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1.
Environ Sci Technol ; 54(22): 14558-14567, 2020 11 17.
Artigo em Inglês | MEDLINE | ID: mdl-33143410

RESUMO

Over the past few years, human exposure to per- and polyfluoroalkyl substances (PFAS) has garnered increased attention. Research has focused on PFAS exposure via drinking water and diet, and fewer studies have focused on exposure in the indoor environment. To support more research on the latter exposure pathway, we conducted a study to evaluate PFAS in indoor dust. Dust samples from 184 homes in North Carolina and 49 fire stations across the United States and Canada were collected and analyzed for a suite of PFAS using liquid and gas chromatography-mass spectrometry. Fluorotelomer alcohols (FTOHs) and di-polyfluoroalkyl phosphoric acid esters (diPAPs) were the most prevalent PFAS in both fire station and house dust samples, with medians of approximately 100 ng/g dust or greater. Notably, perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonate, perfluorononanoic acid, and 6:2 diPAP were significantly higher in dust from fire stations than from homes, and 8:2 FTOH was significantly higher in homes than in fire stations. Additionally, when comparing our results to earlier published values, we see that perfluoroalkyl acid levels in residential dust appear to decrease over time, particularly for PFOA and PFOS. These results highlight a need to better understand what factors contribute to PFAS levels in dust and to understand how much dust contributes to overall human PFAS exposure.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Canadá , Caprilatos , Poeira/análise , Exposição Ambiental/análise , Fluorocarbonos/análise , Humanos , América do Norte , North Carolina
2.
Environ Sci Technol ; 52(1): 277-287, 2018 01 02.
Artigo em Inglês | MEDLINE | ID: mdl-29198103

RESUMO

After several decades of widespread use, some per- and polyfluoroalkyl substances (PFASs) were phased-out of use due to concerns raised by their persistent, bioaccumulative, and toxic properties. Our objective was to evaluate temporal trends in serum PFAS levels among 1257 middle-aged and older California women (ages 40-94) during a four year period, beginning approximately 5-10 years after these phase-outs began. An online SPE-HPLC-MS/MS was used to measure 10 long-chain PFASs in serum from blood collected cross-sectionally during 2011-2015 from a subset of participants in the California Teachers Study. Results from multivariable linear regression analyses indicated that serum concentrations of nearly all PFASs declined on average 10% to 20% per year. Serum levels of perfluorohexanesulfonic acid (PFHxS) did not significantly decline. With the exception of PFHxS, the downward trend in serum concentrations was evident for all PFASs across all ages, although declines were comparatively steeper among the oldest women. These findings suggest that the phase-out of some common PFASs has resulted in reduced human exposures to them. The lack of a decline for PFHxS suggests that these exposures may be ongoing and underscores the importance of continued biomonitoring and research efforts to elucidate current pathways of exposure.


Assuntos
Poluentes Ambientais , Fluorocarbonos , California , Monitoramento Ambiental , Feminino , Humanos , Pessoa de Meia-Idade , Espectrometria de Massas em Tandem
3.
Environ Health ; 17(1): 83, 2018 11 27.
Artigo em Inglês | MEDLINE | ID: mdl-30482205

RESUMO

BACKGROUND: Per- and poly- fluoroalkyl substances (PFASs) are a large family of synthetic chemicals, some of which are mammary toxicants and endocrine disruptors. Their potential as breast carcinogens is unclear. Our objective was to evaluate the risk of breast cancer associated with serum PFAS concentrations in a nested case-control study within the California Teachers Study. METHODS: Participants were 902 women with invasive breast cancer (cases) and 858 with no such diagnosis (controls) who provided 10 mL of blood and were interviewed during 2011-2015, an average of 35 months after case diagnosis. PFASs were measured using automated online SPE-HPLC-MS/MS methods. Statistical analyses were restricted to six PFASs with detection frequencies ≥ 95%: PFOA (Perfluorooctanoic acid), PFNA (Perfluorononanoic acid), PFUnDA (Perfluoroundecanoic acid), PFHxS (Perfluorohexane sulfonic acid), PFOS (Perfluorooctane sulfonic acid), and MeFOSAA (2-(N-Methyl-perfluorooctane sulfonamido) acetic acid. Unconditional logistic regression was used to calculate adjusted odds ratios (ORs), estimating the breast cancer risk associated with each PFAS. RESULTS: For all cases of invasive breast cancer, none of the adjusted ORs were statistically significant but marginally significant ORs < 1.0 were observed for PFUnDA and PFHxS (p-trend = 0.08). Adjusted ORs < 1.0 for PFUnDA and PFHxS were statistically significant (p ≤ 0.05) among the 107 cases with hormone-negative tumors but not the 743 with hormone-positive tumors. CONCLUSION: Overall, these findings do not provide evidence that serum PFAS levels measured after diagnosis are related to breast cancer risk. The few inverse associations found may be due to chance or may be artifacts of study design. Future studies should incorporate information about genetic susceptibility, endogenous estrogen levels, and measurements of PFASs prior to diagnosis and treatment.


