45 results on '"Strynar M"'
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2. Per- and polyfluoroalkyl substances exposure science: current knowledge, information needs, future directions
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Cheng, B., primary, Alapaty, K., additional, Zartarian, V., additional, Poulakos, A., additional, Strynar, M., additional, and Buckley, T., additional
- Published
- 2021
- Full Text
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3. Characterization of enzymatic or abiotic immobilization of xenobiotics in soil
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Bollag, J.-M., primary, Strynar, M., additional, Ahn, M.-Y., additional, and Dec, J., additional
- Published
- 2002
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4. Impact of perfluorinated chemicals on thyroid hormones, markers of ovarian reserve, and natural fertility
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Crawford, N.M., primary, Strynar, M., additional, and Steiner, A., additional
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- 2015
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5. Perfluorooctanoic Acid Induced Developmental Toxicity in the Mouse is Dependent on Expression of Peroxisome Proliferator Activated Receptor-alpha
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Abbott, B. D., primary, Wolf, C. J., additional, Schmid, J. E., additional, Das, K. P., additional, Zehr, R. D., additional, Helfant, L., additional, Nakayama, S., additional, Lindstrom, A. B., additional, Strynar, M. J., additional, and Lau, C., additional
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- 2007
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6. Gestational PFOA Exposure of Mice is Associated with Altered Mammary Gland Development in Dams and Female Offspring
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White, S. S., primary, Calafat, A. M., additional, Kuklenyik, Z., additional, Villanueva, L., additional, Zehr, R. D., additional, Helfant, L., additional, Strynar, M. J., additional, Lindstrom, A. B., additional, Thibodeaux, J. R., additional, Wood, C., additional, and Fenton, S. E., additional
- Published
- 2006
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7. Emissions of fluorinated compounds from the combustion of carpeting
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Paul Lemieux, Strynar, M., Tabor, D., Wood, J., Cooke, M., Rayfield, B., and Kariher, P.
8. Erratum: "Measurement of Novel, Drinking Water-Associated PFAS in Blood from Adults and Children in Wilmington, North Carolina".
- Author
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Kotlarz N, McCord J, Collier D, Lea CS, Strynar M, Lindstrom AB, Wilkie AA, Islam JY, Matney K, Tarte P, Polera ME, Burdette K, DeWitt J, May K, Smart RC, Knappe DRU, and Hoppin JA
- Published
- 2024
- Full Text
- View/download PDF
9. Measurement of Hydro-EVE and 6:2 FTS in Blood from Wilmington, North Carolina, Residents, 2017-2018.
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Kotlarz N, McCord J, Wiecha N, Weed RA, Cuffney M, Enders JR, Strynar M, Knappe DRU, Reich BJ, and Hoppin JA
- Subjects
- North Carolina, Fluorocarbons
- Published
- 2024
- Full Text
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10. Reanalysis of PFO5DoA Levels in Blood from Wilmington, North Carolina, Residents, 2017-2018.
- Author
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Kotlarz N, McCord J, Wiecha N, Weed RA, Cuffney M, Enders JR, Strynar M, Knappe DRU, Reich BJ, and Hoppin JA
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- North Carolina, Humans, Fluorocarbons blood
- Published
- 2024
- Full Text
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11. Per- and polyfluoroalkyl ether acids in well water and blood serum from private well users residing by a fluorochemical facility near Fayetteville, North Carolina.
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Kotlarz N, Guillette T, Critchley C, Collier D, Lea CS, McCord J, Strynar M, Cuffney M, Hopkins ZR, Knappe DRU, and Hoppin JA
- Subjects
- Humans, Serum, North Carolina, Ethyl Ethers, Ethers, Ether, Fluorocarbons, Fluorocarbon Polymers, Propionates
- Abstract
Background: A fluorochemical facility near Fayetteville, North Carolina, emitted per- and polyfluoroalkyl ether acids (PFEAs), a subgroup of per- and polyfluoroalkyl substances (PFAS), to air., Objective: Analyze PFAS in private wells near the facility and in blood from well users to assess relationships between PFEA levels in water and serum., Methods: In 2019, we recruited private well users into the GenX Exposure Study and collected well water and blood samples. We targeted 26 PFAS (11 PFEAs) in water and 27 PFAS (9 PFEAs) in serum using liquid chromatography-mass spectrometry. We used regression modeling to explore relationships between water and serum PFAS. For the only PFEA detected frequently in water and serum, Nafion byproduct 2, we used generalized estimating equation (GEE) models to assess well water exposure metrics and then adjusted for covariates that may influence Nafion byproduct 2 serum concentrations., Results: We enrolled 153 participants ages 6 and older (median = 56 years) using 84 private wells. Most wells (74%) had ≥6 detectable PFEAs; median ∑PFEAs was 842 ng/L (interquartile range = 197-1760 ng/L). Low molecular weight PFEAs (PMPA, HFPO-DA [GenX], PEPA, PFO2HxA) were frequently detected in well water, had the highest median concentrations, but were not detectable in serum. Nafion byproduct 2 was detected in 73% of wells (median = 14 ng/L) and 56% of serum samples (median = 0.2 ng/mL). Cumulative dose (well concentration × duration at address) was positively associated with Nafion byproduct 2 serum levels and explained the most variability (10%). In the adjusted model, cumulative dose was associated with higher Nafion byproduct 2 serum levels while time outside the home was associated with lower levels., Impact: PFAS are a large class of synthetic, fluorinated chemicals. Fluorochemical facilities are important sources of environmental PFAS contamination globally. The fluorochemical industry is producing derivatives of perfluoroalkyl acids, including per- and polyfluoroalkyl ether acids (PFEAs). PFEAs have been detected in various environmental samples but information on PFEA-exposed populations is limited. While serum biomonitoring is often used for PFAS exposure assessment, serum biomarkers were not good measures of long-term exposure to low molecular weight PFEAs in a private well community. Environmental measurements and other approaches besides serum monitoring will be needed to better characterize PFEA exposure., (© 2023. The Author(s), under exclusive licence to Springer Nature America, Inc.)
- Published
- 2024
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12. Estimation of the Half-Lives of Recently Detected Per- and Polyfluorinated Alkyl Ethers in an Exposed Community.
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Wallis DJ, Kotlarz N, Knappe DRU, Collier DN, Lea CS, Reif D, McCord J, Strynar M, DeWitt JC, and Hoppin JA
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- Humans, Child, Adolescent, Young Adult, Adult, Middle Aged, Aged, Aged, 80 and over, Ethers, Caprylates, Water Pollutants, Chemical analysis, Fluorocarbons analysis, Alkanesulfonic Acids
- Abstract
To estimate half-lives for novel fluoroethers, the GenX Exposure Study obtained two serum measurements for per- and polyfluoroalkyl substances (PFAS) for 44 participants of age 12-86 years from North Carolina, collected 5 and 11 months after fluoroether discharges into the drinking water source were controlled. The estimated half-lives for these compounds were 127 days (95% confidence interval (95% CI) = 86, 243 days) for perfluorotetraoxadecanoic acid (PFO4DA), 296 days for Nafion byproduct 2 (95% CI = 176, 924 days), and 379 days (95% CI = 199, 3870 days) for perfluoro-3,5,7,9,11-pentaoxadodecanoic acid (PFO5DoA). Using these estimates and the literature values, a model was built that predicted PFAS half-lives using structural properties. Three chemical properties predicted 55% of the variance of PFAS half-lives based on 15 PFAS. A model with only molecular weight predicted 69% of the variance. Some properties can predict the half-lives of PFAS, but a deeper understanding is needed. These fluoroethers had biological half-lives longer than published half-lives for PFHxA and PFHpA (30-60 days) but shorter than those for PFOA and PFOS (800-1200 days). These are the first and possibly only estimates of human elimination half-lives of these fluoroethers.
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- 2023
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13. Practical application guide for the discovery of novel PFAS in environmental samples using high resolution mass spectrometry.
