS) and long-chain carboxylic acids (C8-C14). Short-chain compounds (C4-C5), as well as the long-chain sulfonic acids (C9-C12), were not quantified. The contamination patterns were similar among species with few differences, suggesting the influence of species-specific accumulation. The PFAS concentrations in livers were comparable among species, while in muscle, the higher values were measured in European eel, followed by goldfish, European perch, and red swamp crayfish. The levels were generally lower than those reported for fish from Northern Italian lakes and rivers. The concentrations of regulated PFASs were lower than the maximum limits set by Regulation EU 2023/915 and did not exceed the Environmental Quality Standards (PFOS in biota). This study provides the first valuable insights on PFASs in freshwater species from Lake Trasimeno.
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... Regardless of the milk fraction, all samples were extracted according to a previously validated method [50] with some modifications. After adding the mixture of ISs to achieve a final concentration of 5 ng g −1 , 10 mL of acetonitrile was added for PFAS extraction and protein precipitation, then samples were homogenized using a high-performance dispersing instrument (T 25 digital ULTRA TURRAX ® , IKA ® -Werke GmBH & Co. KG, Staufen, Germany) for 30 s, vortexed, and sonicated for 15 min. ...
First Investigation of the Physiological Distribution of Legacy and Emerging Perfluoroalkyl Substances in Raw Bovine Milk According to the Component Fraction
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Bovine milk is a pillar of the human diet and plays a key role in the nutrition of infants. Perfluoroalkyl substances (PFASs) are well-recognized highly stable organic compounds that are able to pollute ecosystems persistently and threaten both human and animal health. The study aimed to analyze the distribution of 14 PFASs within the milk matrix by comparing their content in whole milk, and its skimmed and creamed fractions. Raw milk samples were individually collected from 23 healthy cows (10 primiparous and 13 multiparous) reared on a farm in Northern Italy not surrounded by known point sources of PFASs. Each sample was fractioned in whole, skim, and cream components to undergo PFAS analysis using liquid chromatography–high-resolution mass spectrometry. All samples contained at least one PFAS, with perfluorobutanoic acid (PFBA) being the primary contaminant in all three fractions, followed by perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). PFOS was shown to be significantly (p < 0.001) more concentrated in cream than in raw and skimmed milk. Multiparous cows showed a higher frequency of positive samples in all analyzed fractions. Further research is necessary to assess the risk of dairy diets and high-fat dairy products and to investigate the toxicological effects of PFASs on cattle, even in environments without known PFAS sources.
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Per‐ and polyfluoroalkyl substances in blue crabs from the Adriatic Sea and consumer safety evaluation
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The blue crab is one of the most invasive alien species in the Mediterranean Sea. Its remarkable surge in availability suggests an imminent increase in consumption. However, blue crabs are vulnerable to contamination by per‐ and polyfluoroalkyl substances (PFAS), known to accumulate in the food chain and pose health risks to humans. Data on PFAS contamination levels in blue crabs are a few. This study investigates 26 PFAS in 113 blue crabs by UHPLC‐HRMS. Results revealed higher concentrations in cephalothorax than in claws. PFHpA, PFHxS, PFOA, PFNA, PFOS, PFUnDA, PFDoDA, PFTrDA, PFHpS, and PFBA were among the most detected PFAS. Total PFAS mean concentration ranged from 0.65 to 2.61 ng g⁻¹ ww. Three crabs exceeded maximum residue limits for PFOA, PFNA, and PFHxS. Statistical analyses suggested a correlation between contaminants presence and crab size. PCA highlighted the weight as a potential predictor of PFOS concentration. PFAS intake evaluation showed no risk for consumers.
