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1.
Mol Cell ; 81(20): 4271-4286.e4, 2021 10 21.
Artigo em Inglês | MEDLINE | ID: mdl-34403695

RESUMO

Helitrons are widespread eukaryotic DNA transposons that have significantly contributed to genome variability and evolution, in part because of their distinctive, replicative rolling-circle mechanism, which often mobilizes adjacent genes. Although most eukaryotic transposases form oligomers and use RNase H-like domains to break and rejoin double-stranded DNA (dsDNA), Helitron transposases contain a single-stranded DNA (ssDNA)-specific HUH endonuclease domain. Here, we report the cryo-electron microscopy structure of a Helitron transposase bound to the 5'-transposon end, providing insight into its multidomain architecture and function. The monomeric transposase forms a tightly packed assembly that buries the covalently attached cleaved end, protecting it until the second end becomes available. The structure reveals unexpected architectural similarity to TraI, a bacterial relaxase that also catalyzes ssDNA movement. The HUH active site suggests how two juxtaposed tyrosines, a feature of many replication initiators that use HUH nucleases, couple the conformational shift of an α-helix to control strand cleavage and ligation reactions.


Assuntos
Quirópteros/metabolismo , Elementos de DNA Transponíveis , DNA de Cadeia Simples/metabolismo , Transposases/metabolismo , Animais , Domínio Catalítico , Quirópteros/genética , Microscopia Crioeletrônica , DNA de Cadeia Simples/genética , DNA de Cadeia Simples/ultraestrutura , Células HEK293 , Humanos , Modelos Moleculares , Conformação de Ácido Nucleico , Conformação Proteica em alfa-Hélice , Domínios e Motivos de Interação entre Proteínas , Relação Estrutura-Atividade , Transposases/genética , Transposases/ultraestrutura , Tirosina
2.
Environ Sci Technol ; 58(25): 11162-11174, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38857410

RESUMO

Thermal treatment has emerged as a promising approach for either the end-of-life treatment or regeneration of granular activated carbon (GAC) contaminated with per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been limited by the requirement for high temperatures, the generation of products of incomplete destruction, and the necessity to scrub HF in the flue gas. This study investigates the use of common alkali and alkaline-earth metal additives to enhance the mineralization of perfluorooctanesulfonate (PFOS) adsorbed onto GAC. When treated at 800 °C without an additive, only 49% of PFOS was mineralized to HF. All additives tested demonstrated improved mineralization, and Ca(OH)2 had the best performance, achieving a mineralization efficiency of 98% in air or N2. Its ability to increase the reaction rate and shift the byproduct selectivity suggests that its role may be catalytic. Moreover, additives reduced HF in the flue gas by instead reacting with the additive to form inorganic fluorine (e.g., CaF2) in the starting waste material. A hypothesized reaction mechanism is proposed that involves the electron transfer from O2- defect sites of CaO to intermediates formed during the thermal decomposition of PFOS. These findings advocate for the use of additives in the thermal treatment of GAC for disposal or reuse, with the potential to reduce operating costs and mitigate the environmental impact associated with incinerating PFAS-laden wastes.


Assuntos
Ácidos Alcanossulfônicos , Carvão Vegetal , Fluorocarbonos , Carvão Vegetal/química , Ácidos Alcanossulfônicos/química , Fluorocarbonos/química , Metais Alcalinoterrosos/química , Adsorção , Álcalis/química , Temperatura Alta
3.
Environ Sci Technol ; 56(19): 13845-13857, 2022 10 04.
Artigo em Inglês | MEDLINE | ID: mdl-36129192

