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1.
Phys Rev Lett ; 132(21): 214001, 2024 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-38856244

RESUMO

The microscopic stress field inhomogeneity in the interfacial region adjacent to the liquid surface is the fundamental origin of the liquid surface tension, but because of broadening due to capillary fluctuations, a detailed molecular level understanding of the stress field remains elusive. In this work, we deconvolute the capillary fluctuations to reveal the intrinsic stress field and show that the atomic-level contributions to the surface tension are similar in functional form across a variety of monatomic systems. These contributions are confined to an interfacial region approximately 1.5±0.1 times the particle diameter for all systems studied. In addition, the intrinsic density and stress profiles show a strong spatial correlation that should be useful in the development of a statistical mechanical theory for the prediction of surface stress and surface tension.

2.
Environ Monit Assess ; 196(2): 181, 2024 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-38246977

RESUMO

Toenails are a common monitoring tool for arsenic exposure, but the risk of external contamination of toenails has cast doubt on its usefulness. The main objective of this study is to investigate the micro-distribution of arsenic through the dorsoventral plane of nail clippings to understand endogenous vs exogenous sources. We used laser-ablation inductively coupled plasma mass spectrometry to measure arsenic through a dorsoventral cross-section of the nail plate collected from reference (N = 17) and exposed individuals (N = 35). Our main results showed (1) bulk toenail concentrations measured using ICP-MS in this study ranged from 0.54 to 4.35 µg/g; (2) there was a double-hump pattern in arsenic concentrations, i.e., dorsal and ventral layers had higher arsenic than the inner layer; (3) the double-hump was more pronounced in the exposed group (ventral: 6.25 µg/g; inner: 0.75 µg/g; dorsal: 0.95 µg/g) than the reference group (ventral: 0.58 µg/g; inner: 0.15 µg/g; dorsal: 0.29 µg/g) on average; (4) the distribution was, in part, associated with different binding affinity of nail layers (i.e., ventral > dorsal > inner); (5) most individuals in the higher exposure group showed > 25% contamination in ventral and dorsal nail layers; and (6) there were no statistically significant correlations between LA-ICP-MS arsenic with either bulk toenail arsenic or urine arsenic from the same individuals. Our results on micro-distribution and binding affinity provide insight into the impact of external contamination on arsenic concentrations and show how LA-ICP-MS can access the protected inner nail layer to provide a more accurate result.


Assuntos
Arsênio , Terapia a Laser , Humanos , Monitoramento Biológico , Unhas , Monitoramento Ambiental , Espectrometria de Massas
3.
J Phys Chem A ; 127(46): 9831-9841, 2023 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-37938899

RESUMO

Amorphous silica (a-SiO2) surfaces, when grafted with select metals on the active sites of the functionalized surfaces, can act as useful heterogeneous catalysts. From a molecular modeling perspective, one challenge has been generating a-SiO2 slab models with controllable surface roughness to facilitate the study of the effect of surface morphology on the material properties. Previous computational methods either generate relatively flat surfaces or periodically corrugated surfaces that do not mimic the full range of potential surface roughness of the amorphous silica material. In this work, we present a new method, inspired by the capillary fluctuation theory of interfaces, in which rough silica slabs are generated by cleaving a bulk amorphous sample using a cleaving plane with Fourier components randomly generated from a Gaussian distribution. The width of this Gaussian distribution (and thus the degree of surface roughness) can be tuned by varying the surface roughness parameter α. Using the van Beest, Kramer, and van Santen (BKS) force field, we create a large number of silica slabs using cleaving surfaces of varying roughness (α) and using two different system sizes. These surfaces are then characterized to determine their roughness (mean-squared displacement), density profile, and ring size distribution. This analysis shows a higher concentration of surface defects (under-/overcoordinated atoms and strained rings) as the surface roughness increases. To examine the effect of the roughness on surface reactivity, we re-equilibriate a subset of these slabs using the reactive force field ReaxFF and then expose the slabs to water and observe the formation of surface silanols. We observe that the rougher surfaces exhibit higher silanol concentrations as well as bimodal acidity.