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Strynar M, McCord J, Newton S, Washington J, Barzen-Hanson K, Trier X, Liu Y, Dimzon IK, Bugsel B, Zwiener C, and Munoz G
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- Humans, Chromatography, Liquid, Tandem Mass Spectrometry, Fluorocarbons
- Abstract
Background: The intersection of the topics of high-resolution mass spectrometry (HRMS) and per- and polyfluoroalkyl substances (PFAS) bring together two disparate and complex subjects. Recently non-targeted analysis (NTA) for the discovery of novel PFAS in environmental and biological media has been shown to be valuable in multiple applications. Classical targeted analysis for PFAS using LC-MS/MS, though growing in compound coverage, is still unable to inform a holistic understanding of the PFAS burden in most samples. NTA fills at least a portion of this data gap., Objectives: Entrance into the study of novel PFAS discovery requires identification techniques such as HRMS (e.g., QTOF and Orbitrap) instrumentation. This requires practical knowledge of best approaches depending on the purpose of the analyses. The utility of HRMS applications for PFAS discovery is unquestioned and will likely play a significant role in many future environmental and human exposure studies., Methods/results: PFAS have some characteristics that make them standout from most other chemicals present in samples. Through a series of tell-tale PFAS characteristics (e.g., characteristic mass defect range, homologous series and characteristic fragmentation patterns), and case studies different approaches and remaining challenges are demonstrated., Impact Statement: The identification of novel PFAS via non-targeted analysis using high resolution mass spectrometry is an important and difficult endeavor. This synopsis document will hopefully make current and future efforts on this topic easier to perform for novice and experienced alike. The typical time devoted to NTA PFAS investigations (weeks to months or more) may benefit from these practical steps employed., (© 2023. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)
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- 2023
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14. Analytical method interferences for perfluoropentanoic acid (PFPeA) and perfluorobutanoic acid (PFBA) in biological and environmental samples.
- Author
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Bangma J, McCord J, Giffard N, Buckman K, Petali J, Chen C, Amparo D, Turpin B, Morrison G, and Strynar M
- Subjects
- Chromatography, Liquid, Fatty Acids, Tandem Mass Spectrometry, Fluorocarbons analysis
- Abstract
While high-resolution MS (HRMS) can be used for identification and quantification of novel per- and polyfluorinated alkyl substances (PFAS), low-resolution MS/MS is the more commonly used and affordable approach for routine PFAS monitoring. Of note, perfluoropentanoic acid (PFPeA) and perfluorobutanoic acid (PFBA), two of the smaller carboxylic acid containing-PFAS, have only one major MS/MS transition, preventing the use of qualitative transitions for verification on low-resolution instrumentation. Recently our lab has observed widespread chemical interference in the quantitative ion channel for PFPeA (263 → 219) and PFBA (213 → 169) in numerous matrices. PFPeA interference was investigated using HRMS and putatively assigned as a diprotic unsaturated fatty acid (263.1288 Da) in shellfish and a separate interferent (
13 C isotope of 262.1087 Da) in hot cocoa, which had been previously described by the FDA. PFBA interference caused by saturated oxo-fatty acids, previously demonstrated in tissue, was also observed in liquid condensate from a residential air conditioning unit. Therefore, in support of PFAS analysis on low-resolution instrumentation, authors recommend several adjustments to analytical methods including altering liquid chromatography (LC) conditions as well as using matched internal standards to investigate and expressly confirm PFBA and PFPeA detections in both biological and environmental samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Ltd.)- Published
- 2023
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15. A rapid assessment bioaccumulation screening (RABS) study design for emerging per-and polyfluoroalkyl substances in mice exposed to industrially impacted surface water.
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Bangma J, Guillette TC, Strynar M, Lindstrom A, McCord J, Hill D, Lau C, Chernoff N, and Lang JR
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- Animals, Bioaccumulation, Complex Mixtures, Humans, Mammals, Mice, Alkanesulfonic Acids toxicity, Drinking Water, Fluorocarbons analysis, Water Pollutants, Chemical toxicity
- Abstract
The shift away from PFOS and PFOA production in the past 20 years towards shorter chain and replacement PFAS has led to the environmental release of complex mixtures of emerging PFAS for which bioaccumulation potential and toxicology are largely unknown. The rate at which emerging PFAS can be prioritized for research in these complex mixtures is often limited by the lack of available chemical standards. We developed a study design that rapidly assesses which emerging PFAS in an environmentally derived mixture have the potential for mammalian bioaccumulation and thus prioritize these emerging chemicals for standard synthesis and toxicity testing. Surface water was collected at an impacted site downstream of an industrial fluorochemical manufacturing outfall and concentrated 100-fold via weak anion exchange, solid-phase extraction. The concentrated extract contained 13 previously identified emerging PFAS, including hexafluoropropylene oxide-dimer acid (HFPO-DA). BALB/c mice were orally dosed with surface water concentrate once a day for seven days. Twenty-four hours after the last dose, liver, serum, urine, and feces were collected and the emerging PFAS were semi-quantified based on peak area counts. Of the 13 emerging PFAS, Nafion byproduct-2 (Nafion BP2), Hydro-EVE, PFO
4 DA, and PFO5 DoA had the largest increases in percent composition when comparing serum and liver to the dosing solution, suggesting that these PFAS may have the highest bioaccumulation potential. This finding supports other studies that detected bioaccumulation of the same four PFAS in human serum collected from communities with contaminated drinking water. In the future, the Rapid Assessment Bioaccumulation Screening (RABS) study design can be extended to other complex industrial chemical mixtures impacting surface water in order to better inform chemical prioritization for acquisition and in vitro/in vivo toxicity testing of the potential pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Ltd.)- Published
- 2022
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16. Variability of Microcystin-LR Standards Available from Seven Commercial Vendors.
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Hill D, Lang J, McCord J, Strynar M, Rosal C, Schmid J, Le TT, and Chernoff N
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- Humans, Mice, Animals, Trifluoroacetic Acid, Water, Microcystins toxicity, Cyanobacteria Toxins
- Abstract
Microcystins (MCs) are a large group of heptapeptide cyanobacterial toxins commonly produced in harmful algal blooms (HABs) and associated with adverse health effects in wildlife, livestock, pets, and humans. MC chemical standards are extracted from cyanobacteria biomass rather than produced synthetically and are used in water assessment methods and toxicological studies. MC standards are generally supplied in less than 1 mg quantities, and verification of the mass can only be accomplished by analytical chemistry methods using a certified reference of the specific MC for comparison. Analytical quantification of MCs in environmental samples and toxicology studies using accurate doses of test chemicals administered to experimental animals rely on the availability and accuracy of chemical standards. To check the accuracy and purity of available standards, seven individual microcystin-LR (MCLR) standards were purchased from separate commercial vendors and analyzed to determine the actual mass supplied and identify the presence of potential contaminants. To determine the effect of varying toxin mass in toxicological studies, each MCLR standard was administered to CD-1 mice in doses based on mass purchased, by a single 40 µg/kg intraperitoneal injection. The measured mass purchased varied from the vendor label mass by more than 35% for two of the seven MCLR standards. Contaminants, including trifluoroacetic acid (TFA), were identified in four of the seven samples. Comparative in vivo hepatotoxicity between vendor samples closely reflected the actual amount of MCLR present in each standard and demonstrated the toxicological impact of varying cyanotoxin mass.
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- 2022
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17. Per-and polyfluoroalkyl substances (PFAS) and persistent chemical mixtures in dust from U.S. colleges.
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Schildroth S, Rodgers KM, Strynar M, McCord J, Poma G, Covaci A, and Dodson RE
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- Dust analysis, Halogenated Diphenyl Ethers analysis, Humans, Environmental Pollutants analysis, Fluorocarbons, Hydrocarbons, Chlorinated analysis, Pesticides, Polychlorinated Biphenyls analysis
- Abstract
Indoor spaces contain several classes of persistent organic chemicals, including per- and polyfluoroalkyl substances (PFAS), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). However, concentrations of PFAS and persistent chemical mixtures and their associations with building characteristics on college campuses are understudied. We collected dust from 43 nonresidential spaces on four U.S. college campuses in 2016 and evaluated associations of room characteristics (carpeting, upholstered furniture, and years since last furnished) with dust concentrations of PFAS, PBDEs, PCBs, and OCPs. Nine PFAS, twelve PBDEs, two PCBs, and four OCPs were each detected in at least 75% of the spaces, including several chemicals (e.g., DDT) that have been banned for decades. Concentrations were correlated within and, in some cases, between chemical classes. Wall-to-wall carpeting (compared to rooms without wall-to-wall carpeting) was associated with higher concentrations of six individual PFAS and a mixture of PFAS, and the number of pieces of upholstered furniture was associated with increased concentrations of a mixture of PBDEs. These findings indicate that carpeting and furniture are current sources of PFAS and PBDEs, respectively. Building and finish materials should be carefully selected to avoid exposure to persistent chemicals., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)
- Published
- 2022
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18. Desulfonation and defluorination of 6:2 fluorotelomer sulfonic acid (6:2 FTSA) by Rhodococcus jostii RHA1: Carbon and sulfur sources, enzymes, and pathways.
