RESUMO
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.
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Humanos , Criança , Adolescente , Adulto Jovem , Adulto , Pessoa de Meia-Idade , Idoso , Idoso de 80 Anos ou mais , Éteres , Poluentes Químicos da Água/análise , Caprilatos , Fluorocarbonos/análiseRESUMO
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.
Assuntos
Poluentes Ambientais , Fluorocarbonos , Hidrocarbonetos Clorados , Praguicidas , Bifenilos Policlorados , Poeira/análise , Poluentes Ambientais/análise , Éteres Difenil Halogenados/análise , Humanos , Hidrocarbonetos Clorados/análise , Bifenilos Policlorados/análiseRESUMO
PFAS are known bioaccumulative and persistent chemicals which pollute natural waters globally. There exists a lack of granular sorbents to efficiently remove both legacy and emerging PFAS at environmentally relevant concentrations. Herein, we report a class of polymer networks with a synergistic combination of ionic and fluorous components that serve as granular materials for the removal of anionic PFAS from water. A library of Ionic Fluorogels (IFs) with systematic variation in charge density and polymer network architecture was synthesized from hydrolytically stable fluorous building blocks. The IFs were demonstrated as effective sorbents for the removal of 21 legacy and emerging PFAS from a natural water and were regenerable over multiple cycles of reuse. Comparison of one IF to a commercial ion exchange resin in mini-rapid small-scale column tests demonstrated superior performance for the removal of short-chain PFAS from natural water under operationally relevant conditions.
Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Resinas de Troca Iônica , Polímeros , Água , Poluentes Químicos da Água/análiseRESUMO
Per- and polyfluoroalkyl substances (PFASs) have attracted scientific and regulatory attention due to their persistence, bioaccumulative potential, toxicity, and global distribution. We determined the accumulation and trophic transfer of 14 PFASs (5 short-chain and 9 long-chain) within the food web of the Yadkin-Pee Dee River of North Carolina and South Carolina, US. Food web components and pathways were determined by stable isotope analyses of producers, consumers, and organic matter. Analyses of water, sediment, organic matter, and aquatic biota revealed that PFASs were prevalent in all food web compartments. Biofilm, an aggregation of bacteria, fungi, algae, and protozoans and a basal resource for the aquatic food web, showed high PFAS accumulation (in 10 of 14 compounds), particularly for perfluorooctanoic acid, with the greatest mean concentration of 463.73 ng/g. The food web compartment with the most detections and greatest concentrations of PFASs was aquatic insects; all 14 PFASs were detected in individual aquatic insect samples (range of
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Ácidos Alcanossulfônicos/análise , Animais , Monitoramento Ambiental , Fluorocarbonos/análise , Cadeia Alimentar , Humanos , North Carolina , Rios , South Carolina , Poluentes Químicos da Água/análiseRESUMO
Perfluorooctanoic acid (PFOA) was used as a fluoropolymer manufacturing aid at a fluoropolymer production facility in Parkersburg, WV from 1951 to 2013. The manufacturer introduced a replacement surfactant hexafluoropropylene oxide dimer acid (HFPO-DA) that has been in use at this site since 2013. Historical releases of PFOA and related epidemiological work in this area has been primarily focused on communities downstream. To provide an update on the ongoing impacts from this plant, 94 surface water samples and 13 soil samples were collected mainly upstream and downwind of this facility. PFOA was detected in every surface water sample with concentrations exceeding 1000 ng/L at 13 sample sites within an 8 km radius of the plant. HFPO-DA was also found to be widespread with the highest levels (>100 ng/L) found in surface water up to 6.4 km north of the plant. One sample site, 28 km north of the plant, had PFOA at 143 ng/L and HFPO-DA at 42 ng/L. Sites adjacent to landfills containing fluorochemical waste had PFOA concentrations ranging up to >1000 ng/L. These data indicate that downwind atmospheric transport of both compounds has occurred and that the boundaries of the impact zone have yet to be fully delineated.
Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Caprilatos , Monitoramento Ambiental , Fluorocarbonos/análise , Ohio , Óxidos , Solo , Água , Poluentes Químicos da Água/análise , West VirginiaRESUMO
Aqueous film-forming foams (AFFF) are mixtures formulated with numerous hydrocarbon- and fluoro-containing surfactants. AFFF use leads to environmental releases of unknown per- and polyfluoroalkyl substances (PFAS). AFFF composition is seldom disclosed, and their use elicits concerns from both regulatory agencies and the public because PFAS are persistent in the environment and potentially associated with adverse health effects. In this study, we demonstrate the use of coupled liquid chromatography, ion mobility spectrometry, and mass spectrometry (LC-IMS-MS) to rapidly characterize both known and unknown PFAS in AFFF. Ten AFFF formulations from seven brands were analyzed using LC-IMS-MS in both negative and positive ion modes. Untargeted analysis of the formulations was followed by feature identification of PFAS-like features utilizing database matching, mass defect and homologous series evaluation, and MS/MS fragmentation experiments. Across the tested AFFF formulations, we identified 33 homologous series; only ten of these homologous series have been previously reported. Among tested AFFF, the FireStopper (n = 85) contained the greatest number of PFAS-like features and Phos-Check contained zero. This work demonstrates that LC-IMS-MS-enabled untargeted analysis of complex formulations, followed by feature identification using data-processing algorithms, can be used for rapid exposure characterization of known and putative PFAS during fire suppression-related contamination events.
Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Fluorocarbonos/análise , Espectrometria de Mobilidade Iônica , Espectrometria de Massas em Tandem , Água , Poluentes Químicos da Água/análiseRESUMO
Per- and polyfluoroalkyl substances (PFAS) are anthropogenic, globally distributed chemicals. Legacy PFAS, including perfluorooctane sulfonate (PFOS), have been regularly detected in marine fauna but little is known about their current levels or the presence of novel PFAS in seabirds. We measured 36 emerging and legacy PFAS in livers from 31 juvenile seabirds from Massachusetts Bay, Narragansett Bay, and the Cape Fear River Estuary (CFRE), United States. PFOS was the major legacy perfluoroalkyl acid present, making up 58% of concentrations observed across all habitats (range: 11-280 ng/g). Novel PFAS were confirmed in chicks hatched downstream of a fluoropolymer production site in the CFRE: a perfluorinated ether sulfonic acid (Nafion byproduct 2; range: 1-110 ng/g) and two perfluorinated ether carboxylic acids (PFO4DA and PFO5DoDA; PFO5DoDA range: 5-30 ng/g). PFOS was inversely associated with phospholipid content in livers from CFRE and Massachusetts Bay individuals, while δ 13C, an indicator of marine versus terrestrial foraging, was positively correlated with some long-chain PFAS in CFRE chick livers. There is also an indication that seabird phospholipid dynamics are negatively impacted by PFAS, which should be further explored given the importance of lipids for seabirds.
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Ácidos Alcanossulfônicos/análise , Animais , Aves , Monitoramento Ambiental , Fluorocarbonos/análise , Humanos , Massachusetts , Rios , Ácidos Sulfônicos/análise , Estados Unidos , Poluentes Químicos da Água/análiseRESUMO
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 Kow 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.
RESUMO
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.
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Cromatografia Líquida , Monitoramento Ambiental , North Carolina , Rios , Espectrometria de Massas em TandemRESUMO
In August 2015, the US Environmental Protection Agency (EPA) convened a workshop entitled "Advancing non-targeted analyses of xenobiotic chemicals in environmental and biological media." The purpose of the workshop was to bring together the foremost experts in non-targeted analysis (NTA) to discuss the state-of-the-science for generating, interpreting, and exchanging NTA measurement data. During the workshop, participants discussed potential designs for a collaborative project that would use EPA resources, including the ToxCast library of chemical substances, the DSSTox database, and the CompTox Chemicals Dashboard, to evaluate cutting-edge NTA methods. That discussion was the genesis of EPA's Non-Targeted Analysis Collaborative Trial (ENTACT). Nearly 30 laboratories have enrolled in ENTACT and used a variety of chromatography, mass spectrometry, and data processing approaches to characterize ten synthetic chemical mixtures, three standardized media (human serum, house dust, and silicone band) extracts, and thousands of individual substances. Initial results show that nearly all participants have detected and reported more compounds in the mixtures than were intentionally added, with large inter-lab variability in the number of reported compounds. A comparison of gas and liquid chromatography results shows that the majority (45.3%) of correctly identified compounds were detected by only one method and 15.4% of compounds were not identified. Finally, a limited set of true positive identifications indicates substantial differences in observable chemical space when employing disparate separation and ionization techniques as part of NTA workflows. This article describes the genesis of ENTACT, all study methods and materials, and an analysis of results submitted to date. Graphical abstract á .