4.
Environ Res ; 217: 114835, 2023 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-36400218

RESUMO

Biomagnification of mercury (Hg) through lake food webs is understudied in rapidly changing northern regions, where wild-caught subsistence fish are critical to food security. We investigated estimates and among-lake variability of Hg biomagnification rates (BMR), relationships between Hg BMR and Hg levels in subsistence fish, and environmental drivers of Hg BMR in ten remote subarctic lakes in Northwest Territories, Canada. Lake-specific linear regressions between Hg concentrations (total Hg ([THg]) in fish and methyl Hg ([MeHg]) in primary consumers) and baseline-adjusted δ15N ratios were significant (p < 0.001, r2 = 0.58-0.88), indicating biomagnification of Hg through food webs of all studied lakes. Quantified using the slope of Hg-δ15N regressions, Hg BMR ranged from 0.16 to 0.25, with mean ± standard deviation of 0.20 ± 0.03). Using fish [MeHg] rather than [THg] lowered estimates of Hg BMR by ∼10%, suggesting that the use of [THg] as a proxy for [MeHg] in fish can influence estimates of Hg BMR. Among-lake variability of size-standardized [THg] in resident fish species from different trophic guilds, namely Lake Whitefish (Coregonus clupeaformis) and Northern Pike (Esox lucius), was not significantly explained by among-lake variability in Hg BMR. Stepwise multiple regressions indicated that among-lake variability of Hg BMR was best explained by a positive relationship with catchment forest cover (p = 0.009, r2 = 0.59), likely reflecting effects of forest cover on water chemistry of downstream lakes and ultimately, concentrations of biomagnifying MeHg (and percent MeHg of total Hg) in resident biota. These findings improve our understanding of Hg biomagnification in remote subarctic lakes.


Assuntos
Mercúrio , Poluentes Químicos da Água , Animais , Mercúrio/análise , Cadeia Alimentar , Bioacumulação , Canadá , Monitoramento Ambiental , Peixes , Poluentes Químicos da Água/análise
5.
Environ Res ; 233: 116463, 2023 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-37343750

RESUMO

BACKGROUND: Prenatal and childhood mercury (Hg) exposures have been associated with negative impacts on child neurodevelopment. It is unclear if associations persist at the low Hg exposures typical in Western countries. OBJECTIVE: To examine associations between prenatal/childhood blood Hg concentrations and child IQ in Canadian male and female children while considering the potential modifying role of prenatal fish consumption. METHODS: We analyzed data from the Maternal-Infant Research on Environmental Chemicals study. Hg was measured in first trimester (n = 527), cord (n = 430), and child (at 3-4 years of age, n = 355) blood and examined sex-stratified associations between blood Hg and children's Full Scale IQ (FSIQ), Verbal IQ (VIQ), Performance IQ (PIQ), and General Language Composite (GLC) scores (assessed with WPPSI-III). Prenatal Hg analyses were further stratified by prenatal fish consumption (low: 0-2, moderate: 3-7, or high: ≥8 times/month). RESULTS: Higher cord blood Hg concentrations were associated with lower PIQ (ß = -3.27; 95%CI: 6.44, -0.09) in male children with the lowest prenatal fish consumption. Progressively stronger positive associations were observed with PIQ in male children for moderate (ß = 1.08; 95%CI: 0.10, 2.26) and high (ß = 3.07; 95%CI: 1.95, 4.19) prenatal fish consumption. Cord blood Hg concentrations were positively associated with female children's FSIQ (ß = 1.29; 95% CI: 0.77, 1.81) and PIQ (ß = 2.01; 95% CI: 1.19, 2.83); however, when stratified only in the highest fish consumption subgroup. Among female children, higher child blood Hg concentrations were associated with an approximately 1-point increase in FSIQ, VIQ, and GLC. CONCLUSIONS: Prenatal exposure to low levels of Hg was associated with lower PIQ scores in male children with low prenatal fish intake. Positive associations between cord and child blood Hg concentrations and IQ were primarily observed in female children and may be due to beneficial effects of prenatal fish intake.