RESUMO

We analyzed 72 children's textile products marketed as stain-resistant from US and Canadian stores, particularly school uniforms, to assess if clothing represents a significant route of exposure to per- and polyfluoroalkyl substances (PFAS). Products were first screened for total fluorine (total F) using particle-induced γ-ray emission (PIGE) spectroscopy (n = 72), followed by targeted analysis of 49 neutral and ionic PFAS (n = 57). PFAS were detected in all products from both markets, with the most abundant compound being 6:2 fluorotelomer alcohol (6:2 FTOH). Total targeted PFAS concentrations for all products collected from both countries ranged from 0.250 to 153 000 ng/g with a median of 117 ng/g (0.0281-38 100 µg/m2, median: 24.0 µg/m2). Total targeted PFAS levels in school uniforms were significantly higher than in other items such as bibs, hats, stroller covers, and swimsuits, but comparable to outdoor wear. Higher total targeted PFAS concentrations were found in school uniforms made of 100% cotton than synthetic blends. Perfluoroalkyl acids (PFAAs) precursors were abundant in school uniforms based on the results of hydrolysis and total oxidizable precursor assay. The estimated median potential children's exposure to PFAS via dermal exposure through school uniforms was 1.03 ng/kg bw/day. Substance flow analysis estimated that ∼3 tonnes/year (ranging from 0.05 to 33 tonnes/year) of PFAS are used in US children's uniforms, mostly of polymeric PFAS but with ∼0.1 tonne/year of mobile, nonpolymeric PFAS.


Assuntos
Fluorocarbonos , Canadá , Ácidos Carboxílicos/análise , Criança , Vestuário , Monitoramento Ambiental , Flúor/análise , Fluorocarbonos/análise , Humanos
4.
Environ Sci Technol ; 56(2): 974-983, 2022 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-34961317

RESUMO

Firefighter turnout gear is essential for reducing occupational exposure to hazardous chemicals during training and fire events. Per-and polyfluoroalkyl substances (PFASs) are observed in firefighter serum, and possible occupational sources include the air and dust of fires, aqueous film-forming foam, and turnout gear. Limited data exist for nonvolatile and volatile PFASs on firefighter turnout gear and the disposition of fluorine on the individual layers of turnout gear. Further implications for exposure to fluorine on turnout gear are not well understood. Three unused turnout garments purchased in 2019 and one purchased in 2008, were analyzed for 50 nonvolatile and 15 volatile PFASs by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-qTOF-MS) and gas chromatography-mass spectrometry (GC-MS), respectively. Particle-induced gamma ray emission (PIGE), a surface technique, and instrumental neutron activation analysis (INAA), a bulk technique, were used to measure total fluorine. Bulk characterization of the layers by pyrolysis-GC/MS (py-GC/MS) was used to differentiate fluoropolymer (e.g., PTFE) films from textile layers finished with side-chain polymers. The outer layer, moisture barrier, and thermal layers of the turnout gear all yielded measured concentrations of volatile PFASs that exceeded nonvolatile PFAS concentrations, but the summed molar concentrations made up only a small fraction of total fluorine (0.0016-6.7%). Moisture barrier layers comprised a PTFE film, as determined by py-GC-MS, and gave the highest individual nonvolatile (0.159 mg F/kg) and volatile PFAS (20.7 mg F/kg) as well as total fluorine (122,000 mg F/kg) concentrations. Outer and thermal layers comprised aromatic polyamide-based fibers (aramid) treated with side-chain fluoropolymers and had lower levels of individual nonvolatile and volatile PFASs. Equal concentrations of total fluorine by both PIGE and INAA on the outer and thermal layers is consistent with treatment with a side-chain fluoropolymer coating. New turnout gear should be examined as a potential source of firefighter occupational exposure to nonvolatile and volatile PFASs in future assessments.


Assuntos
Bombeiros , Fluorocarbonos , Exposição Ocupacional , Cromatografia Líquida , Flúor/análise , Fluorocarbonos/análise , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Exposição Ocupacional/análise
5.
Nucl Phys A ; 10212022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35967889

RESUMO

Excitation function of the 54Fe(p,α)51Mn reaction was measured from 9.5 to 18 MeV E 0 , p + by activating a foil stack of 54Fe electrodeposited on copper substrates. Residual radionuclides were quantified by HPGe gamma ray spectrometry. Both 51Mn (t 1/2 = 46.2 min, 〈 E ß + 〉 = 963.7 keV , I ß + = 97 % ; E γ = 749.1 keV, I γ = 0.265%) and its radioactive daughter, 51Cr (t 1/2 = 27.704d, E γ = 320.1 keV, I γ = 9.91%), were used to indirectly quantify formation of 51Mn. Results agree within uncertainty to the only other measurement in literature and predictions of default TALYS theoretical code. Final relative uncertainties are within ±12%.

