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P3—Inter-laboratory comparison update: Perfluorinated contaminants in NIST standard reference materials
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Abstracts / Reproductive Toxicology 33 (2012) 1–29
P3—Inter-laboratory comparison update: Perfluorinated contaminants in NIST standard reference materials
P4—Distribution of PFCs in wildlife in China and toxicology of PFCs
Jessica L. Reiner 1,∗ , Jennifer M. Keller 1 , Craig M. Butt 2 , Scott Mabury 2 , Jeff Small 3 , Derek Muir 3 , Amy Delinsky 4 , Mark Strynar 4 , Rania Farag 5 , Sathi Selliah 5 , William K. Reagen 6 , Michelle Malinsky 6 , Christiaan Kwadijk 7 , Dale Hoover 8 , John W. Washington 9 , Michele M. Schantz 10
Hongxia Zhang ∗ , Jianshe Wang, Jiayin Dai
1
Analytical Chemistry Division, National Institute of Standards and Technology, Charleston, SC, United States 2 University of Toronto, Toronto, ON, Canada 3 Water Science and Technology Directorate, Environment Canada, Burlington, ON, Canada 4 US Environmental Protection Agency, Research Triangle Park, NC, United States 5 Ontario Ministry of the Environment, Toronto, ON, Canada 6 Environmental Laboratory, 3M Company, St. Paul, MN, United States 7 Wageningen IMARES, Ijmuiden, The Netherlands 8 Axys Analytical Services Ltd., Sidney, BC, Canada 9 US Environmental Protection Agency, Athens, GA, United States 10 Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD, United States
Standard Reference Materials (SRMs) are homogeneous, wellcharacterized materials that are used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of Standard Reference Materials (SRMs) that have values assigned for legacy organic pollutants. These SRMs can serve as target materials for method development and measurement for contaminants of emerging concern. Since inter-laboratory comparison studies have shown considerable disagreements when measuring perfluorinated compounds (PFCs), future analytical measurements will benefit from the characterization of PFCs in SRMs. NIST and 11 collaborating laboratories have been measuring PFCs in a variety of SRMs, including human serum (SRMs 1957, 1958), human milk (SRMs 1953, 1954), bovine liver (SRM 1577c), fish tissue (SRMs 1946, 1947), mussel tissue (SRM 2974a, 1974b), sediment (SRMs 1941b, 1944), sludge (SRM 2781), soil (SRM 2586) and dust (SRMs 1648a, 1649b, 2786, 2787, 2585) with the goal of eventually assigning reference or certified concentrations. As part of this informal inter-laboratory comparison study, SRMs 1957 and 1958 have recently been assigned reference values for seven and four PFCs, respectively. Inter-laboratory measurements for other SRMs are ongoing. Preliminary measurements in SRMs show an array of PFCs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Preliminary average PFOS concentrations (along with RSD, and number of labs reporting) are 5.07 ng/g dry mass (RSD = 10%, n = 3) for SRM 1577c; 2.91 ng/g wet mass (RSD = 51%, n = 6) for SRM 1946; 6.94 ng/g wet mass (RSD = 46%, n = 6) for SRM 1947; 2.73 ng/g dry mass (RSD = 40%, n = 2 plus one lab reporting <1.6 ng/g dry mass) for SRM 2974a; below detection (n = 2) for SRM 1974b; 0.75 ng/g dry mass (RSD = 44%, n = 5 plus one lab reporting <0.8 ng/g dry mass) for SRM 1941b, 2.62 ng/g dry mass (RSD = 34%, n = 5 plus one lab reporting <0.5 ng/g dry mass) for SRM 1944; 4.44 ng/g dry mass (RSD = 31%, n = 3) for SRMs 2586; 274 ng/g dry mass (RSD = 31%, n = 3) for SRM 2781; 1843 ng/g dry mass (RSD = N/A, n = 1) for SRM 2583, respectively. PFOS measurements are quite variable among labs, suggesting method improvements are needed prior to assigning reference values in NIST SRMs. These reference materials are needed to provide quality assurance measurements for various laboratories throughout the world and work is ongoing to provide reliable measurements. doi:10.1016/j.reprotox.2011.11.037
Key Laboratory of Animal Ecology and Conservation Biology, Institute of Zoology, Chinese Academy of Sciences, PR China PFCs have garnered intense scientific and regulatory interest due to their extraordinary environmental persistence and bioaccumulation tendencies. Our research interests focus on its distribution, and sources, as well as the toxic effects and mechanism on wildlife and humans. 