- Author
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Yang SH, Shi Y, Strynar M, and Chu KH
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- Carbon, Fluorocarbons, Sulfur, Rhodococcus genetics, Sulfonic Acids
- Abstract
6:2 fluorotelomer sulfonic acid (6:2 FTSA) is one per- and poly-fluoroalkyl substances commonly detected in the environment. While biotransformation of 6:2 FTSA has been reported, factors affecting desulfonation and defluorination of 6:2 FTSA remain poorly understood. This study elucidated the effects of carbon and sulfur sources on the gene expression of Rhodococcus jostii RHA1 which is responsible for the 6:2 FTSA biotransformation. While alkane monooxygenase and cytochrome P450 were highly expressed in ethanol-, 1-butanol-, and n-octane-grown RHA1 in sulfur-rich medium, these cultures only defluorinated 6:2 fluorotelomer alcohol but not 6:2 FTSA, suggesting that the sulfonate group in 6:2 FTSA hinders enzymatic defluorination. In sulfur-free growth media, alkanesulfonate monooxygenase was linked to desulfonation of 6:2 FTSA; while alkane monooxygenase, haloacid dehalogenase, and cytochrome P450 were linked to defluorination of 6:2 FTSA. The desulfonation and defluorination ability of these enzymes toward 6:2 FTSA were validated through heterologous gene expression and in vitro assays. Four degradation metabolites were confirmed and one was identified as a tentative metabolite. The results provide a new understanding of 6:2 FTSA biotransformation by RHA1. The genes encoding these desulfonating- and defluorinating-enzymes are potential markers to be used to assess 6:2 FTSA biotransformation in the environment., (Copyright © 2021 Elsevier B.V. All rights reserved.)
- Published
- 2022
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19. Erratum: "Measurement of Novel, Drinking Water-Associated PFAS in Blood from Adults and Children in Wilmington, North Carolina".
- Author
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Kotlarz N, McCord J, Collier D, Lea CS, Strynar M, Lindstrom AB, Wilkie AA, Islam JY, Matney K, Tarte P, Polera ME, Burdette K, DeWitt J, May K, Smart RC, Knappe DRU, and Hoppin JA
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- 2020
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20. Examining NTA performance and potential using fortified and reference house dust as part of EPA's Non-Targeted Analysis Collaborative Trial (ENTACT).
- Author
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Newton SR, Sobus JR, Ulrich EM, Singh RR, Chao A, McCord J, Laughlin-Toth S, and Strynar M
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Non-targeted analysis (NTA) methods are being increasingly used to aid in the identification of unknown compounds in the environment, a problem that has challenged environmental chemists for decades. Despite its increased use, quality assurance practices for NTA have not been well established. Furthermore, capabilities and limitations of certain NTA methods have not been thoroughly evaluated. Standard reference material dust (SRM 2585) was used here to evaluate the ability of NTA to identify previously reported compounds, as well as a suite of 365 chemicals that were spiked at various stages of the analytical procedure. Analysis of the unaltered SRM 2585 extracts revealed that several previously reported compounds can be identified by NTA, and that correct identification was dependent on concentration. A manual inspection of unknown features in SRM 2585 revealed the presence of two chlorinated and fluorinated compounds in high abundance, likely precursors to perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS). A retrospective analysis of data from the American Healthy Homes Survey revealed that these compounds were present in 42% of sampled homes. Spiking the dust at various stages of sample preparation revealed losses from extraction, cleanup, and instrumental analysis; the log K
ow for individual compounds influenced the overall recovery levels but no pattern could be discerned from the various degrees of interference that the matrix had on the ionization efficiency of the spiked chemicals. Analysis of the matrix-free chemical mixture at low, medium, and high concentrations led to more correct identifications than analysis at one, very high concentration. Varying the spiked amount and identifying reported compounds at known concentrations allowed an estimation of the lower limits of identification (LOIs) for NTA, analogous to limits of detection in targeted analysis. The LOIs were much lower than levels in dust that would be likely to cause bioactivity in humans, indicating that NTA is useful for identifying and monitoring compounds that may be of toxicological concern. Graphical abstract.- Published
- 2020
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21. Measurement of Novel, Drinking Water-Associated PFAS in Blood from Adults and Children in Wilmington, North Carolina.
- Author
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Kotlarz N, McCord J, Collier D, Lea CS, Strynar M, Lindstrom AB, Wilkie AA, Islam JY, Matney K, Tarte P, Polera ME, Burdette K, DeWitt J, May K, Smart RC, Knappe DRU, and Hoppin JA
- Subjects
- Adult, Alkanesulfonic Acids, Caprylates, Child, Drinking Water, Female, Fluorocarbons analysis, Humans, Male, North Carolina, Nutrition Surveys, Rivers, Environmental Exposure statistics & numerical data, Fluorocarbons blood, Water Pollutants, Chemical analysis
- Abstract
Background: From 1980 to 2017, a fluorochemical manufacturing facility discharged wastewater containing poorly understood per- and polyfluoroalkyl substances (PFAS) to the Cape Fear River, the primary drinking water source for Wilmington, North Carolina, residents. Those PFAS included several fluoroethers including HFPO-DA also known as GenX. Little is known about the bioaccumulation potential of these fluoroethers., Objective: We determined levels of fluoroethers and legacy PFAS in serum samples from Wilmington residents., Methods: In November 2017 and May 2018, we enrolled 344 Wilmington residents ≥ 6 years of age into the GenX Exposure Study and collected blood samples. Repeated blood samples were collected from 44 participants 6 months after enrollment. We analyzed serum for 10 fluoroethers and 10 legacy PFAS using liquid chromatography-high-resolution mass spectrometry., Results: Participants' ages ranged from 6 to 86 y, and they lived in the lower Cape Fear Region for 20 y on average (standard deviation: 16 y). Six fluoroethers were detected in serum; Nafion by-product 2, PFO4DA, and PFO5DoA were detected in > 85 % of participants. PFO3OA and NVHOS were infrequently detected. Hydro-EVE was present in a subset of samples, but we could not quantify it. GenX was not detected above our analytical method reporting limit ( 2 ng / mL ). In participants with repeated samples, the median decrease in fluoroether levels ranged from 28% for PFO5DoA to 65% for PFO4DA in 6 months due to wastewater discharge control. Four legacy PFAS (PFHxS, PFOA, PFOS, PFNA) were detected in most ( ≥ 97 % ) participants; these levels were higher than U.S. national levels for the 2015-2016 National Health and Nutrition Examination Survey. The sum concentration of fluoroethers contributed 24% to participants' total serum PFAS (median: 25.3 ng / mL )., Conclusion: Poorly understood fluoroethers released into the Cape Fear River by a fluorochemical manufacturing facility were detected in blood samples from Wilmington, North Carolina, residents. Health implications of exposure to these novel PFAS have not been well characterized. https://doi.org/10.1289/EHP6837.
- Published
- 2020
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22. Evaluation of Developmental Toxicity, Developmental Neurotoxicity, and Tissue Dose in Zebrafish Exposed to GenX and Other PFAS.
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Gaballah S, Swank A, Sobus JR, Howey XM, Schmid J, Catron T, McCord J, Hines E, Strynar M, and Tal T
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- Animals, Dose-Response Relationship, Drug, Tissue Distribution, Fluorocarbons toxicity, Neurotoxins toxicity, Propionates toxicity, Water Pollutants, Chemical toxicity, Zebrafish growth & development
- Abstract
Background: Per- and polyfluoroalkyl substances (PFAS) are a diverse class of industrial chemicals with widespread environmental occurrence. Exposure to long-chain PFAS is associated with developmental toxicity, prompting their replacement with short-chain and fluoroether compounds. There is growing public concern over the safety of replacement PFAS., Objective: We aimed to group PFAS based on shared toxicity phenotypes., Methods: Zebrafish were developmentally exposed to 4,8-dioxa-3H-perfluorononanoate (ADONA), perfluoro-2-propoxypropanoic acid (GenX Free Acid), perfluoro-3,6-dioxa-4-methyl-7-octene-1-sulfonic acid (PFESA1), perfluorohexanesulfonic acid (PFHxS), perfluorohexanoic acid (PFHxA), perfluoro- n -octanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), or 0.4% dimethyl sulfoxide (DMSO) daily from 0-5 d post fertilization (dpf). At 6 dpf, developmental toxicity and developmental neurotoxicity assays were performed, and targeted analytical chemistry was used to measure media and tissue doses. To test whether aliphatic sulfonic acid PFAS cause the same toxicity phenotypes, perfluorobutanesulfonic acid (PFBS; 4-carbon), perfluoropentanesulfonic acid (PFPeS; 5-carbon), PFHxS (6-carbon), perfluoroheptanesulfonic acid (PFHpS; 7-carbon), and PFOS (8-carbon) were evaluated., Results: PFHxS or PFOS exposure caused failed swim bladder inflation, abnormal ventroflexion of the tail, and hyperactivity at nonteratogenic concentrations. Exposure to PFHxA resulted in a unique hyperactivity signature. ADONA, PFESA1, or PFOA exposure resulted in detectable levels of parent compound in larval tissue but yielded negative toxicity results. GenX was unstable in DMSO, but stable and negative for toxicity when diluted in deionized water. Exposure to PFPeS, PFHxS, PFHpS, or PFOS resulted in a shared toxicity phenotype characterized by body axis and swim bladder defects and hyperactivity., Conclusions: All emerging fluoroether PFAS tested were negative for evaluated outcomes. Two unique toxicity signatures were identified arising from structurally dissimilar PFAS. Among sulfonic acid aliphatic PFAS, chemical potencies were correlated with increasing carbon chain length for developmental neurotoxicity, but not developmental toxicity. This study identified relationships between chemical structures and in vivo phenotypes that may arise from shared mechanisms of PFAS toxicity. These data suggest that developmental neurotoxicity is an important end point to consider for this class of widely occurring environmental chemicals. https://doi.org/10.1289/EHP5843.