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PFAS accumulation in indigenous and translocated aquatic organisms from Belgium, with translation to human and ecological health risk
Article
Full-text available
  • Mar 2021
Background Despite specific restrictions on their production and use, per- and polyfluoralkyl substances (PFAS) are still omnipresent in the environment, including aquatic ecosystems. Most biomonitoring studies have investigated the PFAS concentrations in indigenous organisms, whereas active biomonitoring has only been used sporadically. In the present study, accumulated PFAS concentrations were measured in indigenous fish, European perch ( Perca fluviatilis ) and European eel ( Anguilla anguilla ), and in translocated freshwater mussels ( Dreissena bugensis and Corbicula fluminea) at 44 sampling locations within the main water basins of Flanders, the northern part of Belgium. Finally, both human health risk and ecological risk were assessed based on accumulated concentrations in fish muscle. Results Among locations, ΣPFAS concentrations ranged from 8.56–157 ng/g ww (median: 22.4 ng/g ww) in mussels, 5.22–67.8 ng/g ww (median: 20.8 ng/g ww) in perch, and 5.73–68.8 ng/g ww (median: 22.1 ng/g ww) in eel. Concentrations of PFOA and PFTeDA were higher in mussels compared to fish, whereas for PFDA and PFUnDA the opposite was true. A comparison of concentrations on a wet weight basis between both fish species showed significantly higher PFDoDA, PFTrDA, PFTeDA and PFOA concentrations in eel compared to perch and significantly higher concentrations of PFDA and PFOS in perch. In mussels, PFAS profiles were dominated by PFOA and showed a higher relative contribution of short-chained PFAS, while PFAS profiles in fish were dominated by PFOS. Furthermore, all mussel species clearly occupied a lower trophic level than both fish species, based on a stable isotope analysis. Conclusions Biomagnification of PFDA, PFUnDA and PFOS and biodilution of PFOA and PFTeDA were observed. Translocated mussels have been proven suitable to determine which PFAS are present in indigenous fish, since similar PFAS profiles were measured in all biota. Finally, mean PFAS concentrations in fish did pose a human health risk for eel, although tolerable daily intake values for perch were close to the reported daily consumption rates in Belgium and exceeded them in highly contaminated locations. Based on the ecological risk of PFOS, the standard was exceeded at about half of the sampling locations (44% for perch and 58% for eel).
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Risk to human health related to the presence of perfluoroalkyl substances in food
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Full-text available
  • Sep 2020
The European Commission asked EFSA for a scientific evaluation on the risks to human health related to the presence of perfluoroalkyl substances (PFASs) in food. Based on several similar effects in animals, toxicokinetics and observed concentrations in human blood, the CONTAM Panel decided to perform the assessment for the sum of four PFASs: PFOA, PFNA, PFHxS and PFOS. These made up half of the lower bound (LB) exposure to those PFASs with available occurrence data, the remaining contribution being primarily from PFASs with short half-lives. Equal potencies were assumed for the four PFASs included in the assessment. The mean LB exposure in adolescents and adult age groups ranged from 3 to 22, the 95th percentile from 9 to 70 ng/kg body weight (bw) per week. Toddlers and ‘other children’ showed a twofold higher exposure. Upper bound exposure was 4- to 49-fold higher than LB levels, but the latter were considered more reliable. ‘Fish meat’, ‘Fruit and fruit products’ and ‘Eggs and egg products’ contributed most to the exposure. Based on available studies in animals and humans, effects on the immune system were considered the most critical for the risk assessment. From a human study, a lowest BMDL10 of 17.5 ng/mL for the sum of the four PFASs in serum was identified for 1-year-old children. Using PBPK modelling, this serum level of 17.5 ng/mL in children was estimated to correspond to longterm maternal exposure of 0.63 ng/kg bw per day. Since accumulation over time is important, a tolerable weekly intake (TWI) of 4.4 ng/kg bw per week was established. This TWI also protects against other potential adverse effects observed in humans. Based on the estimated LB exposure, but also reported serum levels, the CONTAM Panel concluded that parts of the European population exceed this TWI, which is of concern.
