Urs Berger

Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins

The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminology, names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminology for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminology related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main production processes, electrochemical fluorination and telomerization, used for introducing perfluoroalkyl moieties into organic compounds, and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metabolism, into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compounds, providing recommended names and acronyms, and structural formulas, as well as Chemical Abstracts Service registry numbers. Integr Environ Assess Manag 2011;7:513–541.

Levels and trends of poly- and perfluorinated compounds in the arctic environment.

Poly- and perfluorinated organic compounds (PFCs) are ubiquitous in the Arctic environment. Several modeling studies have been conducted in attempt to resolve the dominant transport pathway of PFCs to the arctic-atmospheric transport of precursors versus direct transport via ocean currents. These studies are generally limited by their focus on perfluorooctanoate (PFOA) fluxes to arctic seawater and thus far have only used fluorotelomer alcohols (FTOHs) and sulfonamide alcohols as inputs for volatile precursors. There have been many monitoring studies from the North American and European Arctic, however, almost nothing is known about PFC levels from the Russian Arctic. In general, there are very few measurements of PFCs from the abiotic environment. Atmospheric measurements show the widespread occurrence of PFC precursors, FTOHs and perfluorinated sulfonamide alcohols. Further, PFCAs and PFSAs have been detected on atmospheric particles. The detection of PFCAs and PFSAs in snow deposition is consistent with the volatile precursor transport hypothesis. There are very limited measurements of PFCs in seawater. PFOA is generally detected in the greatest concentrations. Additional seawater measurements are needed to validate existing model predications. The bulk of the monitoring efforts in biological samples have focused on the perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs), although there are very few measurements of PFC precursors. The marine food web has been well studied, particularly the top predators. In contrast, freshwater and terrestrial ecosystems have been poorly studied. Studies show that in wildlife perfluorooctane sulfonate (PFOS) is generally measured in the highest concentration, followed by either perfluorononanoate (PFNA) or perfluoroundecanoate (PFUnA). However, some whale species show relatively high levels of perfluorooctane sulfonamide (PFOSA) and seabirds are typically characterized by high proportions of the C(11)-C(15) PFCAs. PFOA is generally infrequently detected and is present in low concentrations in arctic biota. Food web studies show high bioaccumulation in the upper trophic-level animals, although the mechanism of PFC biomagnification is not understood. Spatial trend studies show some differences between populations, although there are inconsistencies between PFC trends. The majority of temporal trend studies are from the Northern American Arctic and Greenland. Studies show generally increasing levels of PFCs from the 1970s, although some studies from the Canadian Arctic show recent declines in PFOS levels. In contrast, ringed seals and polar bears from Greenland continue to show increasing PFOS concentrations. The inconsistent temporal trends between regions may be representative of differences in emissions from source regions.

Perfluorinated Alkyl Acids in Blood Serum from Primiparous Women in Sweden: Serial Sampling during Pregnancy and Nursing, And Temporal Trends 1996–2010

We investigated temporal trends of blood serum levels of 13 perfluorinated alkyl acids (PFAAs) and perfluorooctane sulfonamide (FOSA) in primiparous women (N = 413) from Uppsala County, Sweden, sampled 3 weeks after delivery 1996-2010. Levels of the short-chain perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS) increased 11%/y and 8.3%/y, respectively, and levels of the long-chain perfluorononanoate (PFNA) and perfluorodecanoate (PFDA) increased 4.3%/y and 3.8%/y, respectively. Concomitantly, levels of FOSA (22%/y), perfluorooctane sulfonate (PFOS, 8.4%/y), perfluorodecane sulfonate (PFDS, 10%/y), and perfluorooctanoate (PFOA, 3.1%/y) decreased. Thus, one or several sources of exposure to the latter compounds have been reduced or eliminated, whereas exposure to the former compounds has recently increased. We explored if maternal levels of PFOS, PFOA, and PFNA during the early nursing period are representative for the fetal development period, using serial maternal serum samples, including cord blood (N = 19). PFAA levels in maternal serum sampled during pregnancy and the nursing period as well as in cord blood were strongly correlated. Strongest correlations between cord blood levels and maternal levels were observed for maternal serum sampled shortly before or after the delivery (r = 0.70-0.89 for PFOS and PFOA). A similar pattern was observed for PFNA, although the correlations were less strong due to levels close to the method detection limit in cord blood.