1. The pattern of PFCs in wildlife species Discharge of municipal wastewater treatment plants (WWTPs) may be an important source of organic contaminants such as PFCs in aquatic environments. PFCs were measured in zooplankton and five fish species collected from Gaobeidian Lake, which receives discharge from a WWTP in Beijing, China. PFOS occurred at the greatest concentrations in five fish species detected. PFDA was the second dominant PFC in fish samples. A positive linear relationship was observed between PFOS concentrations and trophic level (Environ. Pollut., 2008, 156, 1298–1303). We analyzed blood PFC levels in Amur tigers, giant pandas, and red pandas from different captive centers situated in industrialized and nonindustrialized regions of China (Environ. Sci. Technol., 2006, 40, 5647–5652). PFC concentrations were significantly higher in tigers from the industrial areas than those from non-industrialized regions. PFOS was the predominant compound in all samples measured, and the levels of PFOS increased with age in the tigers regardless of the industrial/nonindustrial background (Environ. Sci. Technol., 2008, 42, 7078–7083; Chemosphere, 2008, 73, 1649–1653). These results confirm our hypothesis that captivity in industrialized areas increases PFC levels in endangered species. These data also suggest that PFC accumulation persists and even increase with continued use of PFCs in China. 2. The toxicological effects of PFCs 2.1. Hepatic effects of PFCs We found that acute PFC exposure induced oxidative stress and alteration of mitochondrial function in the livers of female zebrafish. In addition, this exposure led to swollen hepatocytes, vacuolar degeneration, and nuclei pycnosis in the liver in these fish. These results demonstrated that turbulence of fatty acid beta-oxidation and oxidative stress responses were involved in the PFC-induced hepatotoxicity. Furthermore, PFC exposure also altered the transcriptional expression of CYPs, such as CYP1A and CYP3A (Aquatic toxicology, 2008, 88, 183–190; 89, 242–250; Comp. Biochem. Phys., C, 2009, 150, 57–64). To further assess the effects of PFC in fish and identify the mode of action of the observed toxicity, a custom cDNA microarray was applied to hepatic gene expression profile analysis in male and female rare minnows. In addition, two-dimensional electrophoresis coupled with mass spectrometry was used to identify proteins differentially expressed in the livers following PFCs exposure. The results from these toxicogenomic and toxicoproteomic approaches suggested that the mechanism of action of PFCs may involve interfering with intracellular fatty acid transport and oxidative stress pathways (Toxicol. Appl. Pharmacol., 2008, 226, 285–297; J. Proteome Res., 2008, 7, 1729–1739). Since the metabolic network is downstream of both gene expression and protein synthesis, metabonomics technology has shown great promise for understanding toxin-induced endogenous metabolic responses and identifying novel toxicity
Abstracts / Reproductive Toxicology 33 (2012) 1–29
P3—Inter-laboratory comparison update: Perfluorinated contaminants in NIST standard reference materials
P4—Distribution of PFCs in wildlife in China and toxicology of PFCs
Jessica L. Reiner 1,∗ , Jennifer M. Keller 1 , Craig M. Butt 2 , Scott Mabury 2 , Jeff Small 3 , Derek Muir 3 , Amy Delinsky 4 , Mark Strynar 4 , Rania Farag 5 , Sathi Selliah 5 , William K. Reagen 6 , Michelle Malinsky 6 , Christiaan Kwadijk 7 , Dale Hoover 8 , John W. Washington 9 , Michele M. Schantz 10
Hongxia Zhang ∗ , Jianshe Wang, Jiayin Dai
1
Analytical Chemistry Division, National Institute of Standards and Technology, Charleston, SC, United States 2 University of Toronto, Toronto, ON, Canada 3 Water Science and Technology Directorate, Environment Canada, Burlington, ON, Canada 4 US Environmental Protection Agency, Research Triangle Park, NC, United States 5 Ontario Ministry of the Environment, Toronto, ON, Canada 6 Environmental Laboratory, 3M Company, St. Paul, MN, United States 7 Wageningen IMARES, Ijmuiden, The Netherlands 8 Axys Analytical Services Ltd., Sidney, BC, Canada 9 US Environmental Protection Agency, Athens, GA, United States 10 Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD, United States
Standard Reference Materials (SRMs) are homogeneous, wellcharacterized materials that are used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of Standard Reference Materials (SRMs) that have values assigned for legacy organic pollutants. These SRMs can serve as target materials for method development and measurement for contaminants of emerging concern. Since inter-laboratory comparison studies have shown considerable disagreements when measuring perfluorinated compounds (PFCs), future analytical measurements will benefit from the characterization of PFCs in SRMs. NIST and 11 collaborating laboratories have been measuring PFCs in a variety of SRMs, including human serum (SRMs 1957, 1958), human milk (SRMs 1953, 1954), bovine liver (SRM 1577c), fish tissue (SRMs 1946, 1947), mussel tissue (SRM 2974a, 1974b), sediment (SRMs 1941b, 1944), sludge (SRM 2781), soil (SRM 2586) and dust (SRMs 1648a, 1649b, 2786, 2787, 2585) with the goal of eventually assigning reference or certified concentrations. As part of this informal