6.
Anal Chem ; 92(7): 4949-4953, 2020 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-32100538

RESUMO

A novel method for quickly and quantitatively measuring aqueous lead in drinking water has been developed. A commercially available activated carbon felt has been found to effectively capture lead from tap water, and partnered with X-ray fluorescence (XRF) spectrometry, it provides quantitative measurement of aqueous lead in drinking water. Specifically, for a 2 L volume of tap water, the linear range of detection was found to be from 1-150 ppb, encompassing the current EPA limit for lead in drinking water (15 ppb). To make a reproducible and easy to use method for filtering, a 2 L bottle cap with a 1.25 cm diameter hole was used for filtering. Utilizing this filtration method, 75 solutions from 0 to 150 ppb lead gave a 91% sensitivity, 97% specificity, and 93% accuracy, and all the misclassified samples fell between 10 and 15 ppb. This method has also proved reliable for detecting calcium as well as several other divalent metals in drinking water including copper, zinc, iron, and manganese.


Assuntos
Água Potável/química , Monitoramento Ambiental , Chumbo/análise , Espectrometria por Raios X
7.
Environ Sci Technol ; 54(11): 6908-6918, 2020 06 02.
Artigo em Inglês | MEDLINE | ID: mdl-32352763

RESUMO

In this study, we present a holistic analysis of the stock and emissions of poly- and perfluoroalkyl substances (PFAS) in California carpet in 2000-2030. Our high estimate is that, in 2017, the total PFAS accumulated in in-use carpet stock and landfilled carpet are ∼60 and ∼120 tonnes, respectively, and the resultant PFAS emissions are ∼800 and ∼100 kg, respectively. Among the three subclasses (side-chain polymers, PFAA, and nonpolymeric precursors), side-chain polymers dominate the in-use stock and landfill accumulation, while nonpolymeric precursors dominate the resultant emissions. Our low estimate is typically 8-15% of the high estimate and follows similar trends and subclass breakdowns as the high estimate. California's new Carpet Stewardship Regulations (24% recycling of end-of-life carpet) will reduce the landfilled PFAS by 6% (7 tonnes) at the cost of increasing the in-use stock by 2% (2 tonnes) in 2030. Aggressive PFAS phase-out by carpet manufacturers (i.e., reduce PFAS use by 15% annually starting 2020) could reduce the in-use PFAS stock by 50% by 2030, but its impact on the total landfilled PFAS is limited. The shift toward short-chain PFAS will also significantly reduce the in-use stock of long-chain PFAS in carpet by 2030 (only 25% of the total PFAS will be long-chain). Among the data gaps identified, a key one is the current area-based PFAS emission reporting (i.e., g PFAS emitted/area carpet/time), which leads to the counterintuitive result that reducing the PFAS use in carpet production has no impact on the PFAS emissions from in-use stock and landfills. Future technical studies should either confirm this or consider a mass-based unit (e.g., g PFAS emitted/g PFAS used/time) for better integration into regional substance flow analysis. Other noticeable data gaps include the lack of time-series data on emissions from the in-use stock and on leaching of side-chain polymers from landfills.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , California , Pisos e Cobertura de Pisos , Fluorocarbonos/análise , Instalações de Eliminação de Resíduos , Poluentes Químicos da Água/análise
8.
Environ Res ; 181: 108892, 2020 02.
Artigo em Inglês | MEDLINE | ID: mdl-31735346