Assuntos
Comportamento Cooperativo , Poluentes Ambientais/análise , Projetos de Pesquisa , Xenobióticos/análise , Cromatografia/métodos , Misturas Complexas , Coleta de Dados , Poeira , Educação , Exposição Ambiental , Poluentes Ambientais/normas , Poluentes Ambientais/toxicidade , Humanos , Laboratórios/organização & administração , Espectrometria de Massas/métodos , Controle de Qualidade , Padrões de Referência , Soro , Silicones/química , Estados Unidos , United States Environmental Protection Agency , Xenobióticos/normas , Xenobióticos/toxicidadeRESUMO
Safe drinking water at the point-of-use (tapwater, TW) is a United States public health priority. Multiple lines of evidence were used to evaluate potential human health concerns of 482 organics and 19 inorganics in TW from 13 (7 public supply, 6 private well self-supply) home and 12 (public supply) workplace locations in 11 states. Only uranium (61.9 µg L-1, private well) exceeded a National Primary Drinking Water Regulation maximum contaminant level (MCL: 30 µg L-1). Lead was detected in 23 samples (MCL goal: zero). Seventy-five organics were detected at least once, with median detections of 5 and 17 compounds in self-supply and public supply samples, respectively (corresponding maxima: 12 and 29). Disinfection byproducts predominated in public supply samples, comprising 21% of all detected and 6 of the 10 most frequently detected. Chemicals designed to be bioactive (26 pesticides, 10 pharmaceuticals) comprised 48% of detected organics. Site-specific cumulative exposure-activity ratios (∑EAR) were calculated for the 36 detected organics with ToxCast data. Because these detections are fractional indicators of a largely uncharacterized contaminant space, ∑EAR in excess of 0.001 and 0.01 in 74 and 26% of public supply samples, respectively, provide an argument for prioritized assessment of cumulative effects to vulnerable populations from trace-level TW exposures.
Assuntos
Água Potável , Praguicidas , Poluentes Químicos da Água , Monitoramento Ambiental , Humanos , Estados Unidos , Abastecimento de Água , Local de TrabalhoRESUMO
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(Kow) 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.
Assuntos
Oxirredutases do Álcool/química , Microcistinas/química , Água/química , Concentração de Íons de Hidrogênio , Estrutura Molecular , Poluentes Químicos da Água/químicaRESUMO
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 CF2CH2. 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.
Assuntos
Monitoramento Ambiental , Poluentes Químicos da Água , Alabama , Ácidos Alcanossulfônicos , Caprilatos , Fluorocarbonos , Instalações Industriais e de Manufatura , Espectrometria de MassasRESUMO
Although historic perfluorinated compounds are currently under scrutiny and growing regulatory control in the world, little is known about human exposure to other polyfluorinated compounds presently in use. Fluorotelomer alcohols (FTOHs) and polyfluoroalkyl phosphate esters (PAPs) are known to degrade to terminal perfluorinated acids and toxic reactive intermediates through metabolic pathways. Therefore, it is important to characterize their human exposure by the identification of unique biomarkers. With the use of liquid chromatography-mass spectrometry-time-of-flight analysis (LC-MS-TOF), we developed a workflow for the identification of metabolites for the 8:2 FTOH and 8:2 diPAP. Analysis of serum and urine of dosed rats indicated the 8:2 FTOH-sulfate and the 8:2 diPAP as potential biomarkers. These compounds, as well as 25 other fluorinated compounds and metabolites, were analyzed in human serum and urine samples from the general population (n = 100) and office workers (n = 30). The 8:2 FTOH-sulfate was measured for the first time in human samples in 5 to 10% of the serum samples, ranging from 50 to 80 pg/mL. The 8:2 diPAP was measured in 58% of the samples, ranging from 100 to 800 pg/mL. This study indicates the FTOH-sulfate conjugate as a biomarker of exposure to FTOHs and PAPs in humans.
