Polyfluoroalkyl substances (PFSs) are used in industrial and commercial products and can degrade to persistent perfluorocarboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs). Temporal trend studies using human, fish, bird, and marine mammal samples indicate that exposure to PFSs has increased significantly over the past 15-25 years. This review summarizes the biological monitoring of PFCAs, PFSAs, and related PFSs in wildlife and humans, compares concentrations and contamination profiles among species and locations, evaluatesthe bioaccumulation/biomagnification in the environment, discusses possible sources, and identifies knowledge gaps. PFSs can reach elevated concentrations in humans and wildlife inhabiting industrialized areas of North America, Europe, and Asia (2-30,000 ng/ mL or ng/g of wet weight (ww)). PFSs have also been detected in organisms from the Arctic and mid-ocean islands (< or = 3000 ng/g ww). In humans, PFSAs and PFCAs have been shown to vary among ethnic groups and PFCA/PFSA profiles differ from those in wildlife with high proportions of perfluorooctanoic acid and perfluorooctane sulfonate. The pattern of contamination in wildlife varied among species and locations suggesting multiple emission sources. Food web analyses have shown that PFCAs and PFSAs can bioaccumulate and biomagnify in marine and freshwater ecosystems. Knowledge gaps with respect to the transport, accumulation, biodegradation, temporal/spatial trends and PFS precursors have been identified. Continuous monitoring with key sentinel species and standardization of analytical methods are recommended.

The goal of this article is to summarize new biological monitoring information on perfluorinated compounds (PFCs) in aquatic ecosystems (post-2005) as a followup to our critical review published in 2006. A wider range of geographical locations (e.g., South America, Russia, Antarctica) and habitats (e.g., high-mountain lakes, deep-ocean, and offshore waters) have been investigated in recent years enabling a better understanding of the global distribution of PFCs in aquatic organisms. High concentrations of PFCs continue to be detected in invertebrates, fish, reptiles, and marine mammals worldwide. Perfluorooctane sulfonate (PFOS) is still the predominant PFC detected (mean concentrations up to 1900 ng/g ww) in addition to important concentrations of long-chain perfluoroalkyl carboxylates (PFCAs; sum PFCAs up to 400 ng/g ww). More studies have evaluated the bioaccumulation and biomagnification of these compounds in both freshwater and marine food webs. Several reports have indicated a decrease in PFOS levels over time in contrast to PFCA concentrations that have tended to increase in tissues of aquatic organisms at many locations. The detection of precursor metabolites and isomers has become more frequently reported in environmental assessments yielding important information on the sources and distribution of these contaminants. The integration of environmental/ecological characteristics (e.g., latitude/longitude, salinity, and/or trophic status at sampling locations) and biological variables (e.g., age, gender, life cycle, migration, diet composition, growth rate, food chain length, metabolism, and elimination) are essential elements in order to adequately study the environmental fate and distribution of PFCs and should be more frequently considered in study design.

The environmental ubiquity of perfluorooctane sulfonate (PFOS) is well-known. However, little is known about the environmental fate of individual PFOS isomers. In this study, we investigated the fractionation and the bioaccumulation of PFOS isomers in water, sediment and biota collected from Lake Ontario. A total of six isomers, three perfluoro-monomethyl-substituted compounds, and three perfluoro-dimethyl isomers in addition to the linear PFOS (L-PFOS) were detected in water, sediment and biota. L-PFOS represented a much higher proportion of total PFOS (sum of linear and branched) in all organisms (>88%) compared to its proportion in technical PFOS (77%). The predominance of L-PFOS suggests a reduced uptake of branched isomers, a more rapid elimination of the branched isomers and/or a selective retention of the L-PFOS. The PFOS isomer profile found in biota was very similar to sediment, even for pelagic organisms such as zooplankton, suggesting greater partitioning of L-PFOS to biota and to sediment. The bioaccumulation factor (BAF) for L-PFOS between lake trout (whole fish) and water was estimated to be 3.4 x 10(4) L/kg compared with 2.9 x 10(3) L/kg for the monomethyl-substituted group (MM-PFOS). The remarkable difference between L-PFOS and branched isomer BAFs is due to an enrichment of branched isomers in water. The trophic magnification factor of L-PFOS (4.6 +/- 1.0) was greater than MM-PFOS isomers (1.3 +/- 0.17 to 2.6 +/- 0.51), whereas dimethyl-PFOS showed no biomagnification. The results illustrate the important influence of molecular structure on the bioaccumulation of perfluoroalkyl sulfonates.

The environmental distribution and the biomagnification of a suite of perfluoroalkyl compounds (PFCs), including perfluorooctane sulfonate (PFOS) and C8 to C14 perfluorinated carboxylates (PFCAs), was investigated in the food web of the bottlenose dolphin (Tursiops truncatus). Surficial seawater and sediment samples, as well as zooplankton, fish, and bottlenose dolphin tissue samples, were collected at two U.S. locations: Sarasota Bay, FL and Charleston Harbor, SC. Wastewater treatment plant (WWTP) effluents were also collected from the Charleston area (n = 4). A solid-phase extraction was used for seawater and effluent samples and an ion-pairing method was used for sediment and biotic samples. PFCs were detected in seawater (range <1-12 ng/L), sediment (range <0.01-0.4 ng/g wet weight (ww)), and zooplankton (range 0.06-0.3 ng/g ww). The highest PFC concentrations were detected in WWTP effluents, whole fish, and dolphin plasma and tissue samples in which PFOS, C8 and C10-PFCAs predominated in most matrices. Contamination profiles varied with location suggesting different sources of PFC emissions. Biomagnification factors (BMFs) ranged from <1 to 156 at Sarasota Bay and <1 to 30 at Charleston. Trophic magnification factors (TMFs) for PFOS and C8-C11 PFCAs indicated biomagnification in this marine food web. The results indicate that using plasma and liver PFC concentrations as surrogate to whole body burden in a top marine predator overestimates the BMFs and TMFs.