53 resultados para Inorganic electrolytes
Resumo:
Even moderate arsenic exposure may lead to health problems, and thus quantifying inorganic arsenic (iAs) exposure from food for different population groups in China is essential. By analyzing the data from the China National Nutrition and Health Survey (CNNHS) and collecting reported values of iAs in major food groups, we developed a framework of calculating average iAs daily intake for different regions of China. Based on this framework, cancer risks from As in food was deterministically and probabilistically quantified. The article presents estimates for health risk due to the ingestion of food products contaminated with arsenic. Both per individual and for total population estimates were obtained. For the total population, daily iAs intake is around 42 mu g day(-1), and rice is the largest contributor of total iAs intake accounting for about 60%. Incremental lifetime cancer risk from food iAs intake is 106 per 100,000 for adult individuals and the median population cancer risk is 177 per 100,000 varying between regions. Population in the Southern region has a higher cancer risk than that in the Northern region and the total population. Sensitive analysis indicated that cancer slope factor, ingestion rates of rice, aquatic products and iAs concentration in rice were the most relevant variables in the model, as indicated by their higher contribution to variance of the incremental lifetime cancer risk. We conclude that rice may be the largest contributor of iAs through food route for the Chinese people. The population from the South has greater cancer risk than that from the North and the whole population. (C) 2011 Elsevier Ltd. All rights reserved.
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Rice and drinking water are recognized as the dominant sources of arsenic (As) for human intake, while little is known about As accumulation and speciation in Chinese Herbal Medicines (CHMs), which have been available for many hundreds of years for the treatment of diseases in both eastern and western cultures. Inorganic arsenic was the predominant species in all of CHMs samples. The levels of inorganic arsenic in CHMs from fields and markets or pharmacies ranged from 63 to 550 ng/g with a mean of 208 ng/g and 94 to 8683 ng/g with a mean of 1092 ng/g, respectively. The highest concentration was found in the Chrysanthemum from pharmacies. It indicates that the risk of inorganic As in CHMs to human health is higher in medicines from markets or pharmacies than that collected directly from fields. Some CHMs may make a considerable contribution to the human intake of inorganic arsenic.
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The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3 ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85–104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils.
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Rice is comparatively efficient at assimilating inorganic arsenic (As i), a class-one, non-threshold carcinogen, into its grain, being the dominant source of this element to mankind. Here it was investigated how the total arsenic (Ast) and Asi content of Italian rice grain sourced from market outlets varied by geographical origin and type. Total Cr, Cd Se, Mg, K, Zn, Ni were also quantified. Ast concentration on a variety basis ranged from means of 0.18 mg kg-1 to 0.28 mg kg -1, and from 0.11 mg kg-1 to 0.28 mg kg-1 by production region. For Asi concentration, means ranged from 0.08 mg kg-1 to 0.11 mg kg-1 by variety and 0.10 mg kg -1 to 0.06 mg kg-1 by region. There was significant geographical variation for both Ast and Asi; total Se and Ni concentration; while the total concentration of Zn, Cr, Ni and K were strongly influenced by the type of rice.
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We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.
Resumo:
In this work, we present a study on the physical and electrochemical properties of three new Deep Eutectic Solvents (DESs) based on N-methylacetamide (MAc) and a lithium salt (LiX, with X = bis[(trifluoromethyl)sulfonyl]imide, TFSI; hexafluorophosphate, PF; or nitrate, NO). Based on DSC measurements, it appears that these systems are liquid at room temperature for a lithium salt mole fraction ranging from 0.10 to 0.35. The temperature dependences of the ionic conductivity and the viscosity of these DESs are correctly described by using the Vogel-Tammann-Fulcher (VTF) type fitting equation, due to the strong interactions between Li, X and MAc in solution. Furthermore, these electrolytes possess quite large electrochemical stability windows up to 4.7-5 V on Pt, and demonstrate also a passivating behavior toward the aluminum collector at room temperature. Based on these interesting electrochemical properties, these selected DESs can be classified as potential and promising electrolytes for lithium-ion batteries (LIBs). For this purpose, a test cell was then constructed and tested at 25 °C, 60 °C and 80 °C by using each selected DES as an electrolyte and LiFePO (LFP) material as a cathode. The results show a good compatibility between each DES and LFP electrode material. A capacity of up to 160 mA h g with a good efficiency (99%) is observed in the DES based on the LiNO salt at 60 °C despite the presence of residual water in the electrolyte. Finally preliminary tests using a LFP/DES/LTO (lithium titanate) full cell at room temperature clearly show that LiTFSI-based DES can be successfully introduced into LIBs. Considering the beneficial properties, especially, the cost of these electrolytes, such introduction could represent an important contribution for the realization of safer and environmentally friendly LIBs. © 2013 the Owner Societies.