RESUMO

In many states, environmental lead hazards are evaluated only after a lead-poisoned child has been identified. This passive approach is problematic because only a small fraction of children are tested for lead and those with elevated blood lead levels may have irreversible developmental damage. In order to reverse this paradigm, a new lead screening kit was developed. In this study, we validated the accuracy of the kit compared to the conventional methods. Forty-five participants used the kit to collect 3 dust, 3 soil and 2 paint samples in their homes. A researcher performed an in-situ analysis of the lead content in the paint and soil using a portable X-ray fluorescence (XRF) spectrometer. The soil, paint, and dust samples collected by the participants were then analyzed by XRF ex-situ. A strong linear correlation was found between the in-situ and ex-situ measurements for soil and dust samples, and a reasonable correlation was obtained for lead content of paint samples. The kit had very high degrees of specificity (true negative rate) and sensitivity (true positive rate) for detecting hazardous levels of lead in soil and dust samples. The agreement was more moderate for paint samples because some of the paint chips provided gave different readings from the front or back surface, but in-situ XRF only reads from the front surface. Overall, the kit gave a sensitivity of 87%, a specificity of 98% and an accuracy of 96% for detection of environmental lead hazards in samples collected from the home by untrained citizens. This suggests that widespread and inexpensive lead screening could be used to successfully identify hazards and ultimately decrease environmental lead exposure in children.


Assuntos
Exposição Ambiental , Intoxicação por Chumbo , Chumbo , Criança , Poeira , Humanos , Pintura , Solo
9.
Environ Sci Technol ; 51(16): 9022-9032, 2017 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-28712295

RESUMO

Papers and textiles that are treated with per- and polyfluoroalkyl substances (PFASs) are sources of human and environmental exposure. Data for individual PFASs, such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA), are not placed into the context of total fluorine for papers and textiles. Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were used to quantify volatile and ionic PFASs, respectively, and the total oxidizable precursor (TOP) assay was used to quantify precursors that form perfluoroalkyl carboxylates. Molar sums of PFASs obtained by GC-MS, LC-MS/MS, and precursors were compared to total fluorine (nmol F/cm2) determined by particle-induced gamma ray emission (PIGE) spectroscopy, measured before and after extraction. Volatile and ionic PFASs and unknown precursors accounted for 0-2.2%, 0-0.41%, and 0.021-14%, respectively, of the total nmol F/cm2 determined by PIGE. After extraction, papers and textiles retained 64 ± 28% to 110 ± 30% of the original nmol F/cm2 as determined by PIGE, indicating that the majority of fluorine remains associated with the papers and textiles. The sum of PFASs in the volatile, ionic, and precursor fraction, and total fluorine after extraction indicate that mass balance was achieved (within analytical error) of the initial total fluorine measured by PIGE.


Assuntos
Flúor , Têxteis , Poluentes Químicos da Água , Cromatografia Líquida , Fluorocarbonos , Humanos , Espectrometria de Massas em Tandem
10.
Inorg Chem ; 55(23): 12290-12298, 2016 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-27934442

RESUMO

Hydroxyapatite is an inorganic mineral closely resembling the mineral phase in bone. However, as a biological mineral, it is highly disordered, and its composition and atomistic structure remain poorly understood. Here, synchrotron X-ray total scattering and pair distribution function analysis methods provide insight into the nature of atomistic disorder in a synthetic bone mineral analogue, chemically substituted hydroxyapatite. By varying the effective hydrolysis rate and/or carbonate concentration during growth of the mineral, compounds with varied degrees of paracrystallinity are prepared. From advanced simulations constrained by the experimental pair distribution function and density functional theory, the paracrystalline disorder prevalent in these materials appears to result from accommodation of carbonate in the lattice through random displacement of the phosphate groups. Though many substitution modalities are likely to occur in concert, the most predominant substitution places carbonate into the mirror plane of an ideal phosphate site. Understanding the mineralogical imperfections of a biologically analogous hydroxyapatite is important not only to potential bone grafting applications but also to biological mineralization processes themselves.


