Article pubs.acs.org/est
Perfluoroalkylphosphinic Acids in Northern Pike (Esox lucius), Double-Crested Cormorants (Phalacrocorax auritus), and Bottlenose Dolphins (Tursiops truncatus) in Relation to Other Perfluoroalkyl Acids Amila O. De Silva,*,† Christine Spencer,† Ki Chung D. Ho,† Mohammed Al Tarhuni,† Christopher Go,†,○ Magali Houde,§ Shane R. de Solla,† Raphael A. Lavoie,∥ Laura E. King,† Derek C.G. Muir,† Patricia A. Fair,⊥ Randall S. Wells,#,∇ and Gregory D. Bossart∇ †
Environment and Climate Change Canada, Canada Centre for Inland Waters, Burlington, Ontario, L7S 1A1, Canada Environment and Climate Change Canada, Centre Saint-Laurent, Montréal, Quebec H2Y 2E7, Canada ∥ Biology Department, Queen’s University, 116 Barrie Street, Kingston, Ontario K7L3N6 Canada ⊥ Center for Coastal Environmental Health and Biomolecular Research, NOS, NOAA, 219 Fort Johnson Road, Charleston, South Carolina 29142, United States # Chicago Zoological Society’s Sarasota Dolphin Research Program, Mote Marine Laboratory, 1600 Ken Thompson Parkway, Sarasota, Florida 34236, United States ∇ Georgia Aquarium, 225 Baker Street, Atlanta, Georgia 30313, United States §
S Supporting Information *
ABSTRACT: Perfluoroalkyl phosphinic acids (PFPIAs) are perfluoroalkyl acids (PFAAs) that are used for their surfactant properties in a variety of applications, resulting in their presence in environmental waters; however, they have not been widely studied in biota. A survey of PFPIAs was conducted in fish, dolphins, and birds from various locations in North America. Northern pike (Esox lucius) were collected at two locations in 2011 near Montréal Island in the St. Lawrence River, Canada, double-crested cormorants (Phalacrocorax auritus) were collected from bird colonies in the Great Lakes in 2010−2012, and bottlenose dolphins (Tursiops truncatus) from Sarasota Bay, FL and Charleston Harbor, SC were sampled in 2004−2009. PFPIAs had a detection frequency of 100% in all animals. This is the first report of PFPIAs in fish, dolphin, and bird plasma. Total PFPIA levels (mean ± standard deviation, 1.87 ± 2.17 ng/g wet weight (ww), range of 0.112−15.3 ng/g ww) were 1−2 orders of magnitude lower than those of perfluoroalkyl carboxylates (PFCA) and perfluoroalkanesulfonates (PFSA) in the same samples. The predominant congeners were 6:8 PFPIA (cormorants and pike) and 6:6 PFPIA (dolphins). Total PFPIAs in cormorants from Hamilton Harbour (5.02 ± 2.80 ng/g ww) were statistically higher than in other areas and taxonomic groups. The ubiquity of PFPIAs warrants further research on sources and effects of these unique compounds. human blood, fish homogenate, wastewater, surface water, and dust in North America and Hong Kong and suggest that these chemicals are present in low abundance compared to PFCAs and PFSAs.3,4,6,15−19 Like other PFAAs, PFPAs and PFPIAs are surfactants possessing a hydrophobic and lipophobic perfluoroalkyl tail connected to a polar anionic headgroup. Analysis of commercial PFPA and PFPIA formulations show that composition is based on even-numbered perfluorocarbons with varying chain lengths.6,15,17 The naming convention for individual homologues is as follows: Cx PFPA for
1. INTRODUCTION Perfluoroalkyl acids (PFAAs) are anthropogenic organic chemicals utilized in a wide range of commercial and industrial applications for their surface active properties and include perfluoroalkyl carboxylates (PFCAs) and perfluoroalkanesulfonates (PFSAs). The presence of PFCAs and PFSAs is welldocumented, with global measurements in every environmental compartment.1−8 These substances are environmentally persistent and are products of environmental transformation of other labile polyfluoroalkyl substances.9−13 A recent assessment has identified perfluoroalkyl phosphonic acids (PFPAs) and perfluoroalkyl phosphinic acids (PFPIAs) as members of a relatively under-studied class of PFAAs with high persistence and long-range transport potential.14 Environmental data on these chemicals are limited to a few studies on © XXXX American Chemical Society
Received: July 12, 2016 Revised: August 16, 2016 Accepted: August 23, 2016
A
DOI: 10.1021/acs.est.6b03515 Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Article
Environmental Science & Technology
double-crested cormorants (Phalacrocorax auritus), and common bottlenose dolphins (Tursiops truncatus) with the objective of gaining insight into the distribution of these compounds in a diverse array of species. Northern pike, found in freshwater and brackish ecosystems, are generalist ambush predators whose adults feed primarily upon a wide variety of fish.27 Doublecrested cormorants are piscivorous waterbirds that forage flexibly on a wide variety of fish species but in much of the Great Lakes, as sampled here, feed heavily upon alewife (Alosa pseudoharengus) and round goby (Neogobius melanostomus).28 Bottlenose dolphins feed upon crustaceans and squid, but the majority of their diet consists of a wide variety of fish species.29 Plasma is a particularly suitable tissue for monitoring these chemicals, a conclusion made on the basis of the tendency for these substances to bind to blood proteins, the possibility for nonlethal sampling, and the relative ease of sample preparation and extraction for ultrahigh-performance liquid chromatography−tandem mass spectrometry (UHPLC−MS/MS) analysis. The developed method was applied to plasma from piscivorous fish, birds, and mammals from both freshwater and saltwater ecosystems in North America to gain insight as to the presence and distribution of these chemicals in a variety of locations.
F(CF2)xP(O) (OH)2 and x:y PFPIA for (F(CF2)x)(F(CF2)y)P(O)(O)OH in which x and y are typically 4, 6, 8, 10, or 12. Wang et al. recently reviewed usage and production volumes of PFPIA and PFPAs in the United States and Europe.14 In the United States, PFPAs and PFPIAs were used as defoaming components in pesticide formulations, but since 2006, the United States Environmental Protection Agency (U.S. EPA) has restricted their use in this capacity.14 Both PFPAs and PFPIAs had high production volumes in 1998 and 2002 (4.5 to 227 tons per year) in North America20 but are not reported in the 2006 and 2011 U.S. EPA Chemical Data Reporting (CDR) inventory, implying