Assuntos
Ácidos Alcanossulfônicos/sangue , Neoplasias da Mama/sangue , Neoplasias da Mama/epidemiologia , Poluentes Ambientais/sangue , Ácidos Graxos/sangue , Fluorocarbonos/sangue , Adulto , Idoso , Idoso de 80 Anos ou mais , California/epidemiologia , Estudos de Casos e Controles , Monitoramento Ambiental , Feminino , Humanos , Pessoa de Meia-Idade , Razão de Chances , Risco , Adulto Jovem
4.
Environ Sci Technol ; 51(8): 4697-4704, 2017 04 18.
Artigo em Inglês | MEDLINE | ID: mdl-28304169

RESUMO

In response to health concerns and widespread human exposures, two widely used commercial formulations of polybrominated diphenyl ethers (PBDEs) were banned in the United States in 2005. Initial biomonitoring data have provided early indications of reduced human exposures since these bans took effect. Our objective was to evaluate temporal trends in PBDE serum levels among a population of older California women during a four-year period, beginning approximately five years after these formulations were banned. Automated solid phase extraction and gas chromatography/high resolution mass spectrometry were used to measure PBDE levels in blood collected during 2011-2015 among 1253 women (ages 40-94) participating in the California Teachers Study. Only congeners with detection frequencies (DF) ≥ 75% were included in the present analysis: BDE-47 (DF = 88%); BDE-100 (DF = 78%); and BDE-153 (DF = 80%). Results from age- and race/ethnicity-adjusted linear regression analyses indicated modest, but statistically significant, average annual percent increases in the serum concentrations of all three PBDEs over the four-year study period. While not without limitations, these results, in the context of other biomonitoring data, suggest that earlier reported declines in PBDE levels may have plateaued and may now be starting to increase. Further biomonitoring to ascertain current trends and determinants of population exposures is warranted.


Assuntos
Éteres Difenil Halogenados/sangue , Bifenil Polibromatos/sangue , Idoso , California , Monitoramento Ambiental , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Pessoa de Meia-Idade , Extração em Fase Sólida
5.
Environ Sci Technol ; 50(3): 1510-8, 2016 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-26699103

RESUMO

In this study, we measured serum PBDE levels in California (CA) house cats during two time periods: 2008-2010 and 2012-2013 to assess the impacts of the decline in use of these materials after the bans. The median ∑19PBDE level in CA household cats (age ≥10 yr) was 3479 ng/g lipid in 2008-2010 (1st time period, n = 21) and 1518 ng/g lipid in 2012-2013 (2nd time period, n = 22), about 2 times lower than in the first time period (p = 0.006). In contrast, PCB and OCP levels showed no statistically significant changes. With better matched group size and age (HT = 11 vs non-HT = 11, age ≥10 yr) in the second time period, we found that ∑19PBDE level (mean ± SE ng/g lipid) was significantly higher in the HT group (3906 ± 1442) than those in the non-HT group (1125 ± 244) (p = 0.0030). Higher levels of PCBs and OCPs were also found in HT group. Despite the declines of PBDE levels, our findings indicate that the current levels of PBDEs, as well as PCBs and OCPs, may still pose health effects for house cats and, possibly, humans.