Assuntos
Osso e Ossos/química , Durapatita/química , Fosfatos/química , Cristalização , Modelos Moleculares , Difração de Pó , Síncrotrons
11.
Environ Sci Technol ; 50(10): 5024-32, 2016 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-27095439

RESUMO

Discarded carpet and clothing are potential sources of per- and polyfluoroalkyl substances (PFASs) in landfill leachate, but little is known about their release when disposed in landfills. The concentrations of 70 PFASs in the aqueous phase of anaerobic model landfill reactors filled with carpet or clothing were monitored under biologically active and abiotic conditions. For carpet, total PFAS release was greater in live than abiotic reactors, with an average of 8.5 nmol/L and 0.62 nmol/L after 552 days, respectively. Release in live carpet reactors was primarily due to 5:3 fluorotelomer carboxylic acid (FTCA - 3.9 nmol/L) and perfluorohexanoic carboxylic acid (PFHxA - 2.9 nmol/L). For clothing, release was more dependent on sample heterogeneity than the presence of biological activity, with 0.63, 21.7, 2.6, and 6.3 nmol/L for two live and two abiotic reactors after 519 days, respectively. Release in the clothing reactors was largely due to perfluorooctatonic carboxylic acid (PFOA), with low relative concentrations of measured biotransformation precursors (FTCAs). For carpet and clothing reactors, the majority of PFAS release was not measured until after day 100. Results demonstrate that carpet and clothing are likely sources of PFASs in landfill leachate.


Assuntos
Pisos e Cobertura de Pisos , Instalações de Eliminação de Resíduos , Vestuário , Modelos Teóricos , Poluentes Químicos da Água
12.
Anal Chem ; 87(20): 10323-9, 2015 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-26403524

RESUMO

Isotope harvesting is a promising new method to obtain isotopes for which there is no reliable continuous supply at present. To determine the possibility of obtaining radiochemically pure radioisotopes from an aqueous beam dump at a heavy-ion fragmentation facility, preliminary experiments were performed to chemically extract a copper isotope from a large mixture of projectile fragmentation products in an aqueous medium. In this work a 93 MeV/u secondary beam cocktail was collected in an aqueous beam stop at the National Superconducting Cyclotron Laboratory (NSCL) located on the Michigan State University (MSU) campus. The beam cocktail consisted of ∼2.9% (67)Cu in a large mixture of co-produced isotopes ranging in atomic number from ∼19 to 34. The chemical extraction of (67)Cu was achieved via a two-step process: primary extraction using a divalent metal chelation disk followed by anion-exchange chromatography. A significant fraction (74 ± 4%) of the (67)Cu collected in the aqueous beam stop was recovered with >99% radiochemical purity. To illustrate the utility of this product, the purified (67)Cu material was then used to radiolabel an anti-EGFR antibody, Panitumumab, and injected into mice bearing colon cancer xenografts. The tumor uptake at 5 days postinjection was found to be 12.5 ± 0.7% which was in very good agreement with previously reported studies with this radiolabeled antibody. The present results demonstrate that harvesting isotopes from a heavy-ion fragmentation facility could be a promising new method for obtaining high-quality isotopes that are not currently available by traditional methods.


Assuntos
Radioisótopos de Cobre/isolamento & purificação , Ciclotrons , Laboratórios , Animais , Anticorpos Monoclonais/administração & dosagem , Anticorpos Monoclonais/química , Anticorpos Monoclonais/farmacocinética , Linhagem Celular Tumoral , Neoplasias do Colo/metabolismo , Neoplasias do Colo/radioterapia , Radioisótopos de Cobre/administração & dosagem , Radioisótopos de Cobre/química , Radioisótopos de Cobre/farmacocinética , Feminino , Humanos , Camundongos , Camundongos Nus , Neoplasias Experimentais/metabolismo , Neoplasias Experimentais/radioterapia , Panitumumabe , Compostos Radiofarmacêuticos/administração & dosagem , Compostos Radiofarmacêuticos/química , Compostos Radiofarmacêuticos/farmacocinética , Distribuição Tecidual
13.
Nucleic Acids Res ; 40(19): 9964-79, 2012 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-22885300