Assuntos
Mercúrio , Efeitos Tardios da Exposição Pré-Natal , Humanos , Gravidez , Animais , Masculino , Feminino , Mercúrio/análise , Efeitos Tardios da Exposição Pré-Natal/epidemiologia , Canadá , Testes de Inteligência , Escalas de Wechsler
6.
J Chem Phys ; 159(18)2023 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-37955327

RESUMO

The probability of inserting, without overlap, a hard spherical particle of diameter σ in a hard-sphere fluid of diameter σ0 and packing fraction η determines its excess chemical potential at infinite dilution, µex(σ, η). In our previous work [R. L. Davidchack and B. B. Laird, J. Chem. Phys. 157, 074701 (2022)], we used Widom's particle insertion method within molecular dynamics simulations to obtain high precision results for µex(σ, η) with σ/σ0 ≤ 4 and η ≤ 0.5. In the current work, we investigate the behavior of this quantity at small σ. In particular, using the inclusion-exclusion principle, we relate the insertion probability to the hard-sphere fluid distribution functions and thus derive the higher-order terms in the Taylor expansion of µex(σ, η) at σ = 0. We also use direct evaluation of the excluded volume for pairs and triplets of hard spheres to obtain simulation results for µex(σ, η) at σ/σ0 ≤ 0.2247 that are of much higher precision than those obtained earlier with Widom's method. These results allow us to improve the quality of the small-σ correction in the empirical expression for µex(σ, η) presented in our previous work.

7.
Environ Res ; 203: 111800, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34364863

RESUMO

Concentrations of total mercury were measured in blood and hair samples collected as part of a human biomonitoring project conducted in First Nations communities of the Mackenzie Valley, Northwest Territories, Canada. Hair (n = 443) and blood (n = 276) samples were obtained from six communities in the Dehcho region and three communities in the Sahtú region of the Mackenzie Valley. The aim of this paper was to calculate hair to blood mercury ratios (for matched samples) and determine if: 1) ratios differed significantly between the two regions; 2) ratios differed from the 250:1 ratio proposed by the WHO; and, 3) point estimates of hair to blood mercury ratios could be used to estimate blood mercury concentrations. In addition, this paper aims to determine if there were seasonal patterns in hair mercury concentrations in these regions and if so, if patterns were related to among-season variability in fish consumption. The majority of mercury levels in hair and blood were below relevant health-based guidance values. The geometric mean hair (most recent segment) to blood mercury ratio (stratified by region) was 619:1 for the Dehcho region and 1220:1 for the Sahtú region. Mean log-transformed hair to blood mercury ratios were statistically significantly different between the two regions. Hair to blood ratios calculated in this study were far higher (2-5 times higher) than those typically reported in the literature and there was a large amount of inter-individual variation in calculated ratios (range: 114:1 to 4290:1). Using the 250:1 ratio derived by the World Health Organisation to estimate blood mercury concentrations from hair mercury concentrations would substantially over-estimate blood mercury concentrations in the studied regions. However, geometric mean site-specific hair to blood mercury ratios can provide estimates of measures of central tendency for blood mercury concentrations from hair mercury concentrations at a population level. Mercury concentrations were determined in segments of long hair samples to examine exposure of participants to mercury over the past year. Hair segments were assigned to six time periods and the highest hair mercury concentrations were generally observed in hair segments that aligned with September/October and November/December, whereas the lowest hair mercury concentrations were aligned with March/April and May/June. Mean log-transformed hair mercury concentrations were statistically significantly different between time periods. Between time periods (e.g., September/October vs. March/April), the geometric mean mercury concentration in hair differed by up to 0.22 µg/g, and the upper margins of mercury exposure (e.g., 95th percentile of hair mercury) varied by up to 0.86 µg/g. Results from self-reported fish consumption frequency questionnaires (subset of participants; n = 170) showed total fish intake peaked in late summer, decreased during the winter, and then increased during the spring. Visual assessment of results indicated that mean hair mercury concentrations followed this same seasonal pattern. Results from mixed effects models, however, indicated that variability in hair mercury concentrations among time periods was not best explained by total fish consumption frequency. Instead, seasonal trends in hair mercury concentrations may be more related to the consumption of specific fish species (rather than total wild-harvested fish in general). Future work should examine whether seasonal changes in the consumption of specific fish species are associated with seasonal changes in hair mercury concentrations.