Assuntos
Poluentes Ambientais/sangue , Éteres Difenil Halogenados/sangue , Hipertireoidismo/sangue , Animais , California , Gatos , Feminino , Hipertireoidismo/veterinária , Masculino , Bifenilos Policlorados/sangue
6.
Environ Sci Technol ; 50(7): 3945-53, 2016 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-26906616

RESUMO

As consumer products treated with polybrominated diphenyl ethers (PBDEs) reach the end of their life cycle, they often are discarded into solid-waste facilities, offering a potential reservoir for exposure. The likelihood of exposures to PBDEs by residents living near those sites rarely has been explored. This study collected blood samples from 923 female participants in the California Teachers Study in 2011-2013 and examined the association between participants' residential proximity to solid-waste facilities with potential release of PBDEs and serum levels of three congeners (BDE-47, BDE-100, and BDE-153). General linear regression analysis was used to examine the association, adjusting for age, race, body-mass index, neighborhood socioeconomic status, and urban residency. Compared to participants living >10 km from any selected site, those living within 2 km had 45% higher BDE-47 (95% CI: 5-100%) and BDE-100 (95% CI: 0-109%) levels, and those living between 2 and 10 km had 35% higher BDE-47 (95% CI: 0-82%) and 29% higher BDE-100 (95% CI: -9 to 82%) levels. No associations were found for BDE-153. Living close to some solid waste sites may be related to higher serum BDE-47 and BDE-100 levels. Studies with comprehensive exposure assessments are needed to confirm these initial observations.


Assuntos
Monitoramento Ambiental , Éteres Difenil Halogenados/sangue , Características de Residência , Resíduos Sólidos , Idoso , Idoso de 80 Anos ou mais , California , Feminino , Humanos , Lipídeos/química , Pessoa de Meia-Idade , Bifenil Polibromatos/sangue
7.
Environ Sci Technol ; 50(22): 12464-12472, 2016 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-27700069

RESUMO

Exposures to environmental pollutants in utero may increase the risk of adverse health effects. We measured the concentrations of 59 potentially harmful chemicals in 77 maternal and 65 paired umbilical cord blood samples collected in San Francisco during 2010-2011, including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs), and perfluorinated compounds (PFCs) in serum and metals in whole blood. Consistent with previous studies, we found evidence that concentrations of mercury (Hg) and lower-brominated PBDEs were often higher in umbilical cord blood or serum than in maternal samples (median cord:maternal ratio > 1), while for most PFCs and lead (Pb), concentrations in cord blood or serum were generally equal to or lower than their maternal pair (median cord:maternal ratio ≤ 1). In contrast to the conclusions of a recent review, we found evidence that several PCBs and OCPs were also often higher in cord than maternal serum (median cord:maternal ratio > 1) when concentrations are assessed on a lipid-adjusted basis. Our findings suggest that for many chemicals, fetuses may experience higher exposures than their mothers and highlight the need to characterize potential health risks and inform policies aimed at reducing sources of exposure.


Assuntos
Poluentes Ambientais , Éteres Difenil Halogenados , Exposição Materna , Monitoramento Ambiental , Feminino , Humanos , Hidrocarbonetos Clorados , Recém-Nascido , Troca Materno-Fetal , Bifenilos Policlorados , Gravidez , São Francisco , População Urbana
8.
Breast Cancer Res Treat ; 151(2): 335-45, 2015 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-25962693

RESUMO

The purpose of the study is to define AroER tri-screen's utility for identifying endocrine-disrupting chemicals (EDCs) that target aromatase and/or estrogen receptor (ER), and to measure the total estrogenic activity in biological specimens. ER-positive, aromatase-expressing MCF-7 breast cancer cells were stably transfected with an estrogen responsive element (ERE)-driven luciferase reporter plasmid to yield a new high-throughput screening platform-the AroER tri-screen. AroER tri-screen was capable of identifying estrogen precursors, such as cortodoxone, which function as estrogens through a two-step conversion process in aromatase-expressing tissue. Furthermore, the system proved useful for assessing EDC activity in biologically relevant samples. Estimating these activities is critical because natural estrogens and estrogenic EDCs are important factors in ER-positive breast cancer risk. As our research demonstrates, incorporating functionally active aromatase into the AroER tri-screen produces a powerful and unique tool to (1) identify new EDCs targeting aromatase and/or ER; (2) discover novel EDCs activated by aromatase; and (3) estimate overall estrogenic activities in biological samples as a potential intermediate risk factor for breast cancer.