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Per- and polyfluoroalkyl substances in the German environment – Levels and patterns in different matrices
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  • Jun 2020
  • SCI TOTAL ENVIRON
Per- and polyfluoroalkyl substances (PFAS) in the environment mostly originate from emissions of previously unregulated PFAS. However, there are also many documented incidents of accidental releases. To track such releases, it is essential to distinguish between typical background contamination and legally relevant incidents. This requires a comprehensive overview of all PFAS present in the environment, which is currently only possible to a limited extent due to the large variety of individual compounds. In the present study, a multimethod for capturing 41 PFAS including perfluoroalkyl acid (PFAA) precursors is introduced. The applicability of the method was tested on terrestrial, freshwater and marine samples from the German Environmental Specimen Bank (ESB), thereby providing a rough overview of PFAS contamination in German environment. Special focus was put on soil samples from ESB sites across Germany in comparison to soil samples from a polluted site in south-west Germany. The method was successfully applied to environmental samples. In total, 31 PFAS were detected, among them PFAA precursors and fluorinated ethers. Substance patterns differed between sites and matrices. In ESB soil samples from 2014 (n = 11), the sum of all captured PFAS ranged between 0.75 and 19.5 μg kg⁻¹ dry weight (dw), while concentrations between 416 μg kg⁻¹ and 3530 μg kg⁻¹ were detected in samples from the incident site (n = 10). In other matrices, total PFAS concentrations were magnitudes lower. Highest concentrations were observed for PFOS in bream livers from the Saale (226 μg kg⁻¹). Given the heterogeneous patterns, it will require further broadly-based monitoring data to allow for a solid estimation of relevant background levels. The data provided here may support the differentiation between background levels and hotspot contaminations.
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Trophic Magnification of Legacy (PCB, DDT and Hg) and Emerging Pollutants (PFAS) in the Fish Community of a Small Protected Southern Alpine Lake (Lake Mergozzo, Northern Italy)
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  • Jun 2020
The biomagnification of mercury, polychlorobiphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs) and perfluoroalkyl acids substances (PFASs) was evaluated in the trophic web of Lake Mergozzo, a small and deep Italian subalpine lake, which has been chosen because it is a protected environment, and discharges into the lake are mostly avoided. Carbon source and relative trophic levels were calculated by using 13C and 15N stable isotopes, respectively, and trophic magnification factors (TMFs) were derived. Zooplankton and thirteen species of fish were collected and analyzed, and the results showed the elevated level of biota contamination from both legacy and emerging pollutants, even if direct discharges were avoided. Concentrations in biota, expressed as sums of compounds, ranged from 0.4 to 60 µg kg−1 wet weight (ww) for PFASs, from 16 to 1.3 104 µg kg−1 lipid content (lw) for DDTs, from 17 to 1.5 104 µg kg−1 lw for PCBs and from 20.0 to 501 µg kg−1 ww for mercury (Hg). TMFs of this deep, cold lake, with a prevalent pelagic trophic chain, were high and clearly indicated fish biomagnification, except for PFAS. The biomagnification capability of PFAS in a fish-only food web was discussed by using the biomagnification of Hg as a benchmark for assessing their bioaccumulation potential.
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Internal exposure to perfluoroalkyl substances (PFASs) and biological markers in 101 healthy 1-year-old children: associations between levels of perfluorooctanoic acid (PFOA) and vaccine response
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  • Jun 2020
  • ARCH TOXICOL
Perfluoroalkyl substances (PFASs) are a complex group of man-made chemicals with high stability and mobility leading to ubiquitous environmental contamination and accumulation in the food chain. In human serum/plasma samples, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are the lead compounds. They are immunotoxic in experimental animals, and epidemiological studies provided evidence of a diminished production of vaccine antibodies in young children. However, information on children of the first year of age is missing but relevant, as they have a relatively high exposure if breastfed, and may have a higher susceptibility as their immune system is developing. In a cross-sectional study with 101 healthy 1-year-old children, internal levels of persistent organic pollutants and a broad panel of biological parameters were investigated at the end of the 1990s. Additional analysis of PFASs resulted in plasma levels (mean ± SD) of PFOA and PFOS of 3.8 ± 1.1 and 6.8 ± 3.4 µg/L, respectively, in the 21 formula-fed children, and of 16.8 ± 6.6 and 15.2 ± 6.9 µg/L in the 80 children exclusively breastfed for at least 4 months. The study revealed significant associations between levels of PFOA, but not of PFOS, and adjusted levels of vaccine antibodies against Haemophilus influenza type b (Hib, r = 0.32), tetanus (r = 0.25) and diphtheria (r = 0.23), with no observed adverse effect concentrations (NOAECs) determined by fitting a ‘knee’ function of 12.2, 16.9 and 16.2 µg/L, respectively. The effect size (means for PFOA quintiles Q1 vs. Q5) was quantified to be − 86, − 54 and − 53%, respectively. Furthermore, levels of PFOA were inversely associated with the interferon gamma (IFNɣ) production of ex-vivo lymphocytes after stimulation with tetanus and diphtheria toxoid, with an effect size of − 64 and − 59% (means Q1 vs. Q5), respectively. The study revealed no influence of PFOA and PFOS on infections during the first year of life and on levels of cholesterol. Our results confirmed the negative associations of PFAS levels and parameters of immune response observed in other epidemiological studies, with high consistency as well as comparable NOAECs and effects sizes for the three vaccine antibodies investigated, but for PFOA only. Due to reduction of background levels of PFASs during the last 20 years, children in Germany nowadays breastfed for a long duration are for the most part not expected to reach PFOA levels at the end of the breastfeeding period above the NOAECs determined.