Assuntos
Mercúrio , Animais , Canadá , Monitoramento Ambiental , Peixes , Humanos , Mercúrio/análise , Territórios do Noroeste , Estudos Retrospectivos
8.
J Chem Phys ; 157(7): 074701, 2022 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-35987596

RESUMO

The excess chemical potential µex(σ, η) of a test hard spherical particle of diameter σ in a fluid of hard spheres of diameter σ0 and packing fraction η can be computed with high precision using Widom's particle insertion method [B. Widom, J. Chem. Phys. 39, 2808 (1963)] for σ between 0 and just larger than 1 and/or small η. Heyes and Santos [J. Chem. Phys. 145, 214504 (2016)] analytically showed that the only polynomial representation of µex consistent with the limits of σ at zero and infinity has a cubic form. On the other hand, through the solvation free energy relationship between µex and the surface free energy γ of hard-sphere fluids at a hard spherical wall, we can obtain precise measurements of µex for large σ, extending up to infinity (flat wall) [R. L. Davidchack and B. B. Laird, J. Chem. Phys. 149, 174706 (2018)]. Within this approach, the cubic polynomial representation is consistent with the assumptions of morphometric thermodynamics. In this work, we present the measurements of µex that combine the two methods to obtain high-precision results for the full range of σ values from zero to infinity, which show statistically significant deviations from the cubic polynomial form. We propose an empirical functional form for the µex dependence on σ and η, which better fits the measurement data while remaining consistent with the analytical limiting behavior at zero and infinite σ.

9.
J Chem Phys ; 157(5): 054702, 2022 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-35933196

RESUMO

To explore the curvature dependence of solid-fluid interfacial thermodynamics, we calculate, using Grand Canonical Monte Carlo simulation, the surface free energy for a 2d hard-disk fluid confined in a circular hard container of radius R as a function of the bulk packing fraction η and wall curvature C̄=-1/R. (The curvature is negative because the surface is concave.) Combining this with our previous data [Martin et al., J. Phys. Chem. B 124, 7938-7947 (2020)] for the positive curvature case (a hard-disk fluid at a circular wall, C̄=+1/R), we obtain a complete picture of surface thermodynamics in this system over the full range of positive and negative wall curvatures. Our results show that γ is linear in C̄ with a slope that is the same for both positive and negative wall curvatures, with deviations seen only at high negative curvatures (strong confinement) and high density. This observation indicates that the surface thermodynamics of this system is consistent with the predictions of so-called morphometric thermodynamics at both positive and negative curvatures. In addition, we show that classical density functional theory and a generalized scaled particle theory can be constructed that give excellent agreement with the simulation data over most of the range of curvatures and densities. For extremely high curvatures, where only one or two disks can occupy the container at maximum packing, it is possible to calculate γ exactly. In this limit, the simulations and density functional theory calculations are in remarkable agreement with the exact results.

10.
J Chem Phys ; 157(13): 134703, 2022 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-36208999

RESUMO

The equilibrium silica liquid-liquid interface between the high-density liquid (HDL) phase and the low-density liquid (LDL) phase is examined using molecular-dynamics simulation. The structure, thermodynamics, and dynamics within the interfacial region are characterized in detail and compared with previous studies on the liquid-liquid phase transition (LLPT) in bulk silica, as well as traditional crystal-melt interfaces. We find that the silica HDL-LDL interface exhibits a spatial fragile-to-strong transition across the interface. Calculations of dynamics properties reveal three types of dynamical heterogeneity hybridizing within the silica HDL-LDL interface. We also observe that as the interface is traversed from HDL to LDL, the Si/O coordination number ratio jumps to an unexpectedly large value, defining a thin region of the interface where HDL and LDL exhibit significant mixing. In addition, the LLPT phase coexistence is interpreted in the framework of the traditional thermodynamics of alloys and phase equilibria.

11.
J Chem Phys ; 157(8): 084709, 2022 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-36050002

RESUMO

We present a classical molecular-dynamics study of the collective dynamical properties of the coexisting liquid phase at equilibrium body-centered cubic (BCC) Fe crystal-melt interfaces. For the three interfacial orientations (100), (110), and (111), the collective dynamics are characterized through the calculation of the intermediate scattering functions, dynamical structure factors, and density relaxation times in a sequential local region of interest. An anisotropic speedup of the collective dynamics in all three BCC crystal-melt interfacial orientations is observed. This trend differs significantly from the previously observed slowing down of the local collective dynamics at the liquid-vapor interface [del Rio and González, Acta Mater. 198, 281 (2020)]. Examining the interfacial density relaxation times, we revisit the validity of the recently developed time-dependent Ginzburg-Landau theory for the solidification crystal-melt interface kinetic coefficients, resulting in excellent agreement with both the magnitude and the kinetic anisotropy of the crystal-melt interface kinetic coefficients measured from the non-equilibrium molecular-dynamics simulations.