Assuntos
Antineoplásicos Hormonais/farmacologia , Neoplasias da Mama/metabolismo , Ensaios de Seleção de Medicamentos Antitumorais , Disruptores Endócrinos/farmacologia , Estrogênios/metabolismo , Receptores de Estrogênio/metabolismo , Neoplasias da Mama/genética , Linhagem Celular Tumoral , Proliferação de Células , Cortodoxona/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais/métodos , Estrogênios/farmacologia , Feminino , Expressão Gênica , Genes Reporter , Humanos , Receptores de Estrogênio/genética , Reprodutibilidade dos Testes , Transfecção
9.
Environ Sci Technol ; 49(15): 9331-40, 2015 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-26147951

RESUMO

We evaluated relationships between persistent organic pollutant (POP) levels in the blood of children with leukemia and POP levels in dust from their household vacuum cleaners. Blood and dust were collected from participants of the California Childhood Leukemia Study at various intervals from 1999 to 2007 and analyzed for two polybrominated diphenyl ethers (PBDEs), two polychlorinated biphenyls (PCBs), and two organochlorine pesticides using gas chromatography-mass spectrometry. Due to small blood sample volumes (100 µL), dichlorodiphenyldichloroethylene (DDE) and BDE-153 were the only analytes with detection frequencies above 70%. For each analyte, depending on its detection frequency, a multivariable linear or logistic regression model was used to evaluate the relationship between POP levels in blood and dust, adjusting for child's age, ethnicity, and breastfeeding duration; mother's country of origin; household annual income; and blood sampling date. In linear regression, concentrations of BDE-153 in blood and dust were positively associated; whereas, DDE concentrations in blood were positively associated with breastfeeding, maternal birth outside the U.S., and Hispanic ethnicity, but not with corresponding dust-DDE concentrations. The probability of PCB-153 detection in a child's blood was marginally associated with dust-PCB-153 concentrations (p = 0.08) in logistic regression and significantly associated with breastfeeding. Our findings suggest that dust ingestion is a source of children's exposure to certain POPs.


Assuntos
Poeira/análise , Compostos Orgânicos/sangue , Adolescente , Adulto , Aleitamento Materno , California , Criança , Pré-Escolar , Diclorodifenil Dicloroetileno/sangue , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Éteres Difenil Halogenados/sangue , Habitação , Humanos , Hidrocarbonetos Clorados/sangue , Leucemia/sangue , Masculino , Razão de Chances , Praguicidas/sangue , Bifenil Polibromatos/sangue , Bifenilos Policlorados/sangue
10.
Environ Sci Technol ; 49(5): 2948-58, 2015 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-25643236

RESUMO

Concern about persistent organic pollutants (POPs) in Californians prompted the state's biomonitoring program to conduct a study in firefighters, who are occupationally exposed to high levels of POPs. In this work we present serum concentrations of several classes of POPs (polybrominated diphenyl ethers [PBDEs], polychlorinated biphenyls [PCBs], and organochlorine pesticides [OCPs]) in 101 Southern California firefighters. Despite recently reported declining trends of PBDEs in Californians, high levels were measured in firefighters' serum (Σ5PBDEs: median = 59.1 ng/(g of lipid); range = 18.8-714 ng/(g of lipid)) in comparison to other populations in California during the same period. In addition, nearly one-third of subjects had particularly high serum levels of decabromodiphenyl ether (BDE-209), consistent with other recent results in firefighters; this pattern may be a marker of recent firefighting activity. In contrast, serum levels of PCBs and OCPs measured in firefighters' sera were not elevated compared to U.S. levels. Multivariable analysis indicated that lower levels of serum PBDEs were associated with turnout gear cleaning and storage practices after fires. Our study supports the hypothesis that firefighting activities are likely to increase exposure to PBDEs and that good housekeeping and personal hygiene practices may reduce exposure to these compounds.


Assuntos
Bombeiros , Éteres Difenil Halogenados/análise , Exposição Ocupacional/efeitos adversos , California , Monitoramento Ambiental , Humanos , Hidrocarbonetos Clorados/análise , Praguicidas/análise
11.
Environ Sci Technol ; 49(8): 4988-94, 2015 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-25798547

RESUMO

Firefighters are exposed to chemicals during fire events and may also experience chemical exposure in their fire stations. Dust samples from used vacuum cleaner bags were collected from 20 fire stations in California and analyzed for polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) using gas chromatography-mass spectrometry. Median dust concentrations were higher for PBDEs (e.g., 47 000 ng/g for BDE-209) than for PAHs (e.g., 220 ng/g for benzo[a]pyrene) or PCBs (e.g., 9.3 ng/g for PCB-180). BDE-209 concentrations in dust from California fire stations were among the highest of any previously documented homes or occupational settings in the world. We examined factors such as the frequency of emergency responses, the number of fire vehicles on site, and building age, but we could not account for the high levels of BDE-209 observed in fire station dust. Based on the findings of our pilot study, we hypothesize that possible sources of BDE-209 in fire stations include contaminated ash tracked back from fire events via boots, clothing, and other equipment as well as specialized equipment treated with BDE-209, including turnout gear and fire vehicles. We suggest possible follow-up studies to confirm these hypotheses.