RESUMO

Extragenic sequences in genomes, such as microRNA and CRISPR, are vital players in the cell. Repetitive extragenic palindromic sequences (REPs) are a class of extragenic sequences, which form nucleotide stem-loop structures. REPs are found in many bacterial species at a high copy number and are important in regulation of certain bacterial functions, such as Integration Host Factor recruitment and mRNA turnover. Although a new clade of putative transposases (RAYTs or TnpA(REP)) is often associated with an increase in these repeats, it is not clear how these proteins might have directed amplification of REPs. We report here the structure to 2.6 Å of TnpA(REP) from Escherichia coli MG1655 bound to a REP. Sequence analysis showed that TnpA(REP) is highly related to the IS200/IS605 family, but in contrast to IS200/IS605 transposases, TnpA(REP) is a monomer, is auto-inhibited and is active only in manganese. These features suggest that, relative to IS200/IS605 transposases, it has evolved a different mechanism for the movement of discrete segments of DNA and has been severely down-regulated, perhaps to prevent REPs from sweeping through genomes.


Assuntos
DNA Bacteriano/química , Proteínas de Escherichia coli/química , Escherichia coli/enzimologia , Sequências Repetidas Invertidas , Transposases/química , Sequência de Aminoácidos , Domínio Catalítico , Clivagem do DNA , DNA Bacteriano/metabolismo , Desoxirribonucleases/química , Desoxirribonucleases/metabolismo , Escherichia coli/genética , Proteínas de Escherichia coli/metabolismo , Modelos Moleculares , Dados de Sequência Molecular , Alinhamento de Sequência , Transposases/metabolismo
14.
Artigo em Inglês | MEDLINE | ID: mdl-38695667

RESUMO

The main sources of lead exposure for children occur in the home environment, yet no low-cost analytical methods exist to screen homes for lead hazards. Previously, an inexpensive (~$20), quantitative lead screening kit was developed in which residents collect soil, paint, and dust samples that are returned to a laboratory for lead analysis using X-ray fluorescence spectroscopy (XRF). This screening kit was initially validated in 2020; it was determined that in situ and ex situ XRF lead measurements on the same samples exhibited strong sensitivity, specificity, and accuracy. As a follow-up to the initial validation, an implementation study and further statistical analyses were conducted. Correlation analysis using the results from nearly 400 screening kits identified an overall lack of correlation between sample types, reinforcing the utility of all eight sample locations. Principal component analysis searched for underlying correlations in sample types and provided evidence that both interior and exterior paint are major sources of lead hazards for Indiana homes. The implementation study compared the results of the government-standard lead inspection and risk assessment (LIRA) and the lead screening kit in 107 Indiana homes. In the United States, the LIRA is a thorough inspection of paint, dust, and soil that is usually state mandated in response to a child's elevated blood level and is used to identify where remediation efforts should be focused. The lead screening kit and LIRA agreed on the presence of lead in 79 of the 107 homes tested (74%). Discrepancies in agreement are likely the result of differences in the sample location and number of samples collected by each method. Overall, these results suggest that the lead screening kit is an acceptable resource that could be used to expand the services health departments provide for lead prevention. Integr Environ Assess Manag 2024;00:1-10. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