12.
Public Health Nutr ; 24(6): 1229-1239, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33427192

RESUMO

OBJECTIVE: Game bird consumption is an important part of the diet of Indigenous populations in Canada and, as part of country food consumption, is associated with improved nutritional status. The objective of this project was to document the consumption of game birds for Dene First Nations in the Northwest Territories (NWT), Canada. DESIGN: Participants were invited to complete a FFQ using an iPad to document the types of country foods consumed, as well as consumption frequency and preparation methods, including thirteen types of game birds. SETTING: The project was implemented in nine communities in the Dehcho and Sahtú regions of the NWT, Canada. PARTICIPANTS: A total of 237 children and adult participants from Dene First Nations in the Mackenzie Valley region of the NWT took part in the current study. RESULTS: FFQ findings indicated that game birds were frequently consumed in both Dehcho and Sahtú communities. Canada goose and mallard were found to be consumed by the largest number of participants. Five different species (including Canada goose and mallard) were found to be consumed by at least 25 % of participants over the last year. When consuming game birds, most participants reported consuming the meat as well as most, if not all, other parts of the bird. CONCLUSIONS: Differences were observed since the last country food assessment in the 1990s in the same regions. These findings increase knowledge of the current Dene diet patterns and support the understanding of diet transition.


Assuntos
Dieta , Estado Nutricional , Adulto , Animais , Aves , Canadá , Criança , Humanos , Territórios do Noroeste/epidemiologia
13.
Environ Res ; 190: 110008, 2020 11.
Artigo em Inglês | MEDLINE | ID: mdl-32763278

RESUMO

A human biomonitoring project investigating environmental exposures to metals from hair, blood and urine samples was implemented in the Northwest Territories, Canada, between January 2016 and March 2018. This study reports the metal biomarker levels from nine Dene communities located in the Dehcho and Sahtú regions to identify contaminants of interest. Levels of metals in the urine (n = 198), blood (n = 276) and hair (n = 443) samples were generally similar to those seen in other biomonitoring studies in Canada, but lead levels in blood (GM = 16 µg/L; 95th percentile = 71 µg/L) and urine (GM = 0.59 µg/L, 0.69 µg/g of creatinine; 95th percentile = 4.2 µg/L, 4.0 µg/g of creatinine) were higher than those observed in the Canadian Health Measure Survey (CHMS, cycles 2 and 5). Hair mercury (but not blood mercury) appeared higher than observed in participants from the CHMS cycle 5. The vast majority of participants had biomarker levels below the biomonitoring guidance values established for mercury and lead. Based on a comparative analysis of biomarker statistics relative to a nationally-representative survey, metals and essential trace elements of particular interest for follow-up research include: lead, manganese, mercury, and selenium. This project provided baseline biomarker levels in participating regions, which is essential to track changes in the future, and identify the contaminants to prioritize for further investigation of exposure determinants.


Assuntos
Poluentes Ambientais , Chumbo , Regiões Árticas , Monitoramento Biológico , Canadá , Monitoramento Ambiental , Poluentes Ambientais/análise , Humanos , Territórios do Noroeste
14.
Environ Res ; 182: 109112, 2020 03.
Artigo em Inglês | MEDLINE | ID: mdl-32069740