Assuntos
Poeira/análise , Bombeiros , Éteres Difenil Halogenados/análise , California , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Projetos Piloto , Vácuo
12.
Environ Res ; 136: 57-66, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25460621

RESUMO

BACKGROUND: Humans are exposed to persistent organic pollutants (POPs) through various routes, including consumption of contaminated food and accidental ingestion of settled dust. OBJECTIVES: We aimed to identify key routes of exposure to organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in California women of reproductive age. METHODS: Blood was collected from 48 mothers participating in the California Childhood Leukemia Study from 2006 to 2007 and analyzed for POPs using gas chromatography-mass spectrometry. Multivariable linear regression models of natural-log transformed serum concentrations were used to identify determinants of exposure from available questionnaire information on dietary habits, reproductive history, and demographic characteristics, as well as vacuum cleaner dust-POP levels. RESULTS: After adjusting for blood lipid levels, age, body mass index, cumulative lactation, and sampling date, serum concentrations of multiple major PCBs were positively associated with fish consumption, but not dust-PCB levels. After adjusting for blood lipid levels, Hispanic ethnicity, country of origin, and household annual income, serum concentrations of multiple major PBDEs were positively associated with dust-PBDE levels. CONCLUSIONS: Our findings suggest that the relative contribution of specific exposure routes to total POP intake varies by chemical class, with dust being a relatively important source of PBDEs and diet being a relatively important source of PCBs.


Assuntos
Poeira , Poluentes Ambientais/sangue , Compostos Orgânicos/sangue , Adulto , California , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Habitação , Humanos , Inquéritos e Questionários
13.
Environ Sci Technol ; 48(1): 157-64, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24313682

RESUMO

We characterized the variability in concentrations of polychlorinated biphenyls (PCBs) measured in residential dust. Vacuum cleaner samples were collected from 289 homes in the California Childhood Leukemia Study during two sampling rounds from 2001 to 2010 and 15 PCBs were measured by high resolution gas chromatography-mass spectrometry. Median concentrations of the most abundant PCBs (i.e., PCBs 28, 52, 101, 105, 118, 138, 153, and 180) ranged from 1.0-5.8 ng per g of dust in the first sampling round and from 0.8-3.4 ng/g in the second sampling round. For each of these eight PCBs, we used a random-effects model to apportion total variation into regional variability (6-11%), intraregional between-home variability (27-56%), within-home variability over time (18-52%), and within-sample variability (9-16%). In mixed-effects models, differences in PCB concentrations between homes were explained by home age, with older homes having higher PCB levels. Differences in PCB concentrations within homes were explained by decreasing time trends. Estimated half-lives ranged from 5-18 years, indicating that PCBs are removed very slowly from the indoor environment. Our findings suggest that it may be feasible to use residential dust for retrospective assessment of PCB exposures in studies of children's health.


Assuntos
Poluição do Ar em Ambientes Fechados/análise , Poeira/análise , Bifenilos Policlorados/análise , Adolescente , California , Estudos de Casos e Controles , Criança , Pré-Escolar , Exposição Ambiental/análise , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Meia-Vida , Habitação , Humanos , Lactente , Recém-Nascido , Leucemia/etiologia , Masculino , Modelos Teóricos , Estudos Retrospectivos
14.
Environ Res ; 135: 9-14, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-25261858

