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1.
Sci Total Environ ; 868: 161488, 2023 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-36626992

RESUMEN

Very high levels of industrial contaminants in St. Lawrence Estuary (SLE) beluga whales represent one of the major threats to this population classified as endangered under the Species at Risk Act in Canada. Elevated concentrations of short-chained chlorinated paraffins (SCCPs) were recently reported in blubber of adult male SLE belugas. Recent regulations for SCCPs in North America, combined with their replacement by medium- (MCCPs) and long-chained chlorinated paraffins (LCCPs), highlight the importance of tracking this toxic chemical class. The objectives of this study were to evaluate (1) levels and profiles of chlorinated paraffins (CPs) in samples obtained from carcasses of adult male, adult female, juvenile, newborn, and fetus beluga, and (2) trends in adult male belugas between 1997 and 2018. Factors potentially influencing CP temporal trends such as age, feeding ecology and sampling year were also explored. SCCPs dominated (64 to 100%) total CP concentrations across all age and sex classes, MCCPs accounted for the remaining proportion of total CPs, and LCCPs were not detected in any sample. The chlorinated paraffin homolog that dominated the most in beluga blubber was C12Cl8. Adult male SCCP concentrations from this study were considerably lower (> 2000-fold) than those recently reported in Simond et al. (2020), likely reflecting a previously erroneous overestimate due to the lack of a suitable analytical method for SCCPs at the time. Both SCCPs and total CPs declined over time in adult males in our study (rate of 1.67 and 1.33% per year, respectively), presumably due in part to the implementation of regulations in 2012. However, there is a need to better understand the possible contribution of a changing diet to contaminant exposure, as stable isotopic ratios of carbon also changed over time.


Asunto(s)
Ballena Beluga , Hidrocarburos Clorados , Contaminantes Químicos del Agua , Animales , Femenino , Masculino , China , Dieta , Monitoreo del Ambiente/métodos , Estuarios , Hidrocarburos Clorados/análisis , Parafina/análisis , Contaminantes Químicos del Agua/análisis
2.
Sci Total Environ ; 737: 139386, 2020 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-32563110

RESUMEN

To examine the spatial, and temporal variation and potential sources of pesticide concentrations, primarily neonicotinoid insecticides, in hummingbirds in western Canada, we sampled their cloacal fluid from sites in British Columbia and Saskatchewan, Canada in 2017-2018. At a sub-sample of those sites, we also measured pesticides in honey bee (Apis mellifera) nectar, water, and sediment. We collected cloacal fluid from 5 species of hummingbirds (n = 26 sites) in British Columbia (BC) and Saskatchewan, Canada, and nectar from honey bee hives (n = 4 sites), water and sediment (n = 18 sites) in the Fraser Valley, BC. Among those, multiple types of samples were collected at 6 sites. We report the first measurement of flupyradifurone, a relatively new butenolide insecticide, in wildlife which was detected at 4.58 ng/mL in hummingbird cloacal fluid and 2.18 ng/g in honey bee nectar. We also detected three other neonicotinoids (imidacloprid, clothianidin, acetamiprid) and one metabolite desnitro-imidacloprid, and MGK264, a pesticide synergist, in our samples. Among 49 samples of cloacal fluid from rufous (Selasphorus rufus), Anna's (Calypte anna), calliope (Selasphorus calliope) black-chinned (Archilocus alexandri) and ruby-throated hummingbirds (Archilocus colubris), 26.5% (n = 13) contained neonicotinoids. Maximum pesticide concentrations in hummingbirds, water and sediment were found in samples collected in the Fraser Valley, BC within 0.5 km of conventionally sprayed blueberry fields (CSBF) but highest levels in honey bee nectar were detected at a site 1.5 km from a CSBF. Imidacloprid in honey bee nectar at one site exceeded concentrations (>1 ng/g) that can sublethally affect worker bee foraging efficiency. In water, imidacloprid concentrations at another site exceeded Canadian guidelines (230 ng/mL) for the protection of aquatic invertebrates.