RESUMO

Traditional food consumption for Indigenous peoples is associated with improved nutrition and health but can also pose potential risks via exposure to contaminants. Polycyclic aromatic hydrocarbons (PAHs) are compounds of interest due to their widespread presence (e.g., their metabolites are detected in up to 100% of the Canadian population) and their toxicological potential. To better understand the range of exposures faced by Indigenous populations in northern Canada and to address a contaminant of emerging concern identified by the Arctic Monitoring and Assessment Programme, a multi-year biomonitoring study investigated levels of PAH exposure in subarctic First Nations communities of the Northwest Territories, Canada. Secondary data analysis of banked samples from a subset of the cross-sectional study was done. PAHs and cotinine markers in the urine samples (n = 97) of participants from two regions from the Mackenzie Valley (Dehcho and Sahtú) was completed by liquid and gas chromatography coupled with mass spectrometry. Also, participants completed a 24-hr recall food survey. When compared according to age/sex categories, the GM of several biomarkers (1-hydroxypyrene, 1-naphthol, 2-hydroxyfluorene, 2-hydroxyphenanthrene, 2-naphthol, 3-hydroxyfluorene, 3-hydroxyphenanthrene, 4-hydroxyphenanthrene, 9-hydroxyfluorene, 9-hydroxyphenanthrene) appeared higher than observed for the general Canadian population. The PAHs levels observed were, however, below clinical levels associated with adverse health outcomes. Altogether, these elevated biomarkers are metabolites of pyrene, naphthalene, fluorene and phenanthrene. Statistically significant non-parametric associations were observed between several biomarkers and i) the consumption of cooked meat in the last 24 h; and, ii) smoking status (self-reported status and adjusted on urine cotinine level). This work is the first to report PAH levels in a northern Canadian population and provides local baseline data for monitoring the effects of changes to climate and lifestyle over time. These findings will support regional and territorial decision makers in identifying environmental health priorities.


Assuntos
Poluentes Ambientais , Hidrocarbonetos Policíclicos Aromáticos , Regiões Árticas , Biomarcadores , Canadá , Estudos Transversais , Monitoramento Ambiental , Poluentes Ambientais/urina , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Povos Indígenas , Territórios do Noroeste , Hidrocarbonetos Policíclicos Aromáticos/urina
15.
J Chem Phys ; 149(17): 174706, 2018 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-30409005

RESUMO

We report molecular-dynamics (MD) simulation results for the surface free energy of a hard-sphere fluid at cylindrical and spherical hard walls of different radii. The precision of the results is much higher than that in our previous study [B. B. Laird et al., Phys. Rev. E 86, 060602 (2012)], allowing us to estimate the size of deviations from the predictions of Morphometric Thermodynamics (MT). We compare our results to the analytical expressions for the surface energy as a function of wall radius R and fluid density derived from the White Bear II variant of the density functional theory, as well as to the leading terms of the virial expansion. For the cylindrical wall, we observe deviations from MT proportional to R -2 and R -3, which are consistent with the available virial expressions. For the spherical wall, while the precision is not sufficient to detect statistically significant deviations from MT, the MD results indicate the range of densities for which the truncated virial expansions are applicable.

16.
J Chem Phys ; 149(8): 084701, 2018 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-30193513

RESUMO

A generalized scaled-particle theory for the uniform hard-disk mixture is derived in the spirit of the White Bear II free energy of the hard-sphere fluid [H. Hansen-Goos and R. Roth, J. Phys. C: Condens. Matter 18, 8413 (2006)]. The theory provides a very simple result for the interfacial free energy γ of the hard-disk fluid at a planar hard wall (which in d = 2 is a line) in terms of the equation of state. To complement and assess the theory, we perform Monte Carlo simulations from which we obtain γ using Gibbs-Cahn integration. While we find excellent overall agreement between theory and simulation, it also becomes apparent that the set of scaled-particle variables available in d = 2 is too limited, prohibiting a quasi-exact result for γ. Furthermore, this is reflected in the mixture equation of state resulting from our theory, which, similar to a previous attempt by Santos et al. [Mol. Phys. 96, 1 (1999)], displays a small but systematic deviation from simulations.

17.
J Chem Phys ; 149(1): 014704, 2018 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-29981545

RESUMO

We study the hard-sphere fluid in contact with a planar hard wall. By combining the inhomogeneous virial series with simulation results, we achieve a new benchmark of accuracy for the calculation of surface thermodynamics properties such as surface adsorption Γ and the surface free energy (or surface tension), γ. We briefly introduce the problem of choosing a position for the dividing surface and avoid it by proposing the use of alternative functions to Γ and γ that are independent of the adopted frame of reference. Finally, we present analytic expressions for the dependence of system surface thermodynamic properties on packing fraction, ensuring the high accuracy of the parameterized functions for any frame of reference. The proposed parametric expressions for both, Γ and γ, fit the accurate simulation results within the statistical error.