- Published
- 2020
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23. Elevated levels of per- and polyfluoroalkyl substances in Cape Fear River Striped Bass (Morone saxatilis) are associated with biomarkers of altered immune and liver function.
- Author
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Guillette TC, McCord J, Guillette M, Polera ME, Rachels KT, Morgeson C, Kotlarz N, Knappe DRU, Reading BJ, Strynar M, and Belcher SM
- Subjects
- Animals, Liver, Rivers, Bass, Biomarkers, Fluorocarbons toxicity, Water Pollutants, Chemical toxicity
- Abstract
Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals of concern that persist in the environment. Environmental monitoring revealed high concentrations of hexafluoropropylene oxide dimer acid (HFPO-DA) and other novel PFAS in the lower Cape Fear River; however, there is limited information on PFAS exposures and effects of this contamination on aquatic biota. Serum concentrations of 23 PFAS in Striped Bass (Morone saxatilis) from the Cape Fear River (n = 58) and a reference population from an aquaculture laboratory on the Pamlico/Tar watershed (n = 29) were quantified using liquid chromatography and high-resolution mass spectrometry, and correlations between PFAS concentrations and health-related serum biomarkers were evaluated. Perfluorooctane sulfonate, the predominant PFAS in Cape Fear River Striped Bass serum, was detectable in every sample with serum concentrations reaching 977 ng/mL. Perfluorononanoic and perfluorodecanoic acid were also detected in all samples, with perfluorohexanesulfonic acid present in >98% of the samples. HFPO-DA (range <0.24-5.85 ng/mL) and Nafion byproduct 2 (range <0.2-1.03 ng/mL) were detected in 48% and 78% of samples, respectively. The mean total PFAS concentration found in domestic Striped Bass raised in well-water under controlled aquaculture conditions was 40 times lower, with HPFO-DA detected in 10% of the samples, and Nafion byproduct 2 was not detected. The elevated PFAS concentrations found in the Cape Fear River Striped Bass were associated with biomarkers of alterations in the liver and immune system., Competing Interests: Declaration of Competing Interest We declare that we have no conflict of interest., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)
- Published
- 2020
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24. Suspect screening and prioritization of chemicals of concern (COCs) in a forest-water reuse system watershed.
- Author
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Hedgespeth ML, Gibson N, McCord J, Strynar M, Shea D, and Nichols EG
- Abstract
Much research has assessed organic chemicals of concern (COCs) in municipal wastewater and receiving waters, but few studies have examined COCs in land treatment systems. Many prior studies have implemented targeted methods that quantify a relatively small fraction of COCs present in wastewater and receiving waters. This study used suspect screening to assess chemical features in ground- and surface waters from a watershed where secondary-treated wastewater is irrigated onto 900 ha of temperate forest, offering a more holistic view of chemicals that contribute to the exposome. Chemical features were prioritized by abundance and ToxPi scoring across seasonal sampling events to determine if the forest-water reuse system contributed to the chemical exposome of ground- and surface waters. The number of chemical features detected in wastewater was usually higher than on- and off-site ground- and surface waters; in wastewater, chemical features trended with precipitation in which greater numbers of features were detected in months with low precipitation. The number of chemical features detected in off- and on-site waters was similar. The lower overlap between chemical features found in wastewater and downstream surface waters, along with the similar numbers of features being detected in upstream and downstream surface waters, suggests that though wastewater may be a source of chemicals to ground and surface waters on-site, dissipation of wastewater-derived features (in number and peak area abundance) likely occurs with limited off-site surface water export by the forested land treatment system. Further, the numbers of features detected on site and the overlap between wastewater and surface waters did not increase during periods of low rainfall, counter to our initial expectations. The chemical features tentatively identified in this watershed appear common to features identified in other studies, warranting further examination on the potential for resulting impacts of these on humans and the environment., (Copyright © 2019 Elsevier B.V. All rights reserved.)
- Published
- 2019
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25. Triclosan-Selected Host-Associated Microbiota Perform Xenobiotic Biotransformations in Larval Zebrafish.
- Author
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Weitekamp CA, Phelps D, Swank A, McCord J, Sobus JR, Catron T, Keely S, Brinkman N, Zurlinden T, Wheaton E, Strynar M, McQueen C, Wood CE, and Tal T
- Abstract
Microbiota regulate important physiologic processes during early host development. They also biotransform xenobiotics and serve as key intermediaries for chemical exposure. Antimicrobial agents in the environment may disrupt these complex interactions and alter key metabolic functions provided by host-associated microbiota. To examine the role of microbiota in xenobiotic metabolism, we exposed zebrafish larvae to the antimicrobial agent triclosan. Conventionally colonized (CC), microbe-free axenic (AX), or axenic colonized on day 1 (AC1) zebrafish were exposed to 0.16-0.30 µM triclosan or vehicle on days 1, 6, 7, 8, and 9 days post fertilization (dpf). After 6 and 10 dpf, host-associated microbial community structure and putative function were assessed by 16S rRNA gene sequencing. At 10 dpf, triclosan exposure selected for bacterial taxa, including Rheinheimera. Triclosan-selected microbes were predicted to be enriched in pathways related to mechanisms of antibiotic resistance, sulfonation, oxidative stress, and drug metabolism. Furthermore, at 10 dpf, colonized zebrafish contained 2.5-3 times more triclosan relative to AX larvae. Nontargeted chemical analysis revealed that, relative to AX larvae, both cohorts of colonized larvae showed elevations in 23 chemical features, including parent triclosan and putative triclosan sulfate. Taken together, these data suggest that triclosan exposure selects for microbes that harbor the capacity to biotransform triclosan into chemical metabolites with unknown toxicity profiles. More broadly, these data support the concept that microbiota modify the toxicokinetics of xenobiotic exposure., (Published by Oxford University Press on behalf of the Society of Toxicology 2019. This work is written by US Government employees and is in the public domain in the US.)
- Published
- 2019
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26. The Next Generation Blueprint of Computational Toxicology at the U.S. Environmental Protection Agency.
- Author
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Thomas RS, Bahadori T, Buckley TJ, Cowden J, Deisenroth C, Dionisio KL, Frithsen JB, Grulke CM, Gwinn MR, Harrill JA, Higuchi M, Houck KA, Hughes MF, Hunter ES, Isaacs KK, Judson RS, Knudsen TB, Lambert JC, Linnenbrink M, Martin TM, Newton SR, Padilla S, Patlewicz G, Paul-Friedman K, Phillips KA, Richard AM, Sams R, Shafer TJ, Setzer RW, Shah I, Simmons JE, Simmons SO, Singh A, Sobus JR, Strynar M, Swank A, Tornero-Valez R, Ulrich EM, Villeneuve DL, Wambaugh JF, Wetmore BA, and Williams AJ
- Subjects
- Decision Making, Humans, Information Technology, Risk Assessment, Toxicokinetics, United States, United States Environmental Protection Agency, Computational Biology methods, High-Throughput Screening Assays methods, Toxicology methods
- Abstract
The U.S. Environmental Protection Agency (EPA) is faced with the challenge of efficiently and credibly evaluating chemical safety often with limited or no available toxicity data. The expanding number of chemicals found in commerce and the environment, coupled with time and resource requirements for traditional toxicity testing and exposure characterization, continue to underscore the need for new approaches. In 2005, EPA charted a new course to address this challenge by embracing computational toxicology (CompTox) and investing in the technologies and capabilities to push the field forward. The return on this investment has been demonstrated through results and applications across a range of human and environmental health problems, as well as initial application to regulatory decision-making within programs such as the EPA's Endocrine Disruptor Screening Program. The CompTox initiative at EPA is more than a decade old. This manuscript presents a blueprint to guide the strategic and operational direction over the next 5 years. The primary goal is to obtain broader acceptance of the CompTox approaches for application to higher tier regulatory decisions, such as chemical assessments. To achieve this goal, the blueprint expands and refines the use of high-throughput and computational modeling approaches to transform the components in chemical risk assessment, while systematically addressing key challenges that have hindered progress. In addition, the blueprint outlines additional investments in cross-cutting efforts to characterize uncertainty and variability, develop software and information technology tools, provide outreach and training, and establish scientific confidence for application to different public health and environmental regulatory decisions., (Published by Oxford University Press on behalf of the Society of Toxicology 2019.)