Asunto(s)
Insecticidas/análisis , Nitrocompuestos , 4-Butirolactona/análogos & derivados , Animales , Abejas , Colombia Británica , Insectos , Neonicotinoides , Saskatchewan
3.
Phys Rev Lett ; 124(2): 022501, 2020 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-32004026

RESUMEN

Spectroscopic factors of neutron-hole and proton-hole states in ^{131}Sn and ^{131}In, respectively, were measured using one-nucleon removal reactions from doubly magic ^{132}Sn at relativistic energies. For ^{131}In, a 2910(50)-keV γ ray was observed for the first time and tentatively assigned to a decay from a 5/2^{-} state at 3275(50) keV to the known 1/2^{-} level at 365 keV. The spectroscopic factors determined for this new excited state and three other single-hole states provide first evidence for a strong fragmentation of single-hole strength in ^{131}Sn and ^{131}In. The experimental results are compared to theoretical calculations based on the relativistic particle-vibration coupling model and to experimental information for single-hole states in the stable doubly magic nucleus ^{208}Pb.

4.
Environ Sci Technol ; 53(21): 12576-12585, 2019 Nov 05.
Artículo en Inglés | MEDLINE | ID: mdl-31578061

RESUMEN

In this study, we measured the effects of sample type and storage temperature on the stability of 29 per- and polyfluorinated alkyl substances (PFAS) in water. Spiked bottled water, surface water, and two types of effluent samples were stored in HDPE containers at +20, 4, and -20 °C over a period of up to 180 days. The analytes studied included C4 through C14 perfluorinated carboxylates (PFCAs); C4 through C10 and C12 perfluorinated sulfonates (PFSAs); 4:2, 6:2, and 8:2 fluorotelomer sulfonates (FTS); three perfluorooctane sulfonamides (PFOSA, N-MeFOSA, and N-EtFOSA); two perfluorooctane sulfonamide ethanols (N-MeFOSE and N-EtFOSE); and two perfluorooctane sulfonamide acetic acids (N-MeFOSAA and EtFOSAA). Overall, 10 analytes, PFOA, PFNA, 8:2 FTS, PFOSA, N-MeFOSA, NEtFOSA, N-MeFOSAA, N-EtFOSAA, N-MeFOSE, and N-EtFOSE, showed increasing or decreasing concentration trends under at least one of the experimental conditions investigated. Increases in concentrations of N-MeFOSAA and N-EtFOSAA in surface water and effluent samples at +20 and 4 °C correlated with the decreases in the concentrations of N-MeFOSE and N-EtFOSE, respectively, suggesting analyte interconversion during sample storage. This is the first time such analyte conversion is reported in samples under storage, and this work demonstrates the importance of assessing stability of PFAS in environmentally relevant matrices. The significance of this study extends beyond sample storage for analysis, as toxicological and exposure studies conducted at room temperature also need to consider the significance of analyte degradation through the exposure process.


Asunto(s)
Fluorocarburos , Contaminantes Químicos del Agua , Alcanosulfonatos , Monitoreo del Ambiente , Agua
5.
Environ Int ; 106: 135-143, 2017 09.
Artículo en Inglés | MEDLINE | ID: mdl-28645013

RESUMEN

BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) are considered chemicals of emerging concern, in part due to their environmental and biological persistence and the potential for widespread human exposure. In 2007, a PFAS manufacturer near Decatur, Alabama notified the United States Environmental Protection Agency (EPA) it had discharged PFAS into a wastewater treatment plant, resulting in environmental contamination and potential exposures to the local community. OBJECTIVES: To characterize PFAS exposure over time, the Agency for Toxic Substances and Disease Registry (ATSDR) collected blood and urine samples from local residents. METHODS: Eight PFAS were measured in serum in 2010 (n=153). Eleven PFAS were measured in serum, and five PFAS were measured in urine (n=45) from some of the same residents in 2016. Serum concentrations were compared to nationally representative data and change in serum concentration over time was evaluated. Biological half-lives were estimated for perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and perfluorohexane sulfonic acid (PFHxS) using a one-compartment pharmacokinetic model. RESULTS: In 2010 and 2016, geometric mean PFOA and PFOS serum concentrations were elevated in participants compared to the general U.S. POPULATION: In 2016, the geometric mean PFHxS serum concentration was elevated compared to the general U.S. POPULATION: Geometric mean serum concentrations of PFOA, PFOS, and perfluorononanoic acid (PFNA) were significantly (p≤0.0001) lower (49%, 53%, and 58%, respectively) in 2016 compared to 2010. Half-lives for PFOA, PFOS, and PFHxS were estimated to be 3.9, 3.3, and 15.5years, respectively. Concentrations of PFOA in serum and urine were highly correlated (r=0.75) in males. CONCLUSIONS: Serum concentrations of some PFAS are decreasing in this residentially exposed community, but remain elevated compared to the U.S. general population.