Assuntos
Álcoois , Biomarcadores , Hidrocarbonetos Fluorados/toxicidade , Organofosfatos/toxicidade , Ácidos , Animais , Cromatografia Líquida , Fluorocarbonos , Humanos , Espectrometria de Massas , RatosRESUMO
Perfluoroalkyl substances (PFAS), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are persistent, globally distributed, anthropogenic compounds. The primary source(s) for human exposure are not well understood although within home exposure is likely important since many consumer products have been treated with different PFAS, and people spend much of their lives indoors. Herein, domestic cats were used as sentinels to investigate potential exposure and health linkages. PFAS in serum samples of 72 pet and feral cats, including 11 healthy and 61 with one or more primary disease diagnoses, were quantitated using high-resolution time-of-flight mass spectroscopy. All but one sample had detectable PFAS, with PFOS and perfluorohexane sulfonate (PFHxS) ranging from Assuntos
Ácidos Alcanossulfônicos/sangue
, Caprilatos/sangue
, Gatos
, Monitoramento Ambiental/métodos
, Fluorocarbonos/sangue
, Animais
, Doenças do Gato/sangue
, Habitação
, Obesidade/sangue
, Animais de Estimação/sangue
RESUMO
There is increasing emphasis on the use of biomarkers of adverse outcomes in safety assessment and translational research. We evaluated serum biomarkers and targeted metabolite profiles after exposure to pesticides (permethrin, deltamethrin, imidacloprid, carbaryl, triadimefon, fipronil) with different neurotoxic actions. Adult male Long-Evans rats were evaluated after single exposure to vehicle or one of two doses of each pesticide at the time of peak effect. The doses were selected to produce similar magnitude of behavioral effects across chemicals. Serum or plasma was analyzed using commercial cytokine/protein panels and targeted metabolomics. Additional studies of fipronil used lower doses (lacking behavioral effects), singly or for 14 days, and included additional markers of exposure and biological activity. Biomarker profiles varied in the number of altered analytes and patterns of change across pesticide classes, and discriminant analysis could separate treatment groups from control. Low doses of fipronil produced greater effects when given for 14 days compared to a single dose. Changes in thyroid hormones and relative amounts of fipronil and its sulfone metabolite also differed between the dosing regimens. Most cytokine changes reflected alterations in inflammatory responses, hormone levels, and products of phospholipid, fatty acid, and amino acid metabolism. These findings demonstrate distinct blood-based analyte profiles across pesticide classes, dose levels, and exposure duration. These results show promise for detailed analyses of these biomarkers and their linkages to biological pathways.
Assuntos
Biomarcadores/sangue , Praguicidas/química , Praguicidas/toxicidade , Animais , Quimiocinas/sangue , Relação Dose-Resposta a Droga , Hormônios/sangue , Inseticidas/toxicidade , Masculino , Metabolômica , Pirazóis/toxicidade , Ratos , Ratos Long-EvansRESUMO
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.
Assuntos
Ácidos Carboxílicos/análise , Fluorocarbonos/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Poluentes Químicos da Água/análise , Ácidos Carboxílicos/química , Fracionamento Químico , Éteres/análise , Éteres/química , Fluorocarbonos/química , Humanos , North Carolina , Ácidos Sulfônicos/análise , Ácidos Sulfônicos/química , Água/análise , Poluentes Químicos da Água/químicaRESUMO
The National Institute of Standards and Technology (NIST) has a wide range of Standard Reference Materials (SRMs) which have values assigned for legacy organic pollutants and toxic elements. Existing SRMs serve as homogenous materials that can be used for method development, method validation, and measurement for contaminants that are now of concern. NIST and multiple groups have been measuring the mass fraction of a group of emerging contaminants, polyfluorinated substances (PFASs), in a variety of SRMs. Here we report levels determined in an interlaboratory comparison of up to 23 PFASs determined in five SRMs: sediment (SRMs 1941b and 1944), house dust (SRM 2585), soil (SRM 2586), and sludge (SRM 2781). Measurements presented show an array of PFASs, with perfluorooctane sulfonate being the most frequently detected. SRMs 1941b, 1944, and 2586 had relatively low concentrations of most PFASs measured while 23 PFASs were at detectable levels in SRM 2585 and most of the PFASs measured were at detectable levels in SRM 2781. The measurements made in this study were used to add values to the Certificates of Analysis for SRMs 2585 and 2781.
Assuntos
Monitoramento Ambiental/normas , Poluentes Ambientais/normas , Hidrocarbonetos Fluorados/normas , Ácidos Alcanossulfônicos/análise , Ácidos Alcanossulfônicos/normas , Poeira/análise , Monitoramento Ambiental/métodos , Poluentes Ambientais/análise , Fluorocarbonos/análise , Fluorocarbonos/normas , Sedimentos Geológicos/análise , Hidrocarbonetos Fluorados/análise , Padrões de Referência , Poluentes do Solo/análiseRESUMO
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.
Assuntos
Fluorocarbonos/sangue , Adulto , California , Criança , Pré-Escolar , Humanos , Inquéritos e QuestionáriosRESUMO
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.