BackgroundOnly limited data exist on lactation as an exposure source of persistent perfluorinated chemicals (PFCs) for children.ObjectivesWe studied occurrence and levels of PFCs in human milk in relation to maternal serum together with the temporal trend in milk levels between 1996 and 2004 in Sweden. Matched, individual human milk and serum samples from 12 primiparous women in Sweden were analyzed together with composite milk samples (25–90 women/year) from 1996 to 2004.ResultsEight PFCs were detected in the serum samples, and five of them were also above the detection limits in the milk samples. Perfluorooctanesulfonate (PFOS) and perfluorohexanesulfonate (PFHxS) were detected in all milk samples at mean concentrations of 0.201 ng/mL and 0.085 ng/mL, respectively. Perfluorooctanesulfonamide (PFOSA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were detected less frequently.DiscussionThe total PFC concentration in maternal serum was 32 ng/mL, and the corresponding milk concentration was 0.34 ng/mL. The PFOS milk level was on average 1% of the corresponding serum level. There was a strong association between increasing serum concentration and increasing milk concentration for PFOS (r2 = 0.7) and PFHxS (r2 = 0.8). PFOS and PFHxS levels in composite milk samples were relatively unchanged between 1996 and 2004, with a total variation of 20 and 32% coefficient of variation, respectively.ConclusionThe calculated total amount of PFCs transferred by lactation to a breast-fed infant in this study was approximately 200 ng/day. Lactation is a considerable source of exposure for infants, and reference concentrations for hazard assessments are needed.
We synthesize current understanding of the magnitudes and methods for assessing human and wildlife exposures to poly‐ and perfluoroalkyl substances (PFAS). Most human exposure assessments have focused on 2 to 5 legacy PFAS, and wildlife assessments are typically limited to targeted PFAS (up to ~30 substances). However, shifts in chemical production are occurring rapidly, and targeted methods for detecting PFAS have not kept pace with these changes. Total fluorine measurements complemented by suspect screening using high‐resolution mass spectrometry are thus emerging as essential tools for PFAS exposure assessment. Such methods enable researchers to better understand contributions from precursor compounds that degrade into terminal perfluoroalkyl acids. Available data suggest that diet is the major human exposure pathway for some PFAS, but there is large variability across populations and PFAS compounds. Additional data on total fluorine in exposure media and the fraction of unidentified organofluorine are needed. Drinking water has been established as the major exposure source in contaminated communities. As water supplies are remediated, for the general population, exposures from dust, personal care products, indoor environments, and other sources may be more important. A major challenge for exposure assessments is the lack of statistically representative population surveys. For wildlife, bioaccumulation processes differ substantially between PFAS and neutral lipophilic organic compounds, prompting a reevaluation of traditional bioaccumulation metrics. There is evidence that both phospholipids and proteins are important for the tissue partitioning and accumulation of PFAS. New mechanistic models for PFAS bioaccumulation are being developed that will assist in wildlife risk evaluations. Environ Toxicol Chem 2021;40:631–657. © 2020 SETAC
Fluorinated surfactant-based aqueous film-forming foams (AFFFs) are made up of per- and polyfluorinated alkyl substances (PFAS) and are used to extinguish fires involving highly flammable liquids. The use of perfluorooctanesulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in some AFFF formulations has been linked to substantial environmental contamination. Recent studies have identified a large number of novel and infrequently reported fluorinated surfactants in different AFFF formulations. In this study, a strategy based on a case-control approach using quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) and advanced statistical methods has been used to extract and identify known and unknown PFAS in human serum associated with AFFF-exposed firefighters. Two target sulfonic acids [PFOS and perfluorohexanesulfonic acid (PFHxS)], three non-target acids [perfluoropentanesulfonic acid (PFPeS), perfluoroheptanesulfonic acid (PFHpS), and perfluorononanesulfonic acid (PFNS)], and four unknown sulfonic acids (Cl-PFOS, ketone-PFOS, ether-PFHxS, and Cl-PFHxS) were exclusively or significantly more frequently detected at higher levels in firefighters compared to controls. The application of this strategy has allowed for identification of previously unreported fluorinated chemicals in a timely and cost-efficient way.