Asunto(s)
Fluorocarburos/sangre , Fluorocarburos/orina , Contaminantes Químicos del Agua/sangre , Contaminantes Químicos del Agua/orina , Adolescente , Adulto , Anciano , Alabama , Femenino , Humanos , Masculino , Persona de Mediana Edad , Adulto Joven
6.
Phys Rev Lett ; 118(16): 162501, 2017 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-28474951

RESUMEN

Prompt γ-ray spectroscopy of the neutron-rich ^{96}Kr, produced in transfer- and fusion-induced fission reactions, has been performed using the combination of the Advanced Gamma Tracking Array and the VAMOS++ spectrometer. A second excited state, assigned to J^{π}=4^{+}, is observed for the first time, and a previously reported level energy of the first 2^{+} excited state is confirmed. The measured energy ratio R_{4/2}=E(4^{+})/E(2^{+})=2.12(1) indicates that this nucleus does not show a well-developed collectivity contrary to that seen in heavier N=60 isotones. This new measurement highlights an abrupt transition of the degree of collectivity as a function of the proton number at Z=36, of similar amplitude to that observed at N=60 at higher Z values. A possible reason for this abrupt transition could be related to the insufficient proton excitations in the g_{9/2}, d_{5/2}, and s_{1/2} orbitals to generate strong quadrupole correlations or to the coexistence of competing different shapes. An unexpected continuous decrease of R_{4/2} as a function of the neutron number up to N=60 is also evidenced. This measurement establishes the Kr isotopic chain as the low-Z boundary of the island of deformation for N=60 isotones. A comparison with available theoretical predictions using different beyond mean-field approaches shows that these models fail to reproduce the abrupt transitions at N=60 and Z=36.

7.
J Chromatogr A ; 1454: 93-100, 2016 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-27266337

RESUMEN

A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method was developed for quantitative analysis of hydroxy polycyclic aromatic hydrocarbons (OH-PAHs). Four hydroxy metabolites of known and suspected carcinogenic PAHs (benzo[a]pyrene (B[a]P), benz[a]anthracene (B[a]A), and chrysene (CRY)) were selected as suitable biomarkers of PAH exposure and associated risks to human health. The analytical method included enzymatic deconjugation, liquid - liquid extraction, followed by derivatization with methyl-N-(trimethylsilyl) trifluoroacetamide and instrumental analysis. Photo-induced oxidation of target analytes - which has plagued previously published methods - was controlled by a combination of minimizing exposure to light, employing an antioxidant (2-mercaptoethanol) and utilizing a nitrogen atmosphere. Stability investigations also indicated that conjugated forms of the analytes are more stable than the non-conjugated forms. Accuracy and precision of the method were 77.4-101% (<4.9% RSD) in synthetic urine and 92.3-117% (<15% RSD) in human urine, respectively. Method detection limits, determined using eight replicates of low-level spiked human urine, ranged from 13 to 24pg/mL. The method was successfully applied for analysis of a pooled human urine sample and 78 mouse urine samples collected from mice fed with PAH-contaminated diets. In mouse urine, greater than 94% of each analyte was present in its conjugated form.


Asunto(s)
Biomarcadores/análisis , Carcinógenos/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Hidrocarburos Policíclicos Aromáticos/análisis , Animales , Humanos , Ratones
8.
Phys Rev Lett ; 115(22): 222502, 2015 Nov 27.
Artículo en Inglés | MEDLINE | ID: mdl-26650299

RESUMEN

The isospin mixing was deduced in the compound nucleus ^{80}Zr at an excitation energy of E^{*}=54 MeV from the γ decay of the giant dipole resonance. The reaction ^{40}Ca+^{40}Ca at E_{beam}=136 MeV was used to form the compound nucleus in the isospin I=0 channel, while the reaction ^{37}Cl+^{44}Ca at E_{beam}=95 MeV was used as the reference reaction. The γ rays were detected with the AGATA demonstrator array coupled with LaBr_{3}:Ce detectors. The temperature dependence of the isospin mixing was obtained and the zero-temperature value deduced. The isospin-symmetry-breaking correction δ_{C} used for the Fermi superallowed transitions was extracted and found to be consistent with ß-decay data.