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Perfluoroalkyl Substances (PFAS) in Fish from European Lakes: Current Contamination Status, Sources, and Perspectives for Monitoring
Article
  • Jul 2020
Fish concentrations of perfluorocarboxylic and perfluorosulfonic acids were reported for seven deep lakes in the European subalpine area, namely Lake Geneva, L. Lugano and L. Maggiore, L. Iseo, L. Como, L. Garda and L. Mergozzo, one shallow lowland (L. Varese) and two high‐altitude alpine (> 2000 m asl) lakes. Fillets and, in selected cases, other body fractions (viscera, liver and residual carcass) from eight fish species were analyzed. The possibility of harmonizing the monitoring protocols was tested: the results suggest that the sampling season is not critical for PFASs and the total protein content cannot be used for normalization of tissue concentrations because PFASs bind to specific proteins. Moreover, the polar lipid content could be used to reduce the variability of PFAS concentrations in phospholipid rich fractions of fish such as viscera and carcass. The data comparison and analysis demonstrate that the PFAS contamination in lake fish is generally correlated with the degree of the urbanization of the lake catchment, but it is sometimes difficult to compare absolute concentrations in lake fish, because the lake hydro‐morphological characteristics have a substantial role in determining the chemical concentrations of persistent and mobile contaminants. This article is protected by copyright. All rights reserved.
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Spatial profiles of perfluoroalkyl substances and mercury in fish from northern Lake Victoria, East Africa
Article
  • Jul 2020
  • CHEMOSPHERE
There is an acute deficit of data on per- and polyfluoroalkyl substances (PFASs) and mercury (Hg) in the open waters of Lake Victoria, East Africa, relative to nearshore areas. We analyzed stable isotopes (δ¹⁵N and δ¹³C), PFASs and Hg in Nile Perch and Nile Tilapia muscle and liver samples from nearshore and open lake locations from the Ugandan part of the lake. The δ¹⁵N values of Nile Perch muscle indicated a higher trophic level for samples from the open lake than from nearshore locations. Averages of ∑PFAS concentrations in Nile Perch muscle and liver (0.44 and 1.75 ng/g ww, respectively) were significantly higher than in Nile Tilapia (0.24 and 0.50 ng/g ww, respectively). ∑PFAS concentrations in muscle of open lake Nile Perch were significantly higher than for nearshore samples. A similar observation was made for total mercury concentrations in muscle (THg_Muscle) of Nile Perch. THg was dominated by methyl mercury (MeHg⁺, 22-124 ng/g ww) and mercuric mercury (Hg²⁺, <MDL-29 ng/g ww) in Nile Perch muscle. Strong correlation between MeHg⁺ and some PFASs (e.g. PFOS: r = 0.704, P = 0.016) suggested similar exposure routes or factors. Estimated daily intake values of PFOS and Hg were below international limits.