Resumo:
Arsenic (As) species were quantified by HPLC-HG-AFS in water and vegetables from a rural area of West Bengal (India). Inorganic species predominated in vegetables (including rice) and drinking water; in fact, inorganic arsenic (i-As) represented more than 80% of the total arsenic (t-As) content. To evaluate i-As intake in an arsenic affected rural village, a food survey was carried out on 129 people (69 men and 60 women). The data from the survey showed that the basic diet, of this rural population, was mainly rice and vegetables, representing more than 50% of their total daily food intake. During the periods when nonvegetarian foods (fish and meat) were scarce, the importance of rice increased, and rice alone represented more than 70% of the total daily food intake. The food analysis and the food questionnaires administrated led us to establish a daily intake of i-As of about 170 mu g i-As day(-1), which was above the tolerable daily intake of 150 mu g i-As day(-1), generally admitted. Our results clearly demonstrated that food is a very important source of i-As and that this source should never be forgotten in populations depending heavily on vegetables (mainly rice) for their diet.
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Arsenic contamination of rice plants by arsenic-polluted irrigation groundwater could result in high arsenic concentrations in cooked rice. The main objective of the study was to estimate the total and inorganic arsenic intakes in a rural population of West Bengal, India, through both drinking water and cooked rice. Simulated cooking of rice with different levels of arsenic species in the cooking water was carried out. The presence of arsenic in the cooking water was provided by four arsenic species (arsenite, arsenate, methylarsonate or dimethylarsinate) and at three total arsenic concentrations (50, 250 or 500 mu g l(-1)). The results show that the arsenic concentration in cooked rice is always higher than that in raw rice and range from 227 to 1642 mu g kg(-1). The cooking process did not change the arsenic speciation in rice. Cooked rice contributed a mean of 41% to the daily intake of inorganic arsenic. The daily inorganic arsenic intakes for water plus rice were 229, 1024 and 2000 mu g day(-1) for initial arsenic concentrations in the cooking water of 50, 250 and 500 g arsenic l(-1), respectively, compared with the tolerable daily intake which is 150 mu g day(-1).
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A general method to prepare organic-inorganic hybrid aerogels has been presented. A series of organic-inorganic hybrid aerogels were successfully produced from 3d trivalent transition metals (Cr3+, Fe3+) and bridging carboxylic acids. Gelation of the Cr(III) gels was achieved by heating the precursor solution to temperatures above 80 degrees C, which is in sharp contrast to usual supramolecular gels. Among a range of ligands used, highly porous aerogels could be prepared from rigid carboxylate, e.g. 1,4-benzenedicarboxylate and 1,3,5-benzenetricarboxylate. The porous aerogels can be described as a coherent, rigid spongy network of continuous nanometre-sized particles, which is significantly different from the usual fibrous network of supramolecular gels. The aerogels have tunable porous structures with micro-and mesoporosity depending on their reactant concentrations. Their surface areas, pore volumes, and average pore sizes were analysed by using nitrogen sorption, and the accessibility of the pores to bulky molecules was also evaluated. It represents a strategy to prepare hybrid materials with large porosity utilising structurally simple building blocks as precursors.
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A high-capacity diffusive gradients in thin films (DGT) technique has been developed for measurement of total dissolved inorganic arsenic (As) using a long shelf life binding gel layer containing hydrous zirconium oxide (Zr-oxide). Both As(III) and As(V) were rapidly accumulated in the Zr-oxide gel and could be quantitatively recovered by elution using 1.0 M NaOH for freshwater or a mixture of 1.0 M NaOH and 1.0 M H2O2 for seawater. DGT uptake of As(III) and As(V) increased linearly with deployment time and was independent of pH (2.0–9.1), ionic strength (0.01–750 mM), the coexistence of phosphate (0.25–10 mg P L–1), and the aging of the Zr-oxide gel up to 24 months after production. The capacities of the Zr-oxide DGT were 159 μg As(III) and 434 μg As(V) per device for freshwater and 94 μg As(III) and 152 μg As(V) per device for seawater. These values were 5–29 times and 3–19 times more than those reported for the commonly used ferrihydrite and Metsorb DGTs, respectively. Deployments of the Zr-oxide DGT in As-spiked synthetic seawater provided accurate measurements of total dissolved inorganic As over the 96 h deployment, whereas ferrihydrite and Metsorb DGTs only measured the concentrations accurately up to 24 and 48 h, respectively. Deployments in soils showed that the Zr-oxide DGT was a reliable and robust tool, even for soil samples heavily polluted with As. In contrast, As in these soils was underestimated by ferrihydrite and Metsorb DGTs due to insufficient effective capacities, which were likely suppressed by the competing effects of phosphate.