9.
J Chromatogr A ; 1400: 149-55, 2015 Jun 26.
Artículo en Inglés | MEDLINE | ID: mdl-25997845

RESUMEN

A method for quantitative determination of 13 organophosphorous compounds (OPs) was developed and applied to influent, primary sludge, activated sludge, biosolids, primary effluent and final effluent from a wastewater treatment plant (WWTP). The method involved solvent extraction followed by solid phase clean-up and analysis by high performance liquid chromatography positive electrospray ionization-tandem mass spectrometry (HPLC(+ESI)MS/MS). Replicate spike/recovery experiments revealed the method to have good accuracy (70-132%) and precision (<19% RSD) in all matrices. Detection limits of 0.1-5 ng/L for aqueous samples and 0.01-0.5 ng/g for solid samples were achieved. In the liquid waste stream ∑OP concentrations were highest in influent (5764 ng/L) followed by primary effluent (4642 ng/L), and final effluent (2328 ng/L). In the solid waste stream, the highest ∑OP concentrations were observed in biosolids (3167 ng/g dw), followed by waste activated sludge (2294 ng/g dw), and primary sludge (2128 ng/g dw). These concentrations are nearly 30-fold higher than ∑polybrominated diphenyl ether (BDE) concentrations in influents and nearly 200-fold higher than ∑BDE concentrations in effluents from other sites in Canada. Tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6), tripropylphosphate (TnPrP), and Tris(2,3-dibromopropyl)phosphate (TDBPP) are investigated for the first time in a WWTP. While TnPrP and TDBB were not detected, V6 was observed at concentrations up to 7.9 ng/g in solid waste streams and up to 40.7 ng/L in liquid waste streams. The lack of removal of OPs during wastewater treatment is a concern due to their release into the aquatic environment.


Asunto(s)
Cromatografía Líquida de Alta Presión , Monitoreo del Ambiente/métodos , Retardadores de Llama/análisis , Plastificantes/análisis , Espectrometría de Masas en Tándem , Aguas Residuales/química , Canadá , Aguas del Alcantarillado/química , Contaminantes Químicos del Agua/análisis
10.
Phys Rev Lett ; 113(1): 012501, 2014 Jul 04.
Artículo en Inglés | MEDLINE | ID: mdl-25032921

RESUMEN

The properties of pygmy dipole states in 208Pb were investigated using the 208Pb(17O, 17O'γ) reaction at 340 MeV and measuring the γ decay with high resolution with the AGATA demonstrator array. Cross sections and angular distributions of the emitted γ rays and of the scattered particles were measured. The results are compared with (γ, γ') and (p, p') data. The data analysis with the distorted wave Born approximation approach gives a good description of the elastic scattering and of the inelastic excitation of the 2+ and 3- states. For the dipole transitions a form factor obtained by folding a microscopically calculated transition density was used for the first time. This has allowed us to extract the isoscalar component of the 1- excited states from 4 to 8 MeV.

12.
Environ Toxicol Chem ; 32(11): 2576-83, 2013 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-24115123

RESUMEN

Spectacled caiman (Caiman crocodilus) are fish-eating crocodilians that inhabit freshwater habitat in tropical regions of the Americas. To assess the exposure of caiman to pesticides from banana plantations, the authors collected whole blood samples (30 mL) from 14 adult caiman that were captured in the North Atlantic region of Costa Rica. Blood samples were analyzed for 70 legacy- and current-use pesticides and breakdown products using newly developed ultra-trace, high-resolution mass spectrometry (HRMS). Caiman accumulated pesticides ranked by concentration as dieldrin > permethrin > mirex > 4,4'-DDE > alpha-endosulfan > heptachlor epoxide > oxychlordane > heptachlor > cypermethrin. Caiman within the high-intensity banana crop watershed of Rio Suerte had higher pesticide burdens relative to other more remote locations (F = 12.79; p = 0.00). Pesticide concentration decreased with distance from upstream banana plantations in this river system (F = 20.76; p = 0.00). Caiman body condition was negatively correlated with total pesticide concentrations (F = 6.23; p = 0.02) and with proximity to banana plantations (F = 5.05; p = 0.04). This suggests that either pesticides elicited toxic effects in caiman, resulting in diminished overall health, or that the quantity or quality of their prey was reduced by pesticides downstream of plantation waterways. The authors' results indicate that pesticide use in banana plantations is impacting a high trophic level species inhabiting one of the most important wilderness areas in Costa Rica (Tortuguero National Park).