RESUMO

Eleven novel brominated flame retardants (NBFRs) were analyzed in dust samples from California homes as a part of the Northern California Childhood Leukemia Study (NCCLS) and from the living quarters of California fire stations as a part of the Firefighter Occupational Exposure (FOX) study using high resolution gas chromatography/mass spectrometry. The eleven NBFRs were α- and ß-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (α- and ß-DBE-DBCH), 2-bromoallyl 2,3,6-tribromophenylether (BATE), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (TBP-DBPE), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP), and decabromodiphenylethane (DBDPE). Six of the seven NBFRs that are produced in relatively small quantities (i.e., α-, ß-DBE-DBCH, BATE, PBEB, PBT, TBP-DBPE) were measured close to or below the limit of quantitation (0.64 ng/g) in both the NCCLS and FOX samples, and the seventh, HBB, was measured at median concentrations of 1.85 ng/g and 9.40 ng/g in the NCCLS and FOX samples, respectively. The remaining four NBFRs, EH-TBB, BEH-TEBP, BTBPE, and DBDPE, are produced in higher quantities, and were detected at median concentrations of 337 ng/g, 186 ng/g, 22.3 ng/g, and 82.8 ng/g, respectively in the NCCLS samples, and at median concentrations of 2687 ng/g, 2076 ng/g, 28.4 ng/g, and 161 ng/g, respectively, in the FOX samples. Concentrations of NBFRs in the NCCLS and FOX dust samples were several times lower than concentrations of PBDEs previously measured in the same samples. Concentrations of NBFRs in the NCCLS and FOX dust samples were generally comparable to concentrations of NBFRs in other studies of house dust from the US and Canada.


Assuntos
Poeira/análise , Monitoramento Ambiental/estatística & dados numéricos , Bombeiros/estatística & dados numéricos , Retardadores de Chama/análise , Éteres Difenil Halogenados/análise , Exposição Ocupacional/análise , California , Monitoramento Ambiental/métodos , Cromatografia Gasosa-Espectrometria de Massas , Humanos
15.
Rapid Commun Mass Spectrom ; 27(13): 1437-49, 2013 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-23722678

RESUMO

RATIONALE: Concerns about the adverse health effects of ubiquitous flame retardants spurred our interest in the development of a sensitive and reliable analytical method for these toxic compounds in various sample matrices. This study focuses on the investigation of fragmentation pathways and the structures of target ions of thirteen new halogenated flame retardants. METHODS: In this study, we use gas chromatography (GC)/high-resolution double-focusing sector mass spectrometry to characterize the fragmentation pathways of these new flame retardants. Along with the isotope patterns, accurate mass data were acquired to verify the molecular formula. RESULTS: The fragmentation pathways are classified based on the types of bond dissociations, e.g. σ-bond cleavage, α-bond cleavage and multiple-bond dissociations with a hydrogen shift. The α-bond dissociation occurs among 1,2-bis-(2,4,6-tribromophenoxy)ethane, allyl 2,4,6-tribromophenyl ether (ATE), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE) and 2-bromoallyl 2,4,6-tribromophenyl ether (BATE). The peak clusters that dominated ATE, BATE and hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) spectra correspond to two fragments as proved by accurate mass data and isotope patterns. These two fragments are formed as the result of two competing fragmentation pathways of radical loss and hydrogen shift. Fragmentation pathways of the other compounds are complex, involving cleavage of multiple bonds and hydrogen shifts. CONCLUSIONS: The accurate-mass-based GC/MS method offers great selectivity and sensitivity for quantitative analysis of the persistent organic pollutants. Thus, elucidation of the structures of the fragments is of prime importance for building an accurate-mass-based isotopic method. In addition, this study is useful for GC/MS/MS method development because multiple reaction monitoring (MRM) transitions of precursor ions and product ions may be easily elucidated based on these fragmentation patterns.


Assuntos
Monitoramento Ambiental/métodos , Retardadores de Chama/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Halogenação
16.
Environ Sci Technol ; 47(8): 3902-8, 2013 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-23506475

RESUMO

Polybrominated diphenyl ethers (PBDEs) were widely used as flame retardants in the past three decades. These compounds are lipophilic and easily cross the placenta from pregnant woman to fetus. It is not clear whether hydroxylated PBDEs (OH-PBDEs), with greater hydrophilicity, have different concentrations in maternal and cord serum samples. We analyzed PBDEs (BDE-28, -47, -99, -100, -153, -154, -209) and OH-PBDEs (6-OH-BDE-47, 5-OH-BDE-47, 4'-OH-BDE-49, 5'-OH-BDE-99) in 20 pairs of maternal and cord serum samples collected in Cincinnati, OH in 2011. The geometric mean concentration of ∑OH-BDEs (the sum of four OH-PBDEs) was 49.76 pg/mL in cord sera, higher than 32.84 pg/mL in maternal sera. Similarly, cord serum total BDEs had a higher geometric mean than maternal serum (45.51 vs 32.07 ng/g lipid). Equal or higher levels of total OH-BDEs and total BDEs in cord serum were observed in 85% and 80% of the mother-neonate pairs, respectively. The study suggests fetuses might receive higher OH-PBDE and PBDE exposure than their mothers.