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Investigation of levels of perfluoroalkyl substances in surface water, sediment and fish tissue in New Jersey, USA
Article
  • Apr 2020
  • SCI TOTAL ENVIRON
Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative, and toxic substances found in New Jersey (NJ) due to historic and current industrial activities and the use of aqueous film forming foams. This research documents PFAS occurrence in surface water, sediments, and fish tissue at 11 targeted waterbodies in NJ suspected to be impacted by PFAS. Thirteen PFAS compounds were quantified from each media. The profile of detected PFAS differed among media from the same site, with shorter chain PFAS tending to predominate in surface water while longer chain PFAS predominated in fish and sediments. All water samples contained detectable levels of at least four perfluoroalkyl substances. PFOA, PFHpA and PFPeA were detected at every site. ΣPFAS concentrations in water samples ranged from 22.9 to 279.5 ng/L. At least one, and up to eight, PFAS were detected in sediment samples at 10 sites, while there were no detections of PFAS in sediments at the reference site. ΣPFAS concentrations in sediment samples ranged from below detection to 30.9 ng/g. At least one fish of each species at every site had detectable levels of PFAS compounds. ΣPFAS concentrations in fish were highest at sites downstream from a military facility, and lowest at the reference site. PFOS, PFDA, PFUnA and PFDoA were the predominant PFAS detected in fish tissue. PFOS was generally found in fish tissue at higher concentrations than other PFAS, with higher PFOS concentrations found in the tissue of yellow perch, American eel, pumpkinseed, and largemouth bass collected at sites with higher detections of PFOS in surface waters. PFOS levels in nearly all fish species were, on average, high enough to trigger fish consumption advisories. Additional studies are needed to further evaluate the sources and occurrence of PFAS in NJ and to better understand their movement through the environment and potential risks.
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The short-chain perfluorinated compounds PFBS, PFHxS, PFBA and PFHxA, disrupt human mesenchymal stem cell self-renewal and adipogenic differentiation
Article
  • Sep 2019
  • J ENVIRON SCI-CHINA
Per- and polyfluorinated alkyl substances (PFASs) are commonly used in industrial processes and daily life products. Because they are persistent, they accumulate in the environment, wildlife and humans. Although many studies have focused on two of the most representative PFASs, PFOS and PFOA, the potential toxicity of short-chain PFASs has not yet been given sufficient attention. We used a battery of assays to evaluate the toxicity of several four-carbon and six-carbon perfluorinated sulfonates and carboxyl acids (PFBS, PFHxS, PFBA and PFHxA), with a human mesenchymal stem cell (hMSC) system. Our results demonstrate significant cyto- and potential developmental toxicity for all the compounds analyzed, with shared but also distinct mechanisms of toxicity. Moreover, the effects of PFBS and PFHxS were stronger than those of PFBA and PFHxA, but occurred at higher doses compared to PFOS or PFOA.
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Occurrence of perfluoroalkyl substances (PFASs) in a large number of wild and farmed aquatic animals collected in the Netherlands
Article
  • May 2019
  • CHEMOSPHERE
A range of perfluoroalkyl substances (PFASs) was analysed in marine fish, farmed fish, crustaceans, bivalves and European eel caught in (mostly) Dutch waters, or purchased at Dutch markets (approximately 250 samples, collected between 2012 and 2018). ΣPFAS levels were highest in eels collected from rivers and lakes (average 43.6 ng/g and max 172 ng/g), followed by shrimps collected near the Dutch coast (average 6.7 and max. 33 ng/g ww), and seabass (average 4.5 and max. 9.4 ng/g ww). Most of the farmed fish (e.g. trout, catfish, turbot, salmon, tilapia, pangasius) were among the lowest contaminated samples in this study (averages ranged from 0.06 to 1.5 ng/g ww). Geographically, levels in marine fish from the northern North Sea (e.g. haddock, whiting, herring) were lower than in the central and southern North Sea (e.g. cod and flatfish). Concerning eel, no substantial geographical differences were found (apart from two distinct locations). The contamination pattern was similar in all species, where PFOS mostly dominated the profile, and other long-chain PFASs being frequently detected. Short-chain PFASs were rarely found. PFOS concentrations in eel varied from 3.3 ng/g (close to the North Sea) to 67 ng/g ww in eel caught from Ghent-Terneuzen canal. The majority of detected PFOS levels in eels (93%) and 1 shrimp sample from Eems-Dollard exceeded the EU Environmental Quality Standard (EQS) for surface water of 9.1 μg/kg ww. Other samples (e.g. shrimps, bivalves, flounder), subject to the EQS, did not exceed this level.
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