Asunto(s)
Caimanes y Cocodrilos/sangre , Plaguicidas/sangre , Contaminantes Químicos del Agua/sangre , Animales , Costa Rica , Productos Agrícolas , Ecosistema , Musa , Plaguicidas/toxicidad , Ríos , Contaminantes Químicos del Agua/toxicidad
13.
J Chromatogr A ; 1293: 36-43, 2013 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-23628174

RESUMEN

A method for quantitative characterization of naphthenic acid (NA) isomer groups by carbon number and extent of cyclization was developed and validated with water samples from northern Alberta. Following solid phase extraction, NAs undergo derivatization with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) allowing detection by positive electrospray ionization tandem mass spectrometry (+ESI)-MS/MS. NA-EDC derivatives produce a common product ion by MS/MS, regardless of structure of the starting NA. Thus, approximately constant relative response factors (RRFs) were assumed for the various isomer groups that elute at a given point in the elution gradient (supported by calculated RRFs for individual model NAs), facilitating quantification using a single standard (1-pyrenebutyric acid). To reduce the impact of major background fatty acids on NA data, the method employed an optimized liquid chromatography method that separated straight chain (Z=0) analytes from other NAs. Method validation was performed at two spiking levels (7.72µg and 38.6µg total refined Merichem per 500mL of reagent water) and good accuracy (mean recoveries of 82.4±2.5% and 93.0±2.6%, respectively; range ~50-130%) and precision (<17% RSD) were achieved at both spiking levels for all 60 NA isomer groups. The method also performed well in an independent method comparison study in which method accuracy values of 107%, 120%, and 121% were obtained for 2 spiked reagent waters (1mg/L and 50mg/L NAs) and spiked Athabasca River water (0.035mg/L NAs), respectively. Application of the method to samples from northern Alberta revealed that NA concentrations decreased in the order: process water (52.8mg/L)>tailings pond water (30.6mg/L)>well water (0.086mg/L)>surface water (0.007mg/L), and that samples were distinguishable by NA isomer profile using Principal components analysis.


Asunto(s)
Ácidos Carboxílicos/análisis , Cromatografía Liquida/métodos , Espectrometría de Masas en Tándem/métodos , Contaminantes Químicos del Agua/análisis , Ácidos Carboxílicos/química , Ácidos Carboxílicos/aislamiento & purificación , Isomerismo , Yacimiento de Petróleo y Gas/química , Estanques/química , Análisis de Componente Principal , Reproducibilidad de los Resultados , Ríos/química , Extracción en Fase Sólida , Espectrometría de Masa por Ionización de Electrospray/métodos , Contaminantes Químicos del Agua/química
14.
Environ Sci Technol ; 47(3): 1381-9, 2013 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-23305554

RESUMEN

Investigations into the biodegradation potential of perfluorooctane sulfonate (PFOS)-precursor candidates have focused on low molecular weight substances (e.g., N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE)) in wastewater treatment plant sludge. Few data are available on PFOS-precursor biodegradation in other environmental compartments, and nothing is known about the stability of high-molecular-weight perfluorooctane sulfonamide-based substances such as the EtFOSE-based phosphate diester (SAmPAP diester) in any environmental compartment. In the present work, the biodegradation potential of SAmPAP diester and EtFOSE by bacteria in marine sediments was evaluated over 120 days at 4 and 25 °C. At both temperatures, EtFOSE was transformed to a suite of products, including N-ethyl perfluorooctane sulfonamidoacetate, perfluorooctane sulfonamidoacetate, N-ethyl perfluorooctane sulfonamide, perfluorooctane sulfonamide, and perfluorooctane sulfonate. Transformation was significantly more rapid at 25 °C (t(1/2) = 44 ± 3.4 days; error represents standard error of the mean (SEM)) compared to 4 °C (t(1/2) = 160 ± 17 days), but much longer than previous biodegradation studies involving EtFOSE in sludge (t(1/2) ∼0.7-4.2 days). In contrast, SAmPAP diester was highly recalcitrant to microbial degradation, with negligible loss and/or associated product formation observed after 120 days at both temperatures, and an estimated half-life of >380 days at 25 °C (estimated using the lower bounds 95% confidence interval of the slope). We hypothesize that the hydrophobicity of SAmPAP diester reduces its bioavailability, thus limiting biotransformation by bacteria in sediments. The lengthy biodegradation half-life of EtFOSE and recalcitrant nature of SAmPAP diester in part explains the elevated concentrations of PFOS-precursors observed in urban marine sediments from Canada, Japan, and the U.S, over a decade after phase-out of their production and commercial application in these countries.