15.
Sci Total Environ ; 895: 164903, 2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37355115

RESUMO

We measured perfluoroalkyl substances (PFAS) in prey and predator fish from Lake Michigan (USA) to investigate the occurrence and biomagnification of these compounds in this important ecosystem. Twenty-one PFAS were analyzed in 117 prey fish obtained from sites across Lake Michigan and in 87 salmonids collected in four lake quadrants. The mean concentration of sum (∑) PFAS above the method detection limit was 12.7 ± 6.96 ng g-1 wet weight in predator fish (all of which were salmonids) and 10.7 ± 10.4 ng g-1 in prey fish, with outlier levels found in slimy sculpin, Cottus cognatus (187 ± 12.2 ng g-1 ww). Perfluorooctanoic sulfonic acid (PFOS) was the most frequently detected and most abundant compound of the 21 PFAS, occurring in 98 % of individuals with a mean concentration of 9.86 ± 6.36 ng g-1 ww without outliers. Perfluoroalkyl carboxylates (PFCA) concentrations were higher in prey fish than in predators, with some compounds such as perfluorooctanoic acid (PFOA) being detected in higher frequency in prey fish. Besides PFOS, detection of several long-chain (C8-C12) PFCAs were observed in >80 % of the prey fish. Overall, the observed concentrations in Lake Michigan fish were lower than those reported in other Laurentian Great Lakes except for Lake Superior. Biomagnification factors (BMFs) for PFOS exceeded 1.0 (range, 1.80 to 5.12) in all predator-prey relationships analyzed, indicating biomagnification of these compounds, whereas BMFs of other long-chain PFCAs varied according to the fish species. PFAS were found in all fish species measured from Lake Michigan and commonly biomagnified from prey to predator fish, strongly suggesting a dietary connection.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Salmonidae , Poluentes Químicos da Água , Animais , Lagos , Michigan , Ecossistema , Bioacumulação , Peixes , Fluorocarbonos/análise , Ácidos Sulfônicos , Monitoramento Ambiental , Poluentes Químicos da Água/análise , Ácidos Alcanossulfônicos/análise
16.
Environ Sci Technol Lett ; 10(4): 343-349, 2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-37970096

RESUMO

A suite of analytical techniques was used to obtain a comprehensive picture of per- and polyfluoroalkyl substances (PFAS) in selected Canadian food packaging used for fast foods (n = 42). Particle-induced gamma ray emission spectroscopy revealed that 55% of the samples contained <3580, 19% contained 3580-10 800, and 26% > 10 800 µg F/m2. The highest total F (1 010 000-1 300 000 µg F/m2) was measured in molded "compostable" bowls. Targeted analysis of 8 samples with high total F revealed 4-15 individual PFAS in each sample, with 6:2 fluorotelomer methacrylate (FTMAc) and 6:2 fluorotelomer alcohol (FTOH) typically dominating. Up to 34% of the total fluorine was released from samples after hydrolysis, indicating the presence of unknown precursors. Nontargeted analysis detected 22 PFAS from 6 different groups, including degradation products of FTOH. Results indicate the use of side-chain fluorinated polymers and suggest that these products can release short-chain compounds that ultimately can be transformed to compounds of toxicological concern. Analysis after 2 years of storage showed overall decreases in PFAS consistent with the loss of volatile compounds such as 6:2 FTMAc and FTOH. The use of PFAS in food packaging such as "compostable" bowls represents a regrettable substitution of single-use plastic food packaging.

17.
Integr Environ Assess Manag ; 18(6): 1500-1512, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35029321

RESUMO

A review of the published literature on the trophic magnification factor (TMF) for per- and polyfluoroalkyl substances (PFAS) was conducted to assess how biomagnification varies across aquatic systems worldwide. Although the TMF has been recognized as the most reliable tool for assessing the biomagnification of organic contaminants, peer-reviewed studies reporting TMFs for PFAS are few and with limited geographical distribution. We found 25 published studies of the biomagnification of 35 specific PFAS, for which the TMF was generated through linear regression of individual log-PFAS concentration and the δ15 N-based trophic position of each organism in the food webs. Studies were concentrated mainly in China, North America, and Europe, and the most investigated compound was perfluorooctane sulfonate (PFOS), which was frequently shown to be biomagnified in the food web (TMFs ranging from 0.8 to 20). Other long-chain carboxylates displayed substantial variation in trophic magnification. Observed differences in the TMF were associated with length of the food web, geographic location, sampling methodologies, tissue analyzed, and distance from known direct PFAS inputs. In addition to biomagnification of legacy PFAS, precursor substances were observed to bioaccumulate in the food web, which suggests they may biotransform to more persistent PFAS compounds in upper trophic levels. This review discusses the variability of environmental characteristics driving PFAS biomagnification in natural ecosystems and highlights the different approaches used by each study, which can make comparisons among studies challenging. Suggestions on how to standardize TMFs for PFAS are also provided in this review. Integr Environ Assess Manag 2022;18:1500-1512. © 2022 SETAC.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Fluorocarbonos/análise , Ecossistema , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Cadeia Alimentar
18.
Environ Sci Technol Lett ; 9(4): 320-326, 2022 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-37599856