18.
J Chem Phys ; 158(22)2023 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-37290082
19.
Environ Res ; 152: 470-477, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27297029

RESUMO

BACKGROUND: Inuit in Canada have low reported incidence of myocardial infarction (MI) because of their traditional rich n-3 fatty acids marine diet. They are experiencing rapid nutrition transition and ischemic heart disease is now becoming a health concern. OBJECTIVES: Our goal was to describe the modern Inuit diet, the eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and methyl mercury (MeHg) intake and estimate their contributions to the risk of MI. We also estimated the effect of promoting the consumption of more traditional food on Inuit's MI risk. METHODS: We estimated the effect of Inuit diet on MI risk with modelling. Model formulas and assumptions were extracted from various epidemiology studies and literatures. International Polar Year Inuit Health Survey (IHS) was a comprehensive health and nutrition survey conducted in 2007-8 with 2072 participants (aged 18-79) in Canada. Traditional food intake, blood biomarkers values from the IHS served as the baseline parameters of model input. RESULTS: Inuit traditional diet contained both high level of EPA, DHA and MeHg and their combined net effect was estimated to reduce the relative risk of MI by 1% for men and 2% for women. Arctic char meat provided the largest amount of EPA and DHA. Ringed seal liver was the main source for MeHg. Increase intake of selected fish, like salmon, herring and Arctic char by 75g per day can reduce the relative risk of MI (RR 0.70, 0.78 and 0.90 respectively). CONCLUSIONS: In the Inuit diet, the beneficial effect on MI of EPA and DHA is diminished by the adverse effect of MeHg. Promoting the increase consumption of fish species with high EPA+DHA and low MeHg may help to prevent MI among Inuit.


Assuntos
Dieta/efeitos adversos , Poluentes Ambientais/sangue , Ácidos Graxos Ômega-3/sangue , Compostos de Metilmercúrio/sangue , Infarto do Miocárdio/epidemiologia , Adulto , Idoso , Idoso de 80 Anos ou mais , Biomarcadores/sangue , Canadá/epidemiologia , Ácidos Docosa-Hexaenoicos/sangue , Ácido Eicosapentaenoico/sangue , Eritrócitos/química , Feminino , Humanos , Inuíte , Masculino , Pessoa de Meia-Idade , Infarto do Miocárdio/etiologia , Risco , Adulto Jovem
20.
J Toxicol Environ Health A ; 80(1): 18-31, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-27905863

RESUMO

To better understand the risks and benefits of eating wild-harvested fish from the Northwest Territories, Canada, levels of total mercury (HgT) and selenium (Se) and composition of omega-3 fatty acid (n-3 FA) were measured in muscle tissue of fish harvested from lakes in the Dehcho Region, Northwest Territories, Canada. Average HgT levels ranged from 0.057 mg/kg (cisco) to 0.551 mg/kg (northern pike), while average n-3 FA concentrations ranged from 101 mg/100 g (burbot) to 1,689 mg/100 g (lake trout). In contrast to HgT and n-3 FA, mean Se concentrations were relatively similar among species. Consequently, species such as lake whitefish, cisco, and longnose sucker displayed the highest nutrient levels relative to HgT content. Levels of HgT tended to increase with fish size, while Se and n-3 FA levels were typically not associated with fork length or fish weight. Interestingly, HgT concentration was occasionally inversely related to tissue nutrient content. Significant negative correlations were observed between Hg and n-3 FA for lake trout, northern pike, and walleye. There were also significant negative correlations between Hg and Se noted for lake whitefish, cisco, and northern pike. Samples with the highest nutritional content displayed, on occasion, lower levels of HgT. This study provides valuable information for the design of probabilistic models capable of refining public health messaging related to minimizing Hg risks and maximizing nutrient levels in wild-harvested fish in the Canadian subarctic.


Assuntos
Exposição Ambiental , Ácidos Graxos Ômega-3/metabolismo , Peixes/metabolismo , Contaminação de Alimentos/análise , Mercúrio/metabolismo , Selênio/metabolismo , Poluentes Químicos da Água/metabolismo , Animais , Ingestão de Alimentos , Monitoramento Ambiental , Humanos , Territórios do Noroeste
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