Asunto(s)
Ésteres/metabolismo , Fluorocarburos/metabolismo , Sedimentos Geológicos/química , Hidrocarburos Fluorados/metabolismo , Organofosfatos/metabolismo , Sulfonamidas/metabolismo , Bacterias/metabolismo , Biodegradación Ambiental , Sedimentos Geológicos/microbiología , Semivida
15.
Phys Rev Lett ; 111(24): 242504, 2013 Dec 13.
Artículo en Inglés | MEDLINE | ID: mdl-24483649

RESUMEN

The γ-ray strength function of 56Fe has been measured from proton-γ coincidences for excitation energies up to ≈11 MeV. The low-energy enhancement in the γ-ray strength function, which was first discovered in the (3He,αγ)56Fe reaction, is confirmed with the (p,p'γ)56Fe experiment reported here. Angular distributions of the γ rays give for the first time evidence that the enhancement is dominated by dipole transitions.

16.
J Chromatogr A ; 1247: 165-70, 2012 Jul 20.
Artículo en Inglés | MEDLINE | ID: mdl-22695697

RESUMEN

A rapid (<23 min) new HPLC-MS/MS method was developed for simultaneous characterization of 24 per- and polyfluoroalkyl compounds in landfill leachate. In addition to isomer-specific analysis of perfluorooctane sulfonate and perfluorooctanoate, branched from linear isomer separation was accomplished for C6 and C10 perfluoroalkyl sulfonates, C6, C7 and C9-C11 perfluoroalkyl carboxylates, perfluorooctane sulfonamide and, for the first time, 3 perfluorooctane sulfonamidoacetates. The method utilizes a fused-core pentafluorophenylpropyl (PFP) stationary phase and is approximately 4 times faster than previous comprehensive isomer-specific HPLC-MS/MS methods. This is the first isomer-specific methodology which can be adopted for routine analysis without sacrificing throughput from lengthy run times or limited target lists.


Asunto(s)
Ácidos Alcanesulfónicos/química , Caprilatos/química , Cromatografía Líquida de Alta Presión/métodos , Fluorocarburos/química , Sulfonamidas/química , Espectrometría de Masas en Tándem/métodos , Isomerismo , Reproducibilidad de los Resultados
17.
Environ Sci Technol ; 46(12): 6505-14, 2012 Jun 19.
Artículo en Inglés | MEDLINE | ID: mdl-22591467

RESUMEN

The environmental occurrence of perfluorooctane sulfonate (PFOS) can arise from its direct use as well as from transformation of precursors ((N-alkyl substituted) perfluorooctane sulfonamides; FOSAMs). Perfluorooctane sulfonamidoethanol-based phosphate (SAmPAP) esters are among numerous potential PFOS-precursors which have not been previously detected in the environment and for which little is known about their stability. Based on their high production volume during the 1970s-2002 and widespread use in food contact paper and packaging, SAmPAP esters may be potentially significant sources of PFOS. Here we report for the first time on the environmental occurrence of SAmPAP diester in marine sediments from an urbanized marine harbor in Vancouver, Canada. SAmPAP diester concentrations in sediment (40-200 pg/g dry weight) were similar to those of PFOS (71-180 pg/g). A significant (p < 0.05) correlation was observed between SAmPAP diester and N-ethyl perfluorooctane sulfonamido acetate (an anticipated degradation product of SAmPAP diester). ∑PFOS-precursor (FOSAM) concentrations in sediment (120-1100 pg/g) were 1.6-24 times greater than those of PFOS in sediment. Although SAmPAP diester was not detected in water, PFOS was observed at concentrations up to 710 pg/L. Among the per- and polyfluoroalkyl substances monitored in the present work, mean log-transformed sediment/water distribution coefficients ranged from 2.3 to 4.3 and increased with number of CF(2) units and N-alkyl substitution (in the case of FOSAMs). Overall, these results highlight the importance of FOSAMs as potentially significant sources of PFOS, in particular for urban marine environments.