- Published
- 2019
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27. Microbiota alter metabolism and mediate neurodevelopmental toxicity of 17β-estradiol.
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Catron TR, Swank A, Wehmas LC, Phelps D, Keely SP, Brinkman NE, McCord J, Singh R, Sobus J, Wood CE, Strynar M, Wheaton E, and Tal T
- Subjects
- Animals, Embryonic Development drug effects, Estradiol metabolism, Estrogens metabolism, Estrogens pharmacology, Larva drug effects, Larva metabolism, Locomotion drug effects, Microbiota drug effects, Neurogenesis drug effects, RNA, Ribosomal, 16S genetics, Zebrafish metabolism, Estradiol pharmacology, Germ-Free Life drug effects, Microbiota genetics, Zebrafish embryology, Zebrafish microbiology
- Abstract
Estrogenic chemicals are widespread environmental contaminants associated with diverse health and ecological effects. During early vertebrate development, estrogen receptor signaling is critical for many different physiologic responses, including nervous system function. Recently, host-associated microbiota have been shown to influence neurodevelopment. Here, we hypothesized that microbiota may biotransform exogenous 17-βestradiol (E2) and modify E2 effects on swimming behavior. Colonized zebrafish were continuously exposed to non-teratogenic E2 concentrations from 1 to 10 days post-fertilization (dpf). Changes in microbial composition and predicted metagenomic function were evaluated. Locomotor activity was assessed in colonized and axenic (microbe-free) zebrafish exposed to E2 using a standard light/dark behavioral assay. Zebrafish tissue was collected for chemistry analyses. While E2 exposure did not alter microbial composition or putative function, colonized E2-exposed larvae showed reduced locomotor activity in the light, in contrast to axenic E2-exposed larvae, which exhibited normal behavior. Measured E2 concentrations were significantly higher in axenic relative to colonized zebrafish. Integrated peak area for putative sulfonated and glucuronidated E2 metabolites showed a similar trend. These data demonstrate that E2 locomotor effects in the light phase are dependent on the presence of microbiota and suggest that microbiota influence chemical E2 toxicokinetics. More broadly, this work supports the concept that microbial colonization status may influence chemical toxicity.
- Published
- 2019
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28. Identification of Per- and Polyfluoroalkyl Substances in the Cape Fear River by High Resolution Mass Spectrometry and Nontargeted Screening.
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McCord J and Strynar M
- Subjects
- Chromatography, Liquid, Environmental Monitoring, North Carolina, Rivers, Tandem Mass Spectrometry, Alkanesulfonic Acids, Fluorocarbons, Water Pollutants, Chemical
- Abstract
Ongoing chemical development in response to regulation of historical perfluorinated compounds, (i.e., perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS)) has resulted in a proliferation of novel per- and polyfluorinated species. Screening and monitoring for these emerging chemicals benefit from a nontargeted approach due to a lack of necessary standards and a paucity of information about the replacement chemistries. In this paper, we apply nontargeted screening to the Cape Fear River of North Carolina, a fluorochemically impacted watershed. The continued presence of perfluorinated ether acids was confirmed, with a total of 37 unique chemical formulas comprising 58 isomers detected. Structural determination was carried out by LC-MS/MS to determine isomeric structures where possible. Novel structures determined included perfluorinated ether acid species containing two acidic sites, polyfluorinated ether acids containing a single hydrogenation, and previously unreported perfluorinated ether acids. Compounds identified by an initial nontargeted screen were monitored over repeated sampling to track long-term reductions in PFAS content during emission source control. Hierarchical clustering of the time course data was used to associate groups of chemicals based on their trends over time. Six clusters were identified and showed some similarity in chemical class; they are believed to represent the byproducts of different fluorochemical production lines.
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- 2019
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29. Identifying Per- and Polyfluorinated Chemical Species with a Combined Targeted and Non-Targeted-Screening High-Resolution Mass Spectrometry Workflow.
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McCord J and Strynar M
- Subjects
- Environmental Monitoring methods, Fluorocarbons chemistry, Humans, Solid Phase Extraction methods, Workflow, Fluorocarbons analysis, Mass Spectrometry methods, Water Pollutants, Chemical analysis
- Abstract
Historical and emerging per- and polyfluoroalkyl substances (PFASs) have garnered significant interest from the public and government agencies from the local to federal levels. The continuing evolution of PFAS chemistries presents a challenge to the environmental monitoring, where ongoing development of targeted methods necessarily lags the discovery of new chemical compounds. There is a need, therefore, to have forward-looking methodologies that can detect emerging and unexpected compounds, monitor these species over time, and resolve details of their chemical structure to enable future work in human health. To this end, non-targeted analysis by high-resolution mass spectrometry offers a broad base detection approach that can be combined with almost any sample preparation scheme and provides significant capabilities for compound identification after detection. Herein, we describe a solid-phase extraction (SPE) based sample concentration method tuned for shorter chain and more hydrophilic PFAS chemistries, such as per fluorinated ether acids and sulfonates, and describe analysis of samples prepared in this fashion in both targeted and non-targeted modes. Targeted methods provide superior quantification when reference standards are available but are intrinsically limited to expected compounds when performing analysis. In contrast, a non-targeted approach can identify the presence of unexpected compounds and provide some information about their chemical structure. Information about chemical features can be used to correlate compounds across sample locations and track abundance and occurrence over time.
- Published
- 2019
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30. A Chemical Category-Based Prioritization Approach for Selecting 75 Per- and Polyfluoroalkyl Substances (PFAS) for Tiered Toxicity and Toxicokinetic Testing.
- Author
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Patlewicz G, Richard AM, Williams AJ, Grulke CM, Sams R, Lambert J, Noyes PD, DeVito MJ, Hines RN, Strynar M, Guiseppi-Elie A, and Thomas RS
- Subjects
- Hazardous Substances chemistry, Hazardous Substances toxicity, High-Throughput Screening Assays, Molecular Structure, United States, United States Environmental Protection Agency, Fluorocarbons chemistry, Fluorocarbons toxicity, Toxicokinetics
- Abstract
Per- and polyfluoroalkyl substances (PFASs) are a group of fluorinated substances of interest to researchers, regulators, and the public due to their widespread presence in the environment. A few PFASs have comparatively extensive amounts of human epidemiological, exposure, and experimental animal toxicity data (e.g., perfluorooctanoic acid), whereas little toxicity and exposure information exists for much of the broader set of PFASs. Given that traditional approaches to generate toxicity information are resource intensive, new approach methods, including in vitro high-throughput toxicity (HTT) testing, are being employed to inform PFAS hazard characterization and further ( in vivo ) testing. The U.S. Environmental Protection Agency (EPA) and the National Toxicology Program (NTP) are collaborating to develop a risk-based approach for conducting PFAS toxicity testing to facilitate PFAS human health assessments. This article describes the construction of a PFAS screening library and the process by which a targeted subset of 75 PFASs were selected. Multiple factors were considered, including interest to the U.S. EPA, compounds within targeted categories, structural diversity, exposure considerations, procurability and testability, and availability of existing toxicity data. Generating targeted HTT data for PFASs represents a new frontier for informing priority setting. https://doi.org/10.1289/EHP4555.
- Published
- 2019
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31. mRNA transfection retrofits cell-based assays with xenobiotic metabolism.
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DeGroot DE, Swank A, Thomas RS, Strynar M, Lee MY, Carmichael PL, and Simmons SO
- Subjects
- Aflatoxin B1 metabolism, Cytochrome P-450 Enzyme System genetics, Dose-Response Relationship, Drug, HEK293 Cells, Humans, Liver enzymology, Quinazolines metabolism, Transfection, Xenobiotics administration & dosage, Cytochrome P-450 Enzyme System metabolism, High-Throughput Screening Assays methods, RNA, Messenger metabolism, Xenobiotics metabolism
- Abstract
The US EPA's ToxCast program is designed to assess chemical perturbations of molecular and cellular endpoints using a variety of high-throughput screening (HTS) assays. However, existing HTS assays have limited or no xenobiotic metabolism which could lead to false positive (chemical is detoxified in vivo) as well as false negative results (chemical is bioactivated in vivo) and thus potential mischaracterization of chemical hazard. To address this challenge, the ten most prevalent human liver cytochrome P450 (CYP) enzymes were introduced into a human cell line (HEK293T) with low endogenous metabolic capacity. The CYP enzymes were introduced via transfection of modified mRNAs as either singlets or as a mixture in relative proportions as expressed in human liver. Initial experiments using luminogenic substrates demonstrate that CYP enzyme activities are significantly increased when co-transfected with an mRNA encoding a CYP accessory protein, P450 oxidoreductase (POR). Transfected HEK293T cells demonstrate the ability to produce predicted metabolites following treatment with well-studied CYP substrates for at least 18 h post-treatment. As a demonstration of how this method can be used to retrofit existing HTS assays, a proof-of-concept screen for cytotoxicity in HEK293T cells was conducted using 56 test compounds. The results demonstrate that the xenobiotic metabolism conferred by transfection of CYP-encoding mRNAs shifts the dose-response relationship for some of the tested chemicals such as aflatoxin B1 (bioactivation) and fenazaquin (detoxification). Overall, transfection of CYP-encoding mRNAs is an effective and portable solution for retrofitting existing cell-based HTS assays with metabolic competence., (Published by Elsevier Inc.)