inter-laboratory comparison study, SRMs 1957 and 1958 have recently been assigned reference values for seven and four PFCs, respectively. Inter-laboratory measurements for other SRMs are ongoing. Preliminary measurements in SRMs show an array of PFCs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Preliminary average PFOS concentrations (along with RSD, and number of labs reporting) are 5.07 ng/g dry mass (RSD = 10%, n = 3) for SRM 1577c; 2.91 ng/g wet mass (RSD = 51%, n = 6) for SRM 1946; 6.94 ng/g wet mass (RSD = 46%, n = 6) for SRM 1947; 2.73 ng/g dry mass (RSD = 40%, n = 2 plus one lab reporting <1.6 ng/g dry mass) for SRM 2974a; below detection (n = 2) for SRM 1974b; 0.75 ng/g dry mass (RSD = 44%, n = 5 plus one lab reporting <0.8 ng/g dry mass) for SRM 1941b, 2.62 ng/g dry mass (RSD = 34%, n = 5 plus one lab reporting <0.5 ng/g dry mass) for SRM 1944; 4.44 ng/g dry mass (RSD = 31%, n = 3) for SRMs 2586; 274 ng/g dry mass (RSD = 31%, n = 3) for SRM 2781; 1843 ng/g dry mass (RSD = N/A, n = 1) for SRM 2583, respectively. PFOS measurements are quite variable among labs, suggesting method improvements are needed prior to assigning reference values in NIST SRMs. These reference materials are needed to provide quality assurance measurements for various laboratories throughout the world and work is ongoing to provide reliable measurements. doi:10.1016/j.reprotox.2011.11.037
Key Laboratory of Animal Ecology and Conservation Biology, Institute of Zoology, Chinese Academy of Sciences, PR China PFCs have garnered intense scientific and regulatory interest due to their extraordinary environmental persistence and bioaccumulation tendencies. Our research interests focus on its distribution, and sources, as well as the toxic effects and mechanism on wildlife and humans. 1. The pattern of PFCs in wildlife species Discharge of municipal wastewater treatment plants (WWTPs) may be an important source of organic contaminants such as PFCs in aquatic environments. PFCs were measured in zooplankton and five fish species collected from Gaobeidian Lake, which receives discharge from a WWTP in Beijing, China. PFOS occurred at the greatest concentrations in five fish species detected. PFDA was the second dominant PFC in fish samples. A positive linear relationship was observed between PFOS concentrations and trophic level (Environ. Pollut., 2008, 156, 1298–1303). We analyzed blood PFC levels in Amur tigers, giant pandas, and red pandas from different captive centers situated in industrialized and nonindustrialized regions of China (Environ. Sci. Technol., 2006, 40, 5647–5652). PFC concentrations were significantly higher in tigers from the industrial areas than those from non-industrialized regions. PFOS was the predominant compound in all samples measured, and the levels of PFOS increased with age in the tigers regardless of the industrial/nonindustrial background (Environ. Sci. Technol., 2008, 42, 7078–7083; Chemosphere, 2008, 73, 1649–1653). These results confirm our hypothesis that captivity in industrialized areas increases PFC levels in endangered species. These data also suggest that PFC accumulation persists and even increase with continued use of PFCs in China. 2. The toxicological effects of PFCs 2.1. Hepatic effects of PFCs We found that acute PFC exposure induced oxidative stress and alteration of mitochondrial function in the livers of female zebrafish. In addition, this exposure led to swollen hepatocytes, vacuolar degeneration, and nuclei pycnosis in the liver in these fish. These results demonstrated that turbulence of fatty acid beta-oxidation and oxidative stress responses were involved in the PFC-induced hepatotoxicity. Furthermore, PFC exposure also altered the transcriptional expression of CYPs, such as CYP1A and CYP3A (Aquatic toxicology, 2008, 88, 183–190; 89, 242–250; Comp. Biochem. Phys., C, 2009, 150, 57–64). To further assess the effects of PFC in fish and identify the mode of action of the observed toxicity, a custom cDNA microarray was applied to hepatic gene expression profile analysis in male and female rare minnows. In addition, two-dimensional electrophoresis coupled with mass spectrometry was used to identify proteins differentially expressed in the livers following PFCs exposure. The results from these toxicogenomic and toxicoproteomic approaches suggested that the mechanism of action of PFCs may involve interfering with intracellular fatty acid transport and oxidative stress pathways (Toxicol. Appl. Pharmacol., 2008, 226, 285–297; J. Proteome Res., 2008, 7, 1729–1739). Since the metabolic network is downstream of both gene expression and protein synthesis, metabonomics technology has shown great promise for understanding toxin-induced endogenous metabolic responses and identifying novel toxicity