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Tromsø, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.

Fish consumption as a source of human exposure to perfluorinated alkyl substances in Sweden - analysis of edible fish from Lake Vättern and the Baltic Sea.

Perfluorinated alkyl substances (PFAS) were analyzed in muscle tissue from edible fish species caught in the second largest freshwater lake in Sweden, Lake Vättern (LV), and in the brackish water Baltic Sea (BS). Perfluorooctane sulfonate (PFOS) was the predominant PFAS found. PFOS concentrations were higher in LV (medians 2.9-12 ng g(-1) fresh weight) than in BS fish (medians 1.0-2.5 ng g(-1) fresh weight). Moreover, LV fish was more contaminated with several other PFAS than BS fish. This may be due to anthropogenic discharges from urban areas around LV. The PFAS pattern differed between LV and BS fish, indicating different sources of contamination for the two study areas. Human exposure to PFOS via fish intake was calculated for three study groups, based on consumption data from literature. The groups consisted of individuals that reported moderate or high consumption of BS fish or high consumption of LV fish, respectively. The results showed that PFOS intake strongly depended on individual fish consumption as well as the fish catchment area. Median PFOS intakes were estimated to 0.15 and 0.62 ng kg(-1) body weight (bw) d(-1) for the consumers of moderate and high amounts of BS fish, respectively. For the group with high consumption of LV fish a median PFOS intake of 2.7 ng kg(-1)bw d(-1) was calculated. Fish consumption varied considerably within the consumer groups, with maximum PFOS intakes of 4.5 (BS fish) or 9.6 ng kg(-1)bw d(-1) (LV fish). Comparison of our results with literature data on PFOS intake from food suggests that fish from contaminated areas may be a significant source of dietary PFOS exposure.

Estrogen-Like Properties of Fluorotelomer Alcohols as Revealed by MCF-7 Breast Cancer Cell Proliferation

We investigated estrogen-like properties of five perfluorinated compounds using a combination of three in vitro assays. By means of an E-screen assay, we detected the proliferation-promoting capacity of the fluorotelomer alcohols 1H,1H,2H,2H-perfluorooctan-1-ol (6:2 FTOH) and 1H,1H,2H,2H-perfluoro-decan-1-ol (8:2 FTOH). The more widely environmentally distributed compounds perfluoro-1-octane sulfonate, perfluorooctanoic acid, and perfluorononanoic acid did not seem to possess this hormone-dependent proliferation capacity. We investigated cell cycle dynamics using flow cytometric analyses of the DNA content of the nuclei of MCF-7 breast cancer cells. Exposure to both fluorotelomer alcohols stimulated resting MCF-7 cells to reenter the synthesis phase (S-phase) of the cell cycle. After only 24 hr of treatment, we observed significant increases in the percentage of cells in the S-phase. In order to further investigate the resemblance of the newly detected xenoestrogens to the reference compound 17β-estradiol (E2), gene expression of a number of estrogen-responsive genes was analyzed by real-time polymerase chain reaction. With E2, as well as 4-nonylphenol and the fluorotelomer alcohols, we observed up-regulation of trefoil factor 1, progesterone receptor, and PDZK1 and down-regulation of ERBB2 gene expression. We observed small but relevant up-regulation of the estrogen receptor as a consequence of exposures to 6:2 FTOH or 8:2 FTOH. The latter finding suggests an alternative mode of action of the fluorotelomer alcohols compared with that of E2. This study clearly underlines the need for future in vivo testing for specific endocrine-related end points.

Dietary exposure to perfluoroalkyl acids for the Swedish population in 1999, 2005 and 2010.