- Published
- 2018
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32. pH dependent octanol-water partitioning coefficients of microcystin congeners.
- Author
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McCord J, Lang JR, Hill D, Strynar M, and Chernoff N
- Subjects
- Hydrogen-Ion Concentration, Molecular Structure, Water Pollutants, Chemical chemistry, Alcohol Oxidoreductases chemistry, Microcystins chemistry, Water chemistry
- Abstract
Hazardous algal blooms can generate toxic compounds with significant health impacts for exposed communities. The ubiquitous class of algal toxins known as microcystins exhibits significant heterogeneity in its peptide structure, which has been minimally studied, given the significant impact this has on hydrophobicity, acid/base character and related environmental fate and health effects. Octanol-water partition coefficients for the microcystin congeners MCLR, MCRR, MCLY, MCLF, and MCLA were calculated over an environmentally and physiologically relevant pH range. Microcystin-LR log(K
ow ) partition coefficient values were found to be consistent with previously established literature values, 1.67 to -1.41 between pH 1 and 8. Microcystin RR was found to be pH insensitive with a log(Kow ) of -0.7. The remaining congeners exhibit similar pH dependence as MCLR, with systematic increases in hydrophobicity driven by the introduction of more hydrophobic residues to their variable amino acid region. The variation in pH dependent hydrophobicity suggests increased propensity for bioaccumulation and alternate environmental fates for differing microcystin forms, requiring further investigation.- Published
- 2018
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33. Validation of quantitative measurements and semi-quantitative estimates of emerging perfluoroethercarboxylic acids (PFECAs) and hexfluoroprolyene oxide acids (HFPOAs).
- Author
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McCord J, Newton S, and Strynar M
- Subjects
- Chromatography, High Pressure Liquid, Drinking Water analysis, Environmental Monitoring, Fluorocarbons isolation & purification, Rivers chemistry, Solid Phase Extraction, Water Pollutants, Chemical isolation & purification, Fluorocarbons analysis, Tandem Mass Spectrometry, Water Pollutants, Chemical analysis
- Abstract
Legacy perfluorinated compounds exhibit significant environmental persistence and bioaccumulation potential, which has spawned an ongoing effort to introduce replacement compounds with reduced toxicological risk profiles. Many of these emerging chemical species lack validated quantitative methods, and, frequently, appropriate analytical standards for accurate monitoring and identification. To fill this knowledge gap, a general method for the quantitative determination of perfluoroether carboxylic acids (PFECAs) by LC-MS/MS was single-lab validated on spike-recovery samples in surface, drinking, and wastewater for a variety of perfluorinated ether standards. Relative error measurements for spike-recovery samples in each matrix ranged from 0.36% to 25.9%, with an average error of 10% overall. Coefficient of variation (CV) for each compound ranged from 10 to 28% with an average of 17%. The quantitative methodology was applied during repeated weekly monitoring of the Cape Fear River during remediation of PFECA hexafluoropropyloxide dimer-acid (HFPO-DA), known by the brand name "GenX." Semi-quantitative concentration estimates for emerging PFECA compounds lacking analytical standards was also carried out using surrogate calibration curves and mass labeled HFPO-DA as an internal standard. Estimates of the emerging compounds were possible using matched standards, but application of the estimation methodology to compounds with known concentration revealed that such estimates may possess up to an order of magnitude, or more, in uncertainty due to the difficulty of matching with an appropriate standard. Nevertheless, the estimation biases are primarily systematic (extraction efficiency and instrument response) rather than stochastic, enabling the collection of time-course data; both HFPO-DA and the emerging compounds were reduced in surface water and drinking water concentration of several orders of magnitude after removal of the source waste stream., (Published by Elsevier B.V.)
- Published
- 2018
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34. Comparison of emerging contaminants in receiving waters downstream of a conventional wastewater treatment plant and a forest-water reuse system.
- Author
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McEachran AD, Hedgespeth ML, Newton SR, McMahen R, Strynar M, Shea D, and Nichols EG
- Subjects
- Agricultural Irrigation, North Carolina, Environmental Monitoring, Forestry methods, Waste Disposal, Fluid methods, Wastewater analysis, Water Pollutants, Chemical analysis
- Abstract
Forest-water reuse (FWR) systems treat municipal, industrial, and agricultural wastewaters via land application to forest soils. Previous studies have shown that both large-scale conventional wastewater treatment plants (WWTPs) and FWR systems do not completely remove many contaminants of emerging concern (CECs) before release of treated wastewater. To better characterize CECs and potential for increased implementation of FWR systems, FWR systems need to be directly compared to conventional WWTPs. In this study, both a quantitative, targeted analysis and a nontargeted analysis were utilized to better understand how CECs release to waterways from an FWR system compared to a conventional treatment system. Quantitatively, greater concentrations and total mass load of CECs was exhibited downstream of the conventional WWTP compared to the FWR. Average summed concentrations of 33 targeted CECs downstream of the conventional system were ~ 1000 ng/L and downstream of the FWR were ~ 30 ng/L. From a nontargeted chemical standpoint, more tentatively identified chemicals were present, and at a greater relative abundance, downstream of the conventional system as well. Frequently occurring contaminants included phthalates, pharmaceuticals, and industrial chemicals. These data indicate that FWR systems represent a sustainable wastewater treatment alternative and that emerging contaminant release to waterways was lower at a FWR system than a conventional WWTP.
- Published
- 2018
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35. Hydroxy-fipronil is a new urinary biomarker of exposure to fipronil.
- Author
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Vasylieva N, Barnych B, Wan D, El-Sheikh EA, Nguyen HM, Wulff H, McMahen R, Strynar M, Gee SJ, and Hammock BD
- Subjects
- Animals, Chromatography, Liquid, Insecticides pharmacokinetics, Insecticides standards, Limit of Detection, Pyrazoles pharmacokinetics, Pyrazoles standards, Rats, Tandem Mass Spectrometry, Insecticides urine, Pyrazoles urine
- Abstract
Occupational medical surveillance is highly desirable in manufacturing facilities where exposure to chemicals is significant. The insecticide fipronil is generally considered safe for humans but with increasing use, exposure to fipronil is of concern. Identification of urinary metabolites of fipronil may allow development of affordable, cheap and rapid procedures for human exposure evaluation. In this study we developed a fast and easy approach for synthesis of hydroxy-fipronil, a potential urinary metabolite of fipronil. This standard was used to develop a sensitive analytical LC-MS/MS method with a limit of quantification (LOQ) of 0.4ng/mL. Fipronil sulfone, a known metabolite, and hydroxy-fipronil were quantified in urine samples from rats treated with a fipronil containing diet. Fipronil sulfone concentration centered around 20ng/mL, while the concentration of hydroxy-fipronil was dose-dependent ranging in 10-10,000ng/mL and thus being a more sensitive marker of fipronil exposure. A fipronil immunoassay with cross-reactivity to hydroxy-fipronil showed a good correlation in signal intensity with LC-MS data. It was also used to demonstrate the applicability of the method for sample screening in the evaluation of exposure levels., (Copyright © 2017 Elsevier Ltd. All rights reserved.)
- Published
- 2017
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36. Effects of perfluorinated chemicals on thyroid function, markers of ovarian reserve, and natural fertility.