RESUMO

Facemasks are important tools for fighting against disease spread, including Covid-19 and its variants, and some may be treated with per- and polyfluoroalkyl substances (PFAS). Nine facemasks over a range of prices were analyzed for total fluorine and PFAS. The PFAS compositions of the masks were then used to estimate exposure and the mass of PFAS discharged to landfill leachate. Fluorine from PFAS accounted only for a small fraction of total fluorine. Homologous series of linear perfluoroalkyl carboxylates and the 6:2 fluorotelomer alcohol indicated a fluorotelomer origin. Inhalation was estimated to be the dominant exposure route (40%-50%), followed by incidental ingestion (15%-40%) and dermal (11%-20%). Exposure and risk estimates were higher for children than adults, and high physical activity substantially increased inhalation exposure. These preliminary findings indicate that wearing masks treated with high levels of PFAS for extended periods of time can be a notable source of exposure and have the potential to pose a health risk. Despite modeled annual disposal of ~29-91 billion masks, and an assuming 100% leaching of individual PFAS into landfill leachate, mask disposal would contribute only an additional 6% of annual PFAS mass loads and less than 11 kg of PFAS discharged to U.S. wastewater.

19.
Environ Sci Process Impacts ; 24(11): 2032-2042, 2022 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-36218049

RESUMO

Numerous per- and polyfluoroalkyl substances (PFASs) occur in consumer food packaging due to intentional and unintentional addition, despite increasing concern about their health and environmental hazards. We present a substance flow analysis framework to assess the flows of PFASs contained in plant fiber-based and plastic food packaging to the waste stream and environment. Each year between 2018 and 2020, an estimated 9000 (range 1100-25 000) and 940 (range 120-2600) tonnes per year of polymeric PFASs were used in 2% of food packaging in the U.S. and Canada, respectively. At least 11 tonnes per year of non-polymeric PFASs also moved through the food packaging life cycle. Approximately 6100 (range 690-13 000) and 700 (range 70-1600) tonnes per year of these PFASs were landfilled or entered composting facilities in the U.S. and Canada, respectively, with the potential to contaminate the environment. The results suggest that minimal food packaging contains intentionally added PFASs which, nonetheless, has the potential to contaminate the entire waste stream. Further, this indicates that PFASs are not needed for most food packaging. These results serve as a benchmark to judge the effectiveness of future industry and government initiatives to limit PFAS use in food packaging.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Fluorocarbonos/análise , Embalagem de Alimentos , Canadá , Poluentes Químicos da Água/análise
20.
Sci Rep ; 11(1): 15749, 2021 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-34344931

RESUMO

Many radioisotopes with potential medical applications are difficult to produce routinely, especially those on the proton-rich side of the valley of stability. Current production methods typically use light-ion (protons or deuteron) reactions on materials of similar mass to the target radioisotope, which limits the elemental target material available and may require the use of targets with poor thermal properties (as is the case for the production of radiobromine). These reactions may also create significant amounts of proton-rich decay products which require chemical separation from the desired product in a highly radioactive environment. A promising alternative method using heavy-ion fusion-evaporation reactions for the production of the medically relevant bromine radioisotopes 76Br (t1/2 = 16.2 h) and 77Br (t1/2 = 57.0 h) is presented. Heavy-ion beams of 28Si and 16O were used to bombard natural chromium and copper targets just above the Coulomb barrier at the University of Notre Dame's Nuclear Science Laboratory to produce these bromine and precursor radioisotopes by fusion-evaporation reactions. Production yields for these reactions were measured and compared to PACE4 calculations. In addition to using more robust targets for irradiation, a simple physical-chemical separation method is proposed that will lead to very high radiopurity yields. A summary of accelerator facility requirements needed for routine production of these radioisotopes is also presented.

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