Assuntos
Éteres Difenil Halogenados/sangue , Mães , Cordão Umbilical/metabolismo , Adulto , Peso ao Nascer , Intervalos de Confiança , Feminino , Humanos , Hidroxilação , Ohio , Gravidez , Análise de Regressão
17.
Environ Sci Technol ; 47(20): 11776-84, 2013 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-24066858

RESUMO

Prenatal exposures to polybrominated diphenyl ethers (PBDEs) can harm neurodevelopment in humans and animals. In 2003-2004, PentaBDE and OctaBDE were banned in California and phased-out of US production; resulting impacts on human exposures are unknown. We previously reported that median serum concentrations of PBDEs and their metabolites (OH-PBDEs) among second trimester pregnant women recruited from San Francisco General Hospital (2008-2009; n = 25) were the highest among pregnant women worldwide. We recruited another cohort from the same clinic in 2011-2012 (n = 36) and now compare serum concentrations of PBDEs, OH-PBDEs, polychlorinated biphenyl ethers (PCBs) (structurally similar compounds banned in 1979), and OH-PCBs between two demographically similar cohorts. Between 2008-2009 and 2011-2012, adjusted least-squares geometric mean (LSGM) concentrations of ∑PBDEs decreased 65% (95% CI: 18, 130) from 90.0 ng/g lipid (95% CI: 64.7, 125.2) to 54.6 ng/g lipid (95% CI: 39.2, 76.2) (p = 0.004); ∑OH-PBDEs decreased 6-fold (p < 0.0001); and BDE-47, -99, and -100 declined more than BDE-153. There was a modest, nonsignificant (p = 0.13) decline in LSGM concentrations of ∑PCBs and minimal differences in ∑OH-PCBs between 2008-2009 and 2011-2012. PBDE exposures are likely declining due to regulatory action, but the relative stability in PCB exposures suggests PBDE exposures may eventually plateau and persist for decades.


Assuntos
Éteres Difenil Halogenados/sangue , Hospitais Gerais , Bifenilos Policlorados/sangue , Segundo Trimestre da Gravidez/sangue , Adolescente , Adulto , Estudos de Coortes , Demografia , Feminino , Humanos , Análise dos Mínimos Quadrados , Idade Materna , Análise Multivariada , Gravidez , São Francisco , Fatores de Tempo , Adulto Jovem
18.
Environ Health ; 11: 49, 2012 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-22817616

RESUMO

BACKGROUND: Polychlorinated biphenyls (PCBs), known endocrine disruptors, were banned in 1979 but persist in the environment. Previous studies are inconsistent regarding prenatal exposure to PCBs and pregnancy outcomes. We investigated associations between prenatal exposure to PCBs and gestational length and birth weight. METHODS: In a sample of 600 infants (born between 1960 and 1963) randomly selected from Child Health and Development Studies participants followed through adolescence we measured 11 PCB congeners in maternal post partum sera (within three days of delivery). Length of gestation was computed from the reported first day of the last menstrual period (LMP) and delivery date. Linear regression was used to estimate associations between PCB exposure and gestational age and birth weight, adjusting for potential confounders. PCBs were grouped according to hypothesized biological action (1b (sum of weak phenobarbital inducers), 2b (sum of limited dioxin activity), and 3 (sum of CYP1A and CYP2b inducers)) or degree of ortho- substitution (mono, di, tri). Secondary analyses examined associations between total PCB exposure and exposure to individual congeners. RESULTS: Each unit increase in mono-ortho substituted PCBs was associated with a 0.30 week decrease (95% confidence interval (CI) -0.59, -0.016), corresponding to a 2.1 (95% CI -4.13, -0.11) day decrease in length of gestation. Similar associations were estimated for di-ortho substituted PCBs, (1.4 day decrease; (95% CI -2.9, 0.1)) and group 3 PCBs (0.84 day decrease; (95% CI -1.8, 0.11). We found similar associations in congener specific analyses and for the sum of congeners. CONCLUSIONS: Our study provides new evidence that PCB exposure shortens length of gestation in humans. This may have public health implications for population exposures.