Dietary intake has been hypothesized to be the major pathway of human exposure to perfluoroalkyl acids (PFAAs). However, difficulties associated with the analysis of PFAAs at ultra trace levels in food samples have prevented the confirmation of this hypothesis. In this study, the dietary intake of PFAAs for the general Swedish population was estimated by applying a highly sensitive analytical method to a set of archived food market basket samples from 1999, 2005 and 2010. Dietary exposure to perfluorooctane sulfonic acid (PFOS) (860-1440 pg kg⁻¹ day⁻¹), perfluoroundecanoic acid (PFUnDA) (90-210 pg kg⁻¹ day⁻¹), perfluorodecanoic acid (PFDA) (50-110 pg kg⁻¹ day⁻¹) and perfluorononanoic acid (PFNA) (70-80 pg kg⁻¹ day⁻¹) was dominated by the consumption of fish and meat. In contrast, dietary exposure to PFOA (350-690 pg kg⁻¹ day⁻¹) originated from low levels (8-62 pg g⁻¹) found in several high consumption food categories including cereals, dairy products, vegetables and fruit. The dietary intakes of PFOS and PFOA estimated in this study were 4 to 10 times lower compared to previous exposure modeling studies. Nevertheless, the dietary intake of PFOS and PFOA was still a factor of 6 to 10 higher than exposure through ingestion of household dust and drinking water estimated for the general Swedish population. For perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA) and perfluorohexane sulfonic acid (PFHxS) drinking water intake was the major exposure pathway (36-53% of the total exposure) whereas dust ingestion made a significant contribution (27-49%) to the total exposure for PFHxA, PFHpA, PFNA, perfluorotridecanoic acid (PFTrDA) and perfluorotetradecanoic acid (PFTeDA). Dietary intakes varied by less than a factor of three for all PFAAs during the different sampling years which demonstrates that dietary intake has been fairly constant over the past decade when many manufacturing changes occurred.

Trace analysis of per- and polyfluorinated alkyl substances in various matrices - how do current methods perform?

Per- and polyfluorinated alkyl substances (PFAS) are a group of industrial chemicals, some of which have been produced for over 50 years. Scarcely one decade ago, their ubiquity in wildlife, humans and the global environment was discovered. This urged the need for robust and reliable, yet very sensitive analytical methods allowing for their determination in various matrices. This article reviews the state-of-the-art in trace analysis of ionic and neutral PFAS in humans as well as environmental samples such as wildlife, water, solid matrices and air. Analytical protocols for PFAS determination in food and consumer products are also included. The methods are critically discussed in terms of their advantages, shortcomings, possibilities, limitations, and potential for further development.

Analytical challenges hamper perfluoroalkyl research

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.

Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water

A trace analytical method based on high performance liquid chromatography coupled to quadrupole time-of-flight high resolution mass spectrometry was developed for simultaneous determination of perfluoroalkyl phosphonates (PFPAs, carbon chain lengths C6,8,10), perfluoroalkyl carboxylates (PFCAs, C5-12), and perfluoroalkyl sulfonates (PFSAs, C4,6,8,10) in drinking water (tap water). Analytes were enriched on a mixed mode co-polymeric sorbent (C8+quaternary amine) using solid phase extraction. Chromatographic separation was achieved on a Zorbax Extend C18 reversed phase column using a mobile phase gradient consisting of water, methanol, and acetonitrile containing 2mM ammonium acetate and 5 mM 1-methyl piperidine. The mass spectrometer was operated in electrospray negative ion mode. Use of 1-methyl piperidine in the mobile phase resulted in a significant increase in instrument sensitivity for PFPAs through improved chromatographic resolution, background suppression, and increased ionization efficiency. Method detection limits for extraction of 500 mL tap water were in the ranges of 0.095-0.17 ng/L, 0.027-0.17 ng/L, and 0.014-0.052 ng/L for PFPAs, PFCAs, and PFSAs, respectively. Whole method recoveries at a spiking level of 0.5 ng/L to 500 mL HPLC grade water were 40-56%, 56-97%, and 55-77% for PFPAs, PFCAs, and PFSAs, respectively. A matrix effect (signal enhancement) was observed in the detection of PFPAs in tap water extracts, leading to calculated recoveries of 249-297% at a 0.5 ng/L spiking level. This effect resulted in an additional improvement of method sensitivity for PFPAs. To compensate for the matrix effect, PFPAs in tap water were quantified using matrix-matched and extracted calibration standards. The method was successfully applied to the analysis of drinking water collected from six European countries. PFPAs were not detected except for perfluorooctyl phosphonate (PFOPA) at close to the detection limit of 0.095 ng/L in two water samples from Amsterdam, the Netherlands. Highest levels were found for perfluorobutane sulfonate (PFBS, 18.8 ng/L) and perfluorooctanoate (PFOA, 8.6 ng/L) in samples from Amsterdam as well as for perfluorooctane sulfonate (PFOS, 8.8 ng/L) in tap water from Stockholm, Sweden.