- Author
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Crawford NM, Fenton SE, Strynar M, Hines EP, Pritchard DA, and Steiner AZ
- Subjects
- Adult, Environmental Monitoring, Fatty Acids, Female, Fertility, Humans, Ovarian Reserve, Thyroid Gland, Thyroid Hormones blood, Alkanesulfonic Acids blood, Caprylates blood, Endocrine Disruptors blood, Environmental Pollutants blood, Fluorocarbons blood, Sulfonic Acids blood
- Abstract
Perfluorinated chemicals (PFCs) can act as endocrine-disrupting chemicals, but there has been limited study of their effects on ovarian reserve or fecundability. 99 women, 30-44 years old, without infertility were followed until pregnancy. Initially, serum was evaluated for Antimullerian hormone (AMH), thyroid hormones: thyroid stimulating hormone (TSH), thyroxine (T4), free thyroxine (fT4), and triiodothyronine (T3), and PFCs: perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), perfluorononanoic acid (PFNA), and perfluorohexanesulfonic acid (PFHxS). Bivariate analyses assessed the relationship between thyroid hormones, AMH, and PFCs. Fecundability ratios (FR) were determined for each PFC using a discrete time-varying Cox model and a day-specific probability model. PFC levels were positively correlated with each other (r 0.24-0.90), but there was no correlation with TSH (r 0.02-0.15) or AMH (r -0.01 to -0.15). FR point estimates for each PFC were neither strong nor statistically significant. Although increased exposure to PFCs correlates with thyroid hormone levels, there is no significant association with fecundability or ovarian reserve., (Copyright © 2017 Elsevier Inc. All rights reserved.)
- Published
- 2017
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37. Novel Polyfluorinated Compounds Identified Using High Resolution Mass Spectrometry Downstream of Manufacturing Facilities near Decatur, Alabama.
- Author
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Newton S, McMahen R, Stoeckel JA, Chislock M, Lindstrom A, and Strynar M
- Subjects
- Alabama, Alkanesulfonic Acids, Caprylates, Fluorocarbons, Manufacturing and Industrial Facilities, Mass Spectrometry, Environmental Monitoring, Water Pollutants, Chemical
- Abstract
Concern over persistence, bioaccumulation, and toxicity has led to international regulation and phase-outs of certain perfluorinated compounds and little is known about their replacement products. High resolution mass spectrometry was used to investigate the occurrence and identity of replacement fluorinated compounds in surface water and sediment of the Tennessee River near Decatur, Alabama. Analysis of legacy Per- and polyfluoroalkyl substances (PFASs) revealed a marked increase in concentrations downstream of manufacturing facilities, with the most abundant compounds being perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate (PFBS), and perfluorooctanoic acid (PFOA) as high as 220 ng L
-1 , 160 ng L-1 , and 120 ng L-1 , respectively. A series of nine polyfluorinated carboxylic acids was discovered, each differing by CF2 CH2 . These acids are likely products or byproducts of a manufacturing process that uses 1,1-difluoroethene, which is registered to a manufacturing facility in the area. Two other predominant compounds discovered have structures consistent with perfluorobutanesulfonate and perfluoroheptanoic acid but have a single hydrogen substituted for a fluorine someplace in their structure. A polyfluoroalkyl sulfate with differing mixes of hydrogen and fluorine substitution was also observed. N-methyl perfluorobutane sulfonamidoacetic acid (MeFBSAA) was observed at high concentrations and several other perfluorobutane sulfonamido substances were present as well.- Published
- 2017
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38. Footprints of Urban Micro-Pollution in Protected Areas: Investigating the Longitudinal Distribution of Perfluoroalkyl Acids in Wildlife Preserves.
- Author
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Rodriguez-Jorquera IA, Silva-Sanchez C, Strynar M, Denslow ND, and Toor GS
- Subjects
- Ecological and Environmental Phenomena, Geologic Sediments chemistry, Humans, Seasons, Time Factors, Wastewater chemistry, Water chemistry, Water Supply, Cities statistics & numerical data, Conservation of Natural Resources, Environmental Pollution analysis, Fluorocarbons analysis
- Abstract
Current approaches to protect biodiversity by establishing protected areas usually gloss over water pollution as a threat. Our objective was to determine the longitudinal and seasonal distribution of perfluoroalkyl acids (PFAAs) in water column and sediments from a wastewater dominated stream that enters preservation areas. Water samples were collected along the longitudinal section (six sites, 1000 m away from each other) of the stream during the dry and wet seasons. Sediments were collected from three sites along the stream from three depths. Water and sediments were analyzed for PFAAs using high performance liquid chromatography-tandem mass spectrometry. Eleven PFAAs with 5 to 14 carbon atoms were detected in the water column at all sampling points, with a minor reduction at the last point suggesting a dilution effect. The most detected PFAAs was PFOS, followed by perfluorooctanoic acid (PFOA), and perfluorohexanoic acid (PFHxA). Seasonal differences in PFAAs concentrations suggested contribution of stormwater runoff during the wet season. All analyzed PFAAs in sediments were under the limit of quantification, likely due to the high proportion of sand and low organic matter. However, high concentrations of PFAAs were detected in the water column inside the protected areas, which includes PFOS in concentrations considered not safe for avian wildlife. Water samples appear to be more relevant than sediments to determine PFAAs micro-pollution in water bodies with sandy sediments. Inclusion of a management plans on micro-pollution research, monitoring, and mitigation is recommended for protected areas.
- Published
- 2016
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39. Identification of Novel Perfluoroalkyl Ether Carboxylic Acids (PFECAs) and Sulfonic Acids (PFESAs) in Natural Waters Using Accurate Mass Time-of-Flight Mass Spectrometry (TOFMS).
- Author
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Strynar M, Dagnino S, McMahen R, Liang S, Lindstrom A, Andersen E, McMillan L, Thurman M, Ferrer I, and Ball C
- Subjects
- Carboxylic Acids chemistry, Chemical Fractionation, Ethers analysis, Ethers chemistry, Fluorocarbons chemistry, Humans, North Carolina, Sulfonic Acids analysis, Sulfonic Acids chemistry, Water analysis, Water Pollutants, Chemical chemistry, Carboxylic Acids analysis, Fluorocarbons analysis, Spectrometry, Mass, Electrospray Ionization methods, Water Pollutants, Chemical analysis
- Abstract
Recent scientific scrutiny and concerns over exposure, toxicity, and risk have led to international regulatory efforts resulting in the reduction or elimination of certain perfluorinated compounds from various products and waste streams. Some manufacturers have started producing shorter chain per- and polyfluorinated compounds to try to reduce the potential for bioaccumulation in humans and wildlife. Some of these new compounds contain central ether oxygens or other minor modifications of traditional perfluorinated structures. At present, there has been very limited information published on these "replacement chemistries" in the peer-reviewed literature. In this study we used a time-of-flight mass spectrometry detector (LC-ESI-TOFMS) to identify fluorinated compounds in natural waters collected from locations with historical perfluorinated compound contamination. Our workflow for discovery of chemicals included sequential sampling of surface water for identification of potential sources, nontargeted TOFMS analysis, molecular feature extraction (MFE) of samples, and evaluation of features unique to the sample with source inputs. Specifically, compounds were tentatively identified by (1) accurate mass determination of parent and/or related adducts and fragments from in-source collision-induced dissociation (CID), (2) in-depth evaluation of in-source adducts formed during analysis, and (3) confirmation with authentic standards when available. We observed groups of compounds in homologous series that differed by multiples of CF2 (m/z 49.9968) or CF2O (m/z 65.9917). Compounds in each series were chromatographically separated and had comparable fragments and adducts produced during analysis. We detected 12 novel perfluoroalkyl ether carboxylic and sulfonic acids in surface water in North Carolina, USA using this approach. A key piece of evidence was the discovery of accurate mass in-source n-mer formation (H(+) and Na(+)) differing by m/z 21.9819, corresponding to the mass difference between the protonated and sodiated dimers.
- Published
- 2015
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40. Serum concentrations of perfluorinated compounds (PFC) among selected populations of children and adults in California.
- Author
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Wu XM, Bennett DH, Calafat AM, Kato K, Strynar M, Andersen E, Moran RE, Tancredi DJ, Tulve NS, and Hertz-Picciotto I
- Subjects
- Adult, California, Child, Child, Preschool, Humans, Surveys and Questionnaires, Fluorocarbons blood
- Abstract
Perfluorinated compounds (PFCs) have been widely used in industrial applications and consumer products. Their persistent nature and potential health impacts are of concern. Given the high cost of collecting serum samples, this study is to understand whether we can quantify PFC serum concentrations using factors extracted from questionnaire responses and indirect measurements, and whether a single serum measurement can be used to classify an individual's exposure over a one-year period. The study population included three demographic groups: young children (2-8 years old) (N=67), parents of young children (<55 years old) (N=90), and older adults (>55 years old) (N=59). PFC serum concentrations, house dust concentrations, and questionnaires were collected. The geometric mean of perfluorooctane sulfonic acid (PFOS) was highest for the older adults. In contrast, the geometric mean of perfluorooctanoic acid (PFOA) was highest for children. Serum concentrations of the parent and the child from the same family were moderately correlated (Spearman correlation (r)=0.26-0.79, p<0.05), indicating common sources within a family. For adults, age, having occupational exposure or having used fire extinguisher, frequencies of consuming butter/margarine, pork, canned meat entrées, tuna and white fish, freshwater fish, and whether they ate microwave popcorn were significantly positively associated with serum concentrations of individual PFCs. For children, residential dust concentrations, frequency of wearing waterproof clothes, frequency of having canned fish, hotdogs, chicken nuggets, French fries, and chips, and whether they ate microwave popcorn were significant positive predictors of individual PFC serum concentrations. In addition, the serum concentrations collected in a subset of young children (N=20) and the parents (N=42) one year later were strongly correlated (r=0.68-0.98, p<0.001) with the levels measured at the first visits, but showed a decreasing trend. Children had moderate correlation (r=0.43) between serum and dust concentrations of PFOS, indicating indoor sources contribute to exposure. In conclusion, besides food intake, occupational exposure, consumer product use, and exposure to residential dust contribute to PFC exposure. The downward temporal trend of serum concentrations reflects the reduction of PFCs use in recent years while the year-to-year correlation indicates that a single serum measurement could be an estimate of exposure relative to the population for a one-year period in epidemiology studies., (Copyright © 2014 Elsevier Inc. All rights reserved.)