Assuntos
Peso ao Nascer/efeitos dos fármacos , Exposição Ambiental , Poluentes Ambientais/toxicidade , Bifenilos Policlorados/toxicidade , Efeitos Tardios da Exposição Pré-Natal/induzido quimicamente , Tireotropina/sangue , Tiroxina/sangue , Adolescente , Adulto , California/epidemiologia , Criança , Pré-Escolar , Estudos de Coortes , Poluentes Ambientais/análise , Poluentes Ambientais/sangue , Feminino , Seguimentos , Humanos , Modelos Lineares , Masculino , Bifenilos Policlorados/análise , Bifenilos Policlorados/sangue , Gravidez , Efeitos Tardios da Exposição Pré-Natal/epidemiologia , Fatores de Tempo
19.
Breast Cancer Res Treat ; 129(2): 505-11, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21468638

RESUMO

We conducted a case-control study to evaluate the risk of breast cancer associated with adipose concentrations of polybrominated diphenyl ethers (PBDEs) among women undergoing surgical breast biopsies in the San Francisco Bay Area of California (n=78 cases; 56 controls). Adipose tissue was analyzed for the five major congeners of PBDEs. Unconditional logistic regression was used to estimate age- and race-adjusted exposure-specific odds ratios (ORs) and 95% confidence intervals (95% CI). Adipose levels of PBDEs were among the highest ever reported. Adjusted ORs for the highest compared with lowest levels of exposures were as follows: 0.56 (95% CI 0.19-1.68) for BDE-47; 1.19 (95% CI 0.35-4.10) for BDE-99; 0.91 (95% CI 0.33-2.53) for BDE-100; 0.52 (95% CI 0.19-1.39) for BDE-153; 1.67 (95% CI 0.44-6.29) for BDE-154; 2.04 (95% CI 0.45-9.20) for total BDEs. These results provide no evidence of an association between PBDE adipose concentrations measured at or near the time of diagnosis and breast cancer risk. Our study was limited by a small sample size. Given the high levels of PBDEs found in this population of California women, future studies are warranted. Such studies would benefit from a larger sample size, a more representative control series, and/or a prospective design.


Assuntos
Tecido Adiposo/química , Neoplasias da Mama/epidemiologia , Carcinógenos Ambientais/análise , Éteres Difenil Halogenados/análise , Adulto , Biópsia , Carga Corporal (Radioterapia) , Neoplasias da Mama/patologia , Carcinógenos Ambientais/efeitos adversos , Estudos de Casos e Controles , Distribuição de Qui-Quadrado , Feminino , Éteres Difenil Halogenados/efeitos adversos , Humanos , Modelos Logísticos , Pessoa de Meia-Idade , Razão de Chances , Medição de Risco , Fatores de Risco , São Francisco/epidemiologia
20.
Environ Sci Technol ; 45(17): 7510-6, 2011 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-21732675

RESUMO

Serum samples collected from California women at different time periods: 1960s (n = 40), 1980s (n = 30), and 2009 (n = 35) were examined for the presence of 12 perfluorinated compounds (PFCs) using an online SPE-HPLC-MS/MS method. At each time period, perfluorooctane sulfonate (PFOS) was present at the highest concentration, followed by perfluorooctanoic acid (PFOA, except in the 1960s). We found the highest levels of PFOS (median = 42.1 ng/mL) and perfluorohexane sulfonate (PFHxS, median = 1.56 ng/mL) in the 1960s samples, possibly reflecting widespread use of precursor PFCs. PFOS showed a statistically significant drop from the 1960s to the 1980s (28.8 ng/mL ) and to 2009 (9.0 ng/mL ), the latter being in agreement with national data. For PFOA, there was an approximately 10-fold increase in median concentrations from the 1960s (0.27 ng/mL) to the 1980s (2.71 ng/mL), and a slight drop in the 2009 samples (2.08 ng/mL). For longer chain perfluorocarboxylic acids (PFCAs), there was a continuous build-up in serum from the 1960s to 2009. To our knowledge, this is the first study to investigate temporal changes of PFCs over the past 50 years.


Assuntos
Poluentes Ambientais/sangue , Fluorocarbonos/sangue , Adulto , California , Cromatografia Líquida de Alta Pressão/métodos , Feminino , Humanos , Limite de Detecção , Estudos Longitudinais , Gravidez , Controle de Qualidade , Espectrometria de Massas em Tandem/métodos , Fatores de Tempo
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