Asunto(s)
Ácidos Alcanesulfónicos/análisis , Fluorocarburos/análisis , Sedimentos Geológicos/química , Agua de Mar , Contaminantes Químicos del Agua/química , Ácidos Alcanesulfónicos/química , Fluorocarburos/química , Control de Calidad
18.
Phys Rev Lett ; 102(9): 092502, 2009 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-19392515

RESUMEN

The gamma decay from Coulomb excitation of 68Ni at 600 MeV/nucleon on a Au target was measured using the RISING setup at the fragment separator of GSI. The 68Ni beam was produced by a fragmentation reaction of 86Kr at 900 MeV/nucleon on a 9Be target and selected by the fragment separator. The gamma rays produced at the Au target were measured with HPGe detectors at forward angles and with BaF2 scintillators at backward angles. The measured spectra show a peak centered at approximately 11 MeV, whose intensity can be explained in terms of an enhanced strength of the dipole response function (pygmy resonance). Such pygmy structure has been predicted in this unstable neutron-rich nucleus by theory.

19.
J Environ Qual ; 38(3): 940-7, 2009.
Artículo en Inglés | MEDLINE | ID: mdl-19329682

RESUMEN

In the period 2003 to 2005, a study was conducted to determine the occurrence, and spatial and temporal distribution of 78 pesticides in surface waters of the Lower Fraser Valley (LFV) region of British Columbia, Canada. A high resolution gas chromatography/electron impact high resolution mass spectrometry (HRGC/[EI]HRMS) method capable of detecting analytes at the subnanograms per liter level was developed for this study. Samples were collected and analyzed from three reference, five agricultural and two urban sites. Endosulfan sulfate was detected in all samples collected during the study period including the samples from the reference sites. The maximum concentration of a pesticide detected at the reference sites was 0.261 ng L(-1) for beta-endosulfan. Over the study period, the numbers of pesticides detected at the agricultural sites ranged from 22 to 33 of which 20.8 to 40.9% had a 100% detection frequency. At the agricultural sites, the greatest concentration was detected for diazinon (12,500 ng L(-1)), followed by linuron (1050 ng L(-1)) and simazine (896 ng L(-1)). The greatest pesticide concentration observed for the urban sites was 90.4 ng L(-1) for simazine followed by diazinon (5.39 ng L(-1)). With few exceptions, greater concentrations of herbicides were observed for samples collected during spring than for samples collected during fall. Pesticide data presented in this study provide reference levels for future pesticide monitoring programs in the region.


Asunto(s)
Residuos de Plaguicidas/análisis , Ríos/química , Abastecimiento de Agua/normas , Agricultura , Colombia Británica , Monitoreo del Ambiente , Estándares de Referencia , Estaciones del Año , Urbanización
20.
J Environ Qual ; 38(3): 948-54, 2009.
Artículo en Inglés | MEDLINE | ID: mdl-19329683

RESUMEN

In Part I of this work we presented pesticide levels in the surface waters of the Lower Fraser Valley (LFV) region of British Columbia, Canada. In Part II pesticide levels in the groundwater of the LFV are presented. During the period 2003 to 2005 a study was conducted to determine the occurrence and spatial distribution of 78 pesticides in the groundwater of the LFV. Samples were collected and analyzed from one reference, nine agricultural, one urban, and three urban-agriculture mixed sites. Overall 24 different pesticides were detected in the sites monitored. The maximum single pesticide concentration observed was for simazine (90 ng L(-1)) at one of the agricultural sites. All concentrations of pesticides detected in groundwater samples were below Canadian surface water quality criteria and below available drinking water quality criteria set by World Health Organization (WHO), Health Canada, USEPA, and the European Union (EU). Pesticide levels in surface and groundwater were compared in the Abbotsford area. Generally, a pesticide with a high groundwater concentration tended to also have a high surface water concentration (Simazine 29 ng L(-1) in groundwater and 58 ng L(-1) in surface water, atrazine 5.5 ng L(-1) in groundwater and 14 ng L(-1) in surface water). For pesticides that were detected above 1 ng L(-1) concentration the only exception to this was desethylatrazine that showed greater concentration in groundwater (2.2 ng L(-1)) than surface water (1.5 ng L(-1)). Herbicides were the predominant pesticides detected in the agricultural sites and insecticides were predominant in the urban sites. Pesticide data presented in this study provide reference levels for future pesticide monitoring programs in the region.


Asunto(s)
Agua Dulce/análisis , Residuos de Plaguicidas/análisis , Abastecimiento de Agua/normas , Agricultura , Colombia Británica , Monitoreo del Ambiente , Estándares de Referencia , Estaciones del Año , Urbanización
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