- Published
- 2015
- Full Text
- View/download PDF
41. Estimating common parameters of lognormally distributed environmental and biomonitoring data: harmonizing disparate statistics from publications.
- Author
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Pleil JD, Sobus JR, Stiegel MA, Hu D, Oliver KD, Olenick C, Strynar M, Clark M, Madden MC, and Funk WE
- Subjects
- Humans, Publishing standards, Research Design, Biomedical Research standards, Data Interpretation, Statistical, Environmental Health, Environmental Monitoring, Models, Statistical
- Abstract
The progression of science is driven by the accumulation of knowledge and builds upon published work of others. Another important feature is to place current results into the context of previous observations. The published literature, however, often does not provide sufficient direct information for the reader to interpret the results beyond the scope of that particular article. Authors tend to provide only summary statistics in various forms, such as means and standard deviations, median and range, quartiles, 95% confidence intervals, and so on, rather than providing measurement data. Second, essentially all environmental and biomonitoring measurements have an underlying lognormal distribution, so certain published statistical characterizations may be inappropriate for comparisons. The aim of this study was to review and develop direct conversions of different descriptions of data into a standard format comprised of the geometric mean (GM) and the geometric standard deviation (GSD) and then demonstrate how, under the assumption of lognormal distribution, these parameters are used to answer questions of confidence intervals, exceedance levels, and statistical differences among distributions. A wide variety of real-world measurement data sets was reviewed, and it was demonstrated that these data sets are indeed of lognormal character, thus making them amenable to these methods. Potential errors incurred from making retrospective estimates from disparate summary statistics are described. In addition to providing tools to interpret "other people's data," this review should also be seen as a cautionary tale for publishing one's own data to make it as useful as possible for other researchers.
- Published
- 2014
- Full Text
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42. Dosimetric anchoring of in vivo and in vitro studies for perfluorooctanoate and perfluorooctanesulfonate.
- Author
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Wambaugh JF, Setzer RW, Pitruzzello AM, Liu J, Reif DM, Kleinstreuer NC, Wang NC, Sipes N, Martin M, Das K, DeWitt JC, Strynar M, Judson R, Houck KA, and Lau C
- Subjects
- Alkanesulfonic Acids pharmacokinetics, Animals, Caprylates pharmacokinetics, Dose-Response Relationship, Drug, Female, Fluorocarbons pharmacokinetics, In Vitro Techniques, Macaca fascicularis, Male, Mice, Mice, Inbred C57BL, Rats, Rats, Sprague-Dawley, Alkanesulfonic Acids toxicity, Caprylates toxicity, Fluorocarbons toxicity
- Abstract
In order to compare between in vivo toxicity studies, dosimetry is needed to translate study-specific dose regimens into dose metrics such as tissue concentration. These tissue concentrations may then be compared with in vitro bioactivity assays to perhaps identify mechanisms relevant to the lowest observed effect level (LOEL) dose group and the onset of the observed in vivo toxicity. Here, we examine the perfluorinated compounds (PFCs) perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS). We analyzed 9 in vivo toxicity studies for PFOA and 13 in vivo toxicity studies for PFOS. Both PFCs caused multiple effects in various test species, strains, and genders. We used a Bayesian pharmacokinetic (PK) modeling framework to incorporate data from 6 PFOA PK studies and 2 PFOS PK studies (conducted in 3 species) to predict dose metrics for the in vivo LOELs and no observed effect levels (NOELs). We estimated PK parameters for 11 combinations of chemical, species, strain, and gender. Despite divergent study designs and species-specific PK, for a given effect, we found that the predicted dose metrics corresponding to the LOELs (and NOELs where available) occur at similar concentrations. In vitro assay results for PFOA and PFOS from EPA's ToxCast project were then examined. We found that most in vitro bioactivity occurs at concentrations lower than the predicted concentrations for the in vivo LOELs and higher than the predicted concentrations for the in vivo NOELs (where available), for a variety of nonimmunological effects. These results indicate that given sufficient PK data, the in vivo LOELs dose regimens, but not necessarily the effects, could have been predicted from in vitro studies for these 2 PFCs.
- Published
- 2013
- Full Text
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43. Determination of perfluorinated alkyl acid concentrations in human serum and milk standard reference materials.
- Author
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Keller JM, Calafat AM, Kato K, Ellefson ME, Reagen WK, Strynar M, O'Connell S, Butt CM, Mabury SA, Small J, Muir DC, Leigh SD, and Schantz MM
- Subjects
- Animals, Environmental Monitoring methods, Environmental Pollutants analysis, Environmental Pollutants standards, Environmental Pollutants urine, Fluorocarbons standards, Humans, Reference Standards, Fluorocarbons analysis, Fluorocarbons urine, Milk chemistry
- Abstract
Standard Reference Materials (SRMs) are certified reference materials produced by the National Institute of Standards and Technology that are homogeneous materials well characterized with values for specified properties, such as environmental contaminant concentrations. They can be used to validate measurement methods and are critical in improving data quality. Disagreements in perfluorinated alkyl acid (PFAA) concentrations measured in environmental matrices during past interlaboratory comparisons emphasized the need for SRMs with values assigned for PFAAs. We performed a new interlaboratory comparison among six laboratories and provided, for the first time, value assignment of PFAAs in SRMs. Concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other PFAAs in two human serum and two human milk SRMs are reported. PFAA concentration measurements agreed for serum SRM 1957 using different analytical methods in six laboratories and for milk SRM 1954 in three laboratories. The interlaboratory relative standard deviation for PFOS in SRM 1957 was 7%, which is an improvement over past interlaboratory studies. Matrix interferences are discussed, as well as temporal trends and the percentage of branched vs. linear isomers. The concentrations in these SRMs are similar to the present-day average concentrations measured in human serum and milk, resulting in representative and useful control materials for PFAA human monitoring studies.
- Published
- 2010
- Full Text
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44. Correction to "Method development and measurement of perfluorinated compounds in U.S. chicken eggs".
- Author
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Lindstrom A, Reiner J, Nakayama S, Delinsky A, and Strynar M
- Published
- 2009
- Full Text
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45. Using 19F NMR spectroscopy to determine trifluralin binding to soil.
- Author
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Strynar M, Dec J, Benesi A, Jones AD, Fry RA, and Bollag JM
- Subjects
- Adsorption, Magnetic Resonance Spectroscopy, Environmental Monitoring methods, Fluorine Radioisotopes analysis, Herbicides analysis, Soil Pollutants analysis, Trifluralin analysis
- Abstract
Trifluralin is a widely used herbicide for the control of broad leaf weeds in a variety of crops. Its binding to soil may result in significant losses in herbicidal activity and a delayed pollution problem. To investigate the nature of soil-bound trifluralin residues, 14C-labeled herbicide was incubated for 7 weeks with four soils under anoxic conditions. As determined by radiocounting, trifluralin binding ranged between 10 and 53% of the initial 14C depending on the soil tested. 19F NMR analyses of the methanol extracts and different fractions of the extracted soil suggested that bound residue formation largely involved reduced metabolites of the herbicide. A 2,6-diamino product of trifluralin reduction with zero-valent iron (Fe-TR), and the standard of a 1,2-diaminotrifluralin derivative (TR6) formed covalent bonds with fulvic acid (FA), as indicated by the 19F NMR spectra taken periodically over a 3-week contact time. At short contact times, TR6 and Fe-TR formed weak physical bonds with FA, as the respective spin-lattice relaxation times (T1) decreased from the range 1300-1831 ms for TR6 or Fe-TR analyzed in the absence of FA to the range 150-410 ms for TR6/FA or Fe-TR/FA mixtures. In general, the results indicated that trifluralin immobilization involved a variety of mechanisms (covalent binding, adsorption, sequestration), and with time it became increasingly stable.
- Published
- 2004
- Full Text
- View/download PDF
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