A time trend study focusing on ski waxing technicians' exposure to perfluorinated chemicals (PFCs) from fluorinated wax fumes was performed in 2007/2008. Levels of eight perfluorocarboxylates and three perfluorosulfonates were analyzed in monthly blood samples from eight technicians. Samples were collected before the ski season, i.e., preseason, then at four FIS World Cup competitions in cross country skiing, and finally during an unexposed 5-month postseason period. The perfluorinated carboxylates perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) bioaccumulate, and continued exposure may contribute to elevated levels in ski technicians compared to the general population. The wax technicians' median blood level of PFOA is 112 ng/mL compared to 2.5 ng/mL in the general Swedish population. A significant correlation was found between number of working years and levels of perfluorocarboxylates. The PFOA levels in three technicians with "low" initial levels of PFOA (<10.0 ng/mL in preseason blood) increased by 254, 134, and 120%, whereas five technicians with "high" initial levels (>100 ng/mL in preseason sample) were at steady state. PFHxA is suggested to have a short half-life in humans relative the other perfluorocarboxylates. The levels of perfluorosulfonates were unaffected by the wax exposure.
Pooled serum samples from 3802 Australian residents were analyzed for four perfluoroalkylsulfonates, seven perfluoroalkylcarboxylates, and perfluorooctanesulfonamide (PFOSA). Serum was collected from men and women of five different age groups and from rural and urban regions in Australia. The highest mean concentration was obtained for perfluorooctane sulfonate (PFOS, 20.8 ng/mL) followed by perfluorooctanoic acid (PFOA, 7.6 ng/mL), perfluorohexane sulfonate (PFHxS, 6.2 ng/mL), perfluorononanoic acid (PFNA, 1.1 ng/mL), and PFOSA (0.71 ng/mL). Additional four PFCs were detected in 5−18% of the samples at concentrations near the detection limits (0.1−0.5 ng/mL). An increase in PFOS concentration with increasing age in both regions and genders was observed. The male pool levels of some of the age groups compared to females were higher for PFOS, PFOA, and PFHxS. In contrast, PFNA concentrations were higher in the female pools. No substantial difference was found in levels of PFCs between the urban and rural regions. The levels are equal or higher than previously reported serum levels in Europe and Asia but lower compared to the U.S.A. These results suggest that emissions from production in the Northern Hemisphere are of less importance for human exposure.
Environmental context. Perfluoroalkyl acids are used in many products and have spread into the environment where their persistence and potential toxicity pose a threat to humans and wildlife. The present study describes environmental contamination from usage of aqueous film forming foams, and investigates the distribution of structural isomers of perfluoroalkyl acids from a point source to the surrounding environment. Isomer patterns might be used to track contamination sources since isomer composition differs in the various products containing perfluoroalkyl acids. The environmental behaviour of these structural isomers is described, and limitations of their use to track contamination sources are identified.Abstract. The environment (soil, water, sediment, fish, crab and mussel) around a training facility using aqueous film forming foams (AFFFs) was studied with respect to perfluorinated alkyl acids (PFAAs) and 6 : 2 fluorotelomer sulfonate (FTS) and their structural isomers. High levels of many PFAAs and 6 : 2 FTS were detected in soil, seepage water, sediment and fish liver. Structural isomers were found for sulfonates, except PFBuS, and for PFOA. Quantification using authentic standards revealed an isomer pattern of 63% linear PFOS (L-PFOS) and 80% linear PFOA (L-PFOA) in the soil at the contamination site, which indicated a source produced by electrochemical fluorination (ECF). The 6 : 2 FTS was 100% linear in all compartments thus coming from a telomerisation product. Enrichment of the linear structure of PFOS and PFOA in soil was seen with increasing distance from the training centre, and an enrichment of branched isomers for both compounds could be found in the seepage water. Sorption to sediment and accumulation in fish liver led to an enrichment of L-PFOS whereas all PFOA remained in the water body.
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