Resumo:
Inorganic arsenic (Asi) is a chronic, non-threshold carcinogen. Rice and rice-based products can be the major source of Asi for many subpopulations. Baby rice, rice cereals and rice crackers are widely used to feed infants and young children. The Asi concentration in rice-based products may pose a health risk for infants and young children. Asi concentration was determined in rice-based products produced in the European Union and risk assessment associated with the consumption of these products by infants and young children, and compared to an identical US FDA survey. There are currently no European Union or United States of America regulations applicable to Asi in food. However, this study suggests that the samples evaluated may introduce significant concentration of Asi into infants’ and young children’s diets. Thus, there is an urgent need for regulatory limits on Asi in food, especially for baby rice-based products.
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Herein, we present the formulation and the characterization of novel adiponitrile-based electrolytes as a function of the salt structure, concentration, and temperature for supercapacitor applications using activated carbon based electrode material. To drive this study two salts were selected, namely, the tetraethylammonium tetrafluoroborate and the 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide. Prior to determination of their electrochemical performance, formulated electrolytes were first characterized to quantify their thermal, volumetric, and transport properties as a function of temperature and composition. Then, cyclic voltammetry and electrochemical impedance spectroscopy techniques were used to investigate their electrochemical properties as electrolyte for supercapacitor applications in comparison with those reported for the currently used model electrolyte based on the dissolution of 1 mol·dm–3 of tetraethylammonium tetrafluoroborate in acetonitrile. Surprisingly, excellent electrochemical performances were observed by testing adiponitrile-based electrolytes, especially those containing the 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide room-temperature molten salt. Differences observed on electrochemical performances between the selected adiponitrile electrolytes based on high-temperature (tetraethylammonium tetrafluoroborate) and the room-temperature (1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide) molten salts are mainly driven by the salt solubility in adiponitrile, as well as by the charge and the structure of each involved species. Furthermore, in comparison with classical electrolytes, the selected adiponitrile +1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide solution exhibits almost similar specific capacitances and lower equivalent serial resistance. These results demonstrate in fact that the adiponitrile +1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide mixture can be used for the formulation of safer electrolytes presenting a very low vapor pressure even at high temperatures to design acetonitrile-free supercapacitor devices with comparable performances.
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The methane solubility in five pure electrolyte solvents and one binary solvent mixture for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and the (50:50 wt%) mixture of EC:DMC was studied experimentally at pressures close to atmospheric and as a function of temperature between (280 and 343) K by using an isochoric saturation technique. The effect of the selected anions of a lithium salt LiX (X = hexafluorophosphate,
<img height="16" border="0" style="vertical-align:bottom" width="27" alt="View the MathML source" title="View the MathML source" src="http://origin-ars.els-cdn.com/content/image/1-s2.0-S0021961414002146-si1.gif">PF6-; tris(pentafluoroethane)trifluorurophosphate, FAP−; bis(trifluoromethylsulfonyl)imide, TFSI−) on the methane solubility in electrolytes for lithium ion batteries was then investigated using a model electrolyte based on the binary mixture of EC:DMC (50:50 wt%) + 1 mol · dm−3 of lithium salt in the same temperature and pressure ranges. Based on experimental solubility data, the Henry’s law constant of the methane in these solutions were then deduced and compared together and with those predicted by using COSMO-RS methodology within COSMOthermX software. From this study, it appears that the methane solubility in each pure solvent decreases with the temperature and increases in the following order: EC < PC < EC:EMC (50:50 wt%) < DMC < EMC < DEC, showing that this increases with the van der Walls force in solution. Additionally, in all investigated EC:DMC (50:50 wt%) + 1 mol · dm−3 of lithium salt electrolytes, the methane solubility decreases also with the temperature and the methane solubility is higher in the electrolyte containing the LiFAP salt, followed by that based on the LiTFSI one. From the variation of the Henry’s law constants with the temperature, the partial molar thermodynamic functions of solvation, such as the standard Gibbs free energy, the enthalpy, and the entropy where then calculated, as well as the mixing enthalpy of the solvent with methane in its hypothetical liquid state. Finally, the effect of the gas structure on their solubility in selected solutions was discussed by comparing methane solubility data reported in the present work with carbon dioxide solubility data available in the same solvents or mixtures to discern the more harmful gas generated during the degradation of the electrolyte, which limits the battery lifetime.
Resumo:
This study describes the utilization of deep eutectic solvents (DESs) based on the mixture of the N-methylacetamide (MAc) with a lithium salt (LiX, with X = bis[(trifluoromethyl)sulfonyl]imide, TFSI; hexafluorophosphate, PF6; or nitrate, NO3) as electrolytes for carbon-based supercapacitors at 80 °C. The investigated DESs were formulated by mixing a LiX with the MAc (at xLi = 0.25). All DESs show the typical eutectic characteristic with eutectic points localized in the temperature range from −85 to −52 °C. Using thermal properties measured by differential scanning calorimetry (DSC), solid–liquid equilibrium phase diagrams of investigated LiX–MAc mixtures were then depicted and also compared with those predicted by using the COSMOThermX software. However, the transport properties of selected DESs (such as the conductivity (σ) and the fluidity (η–1)) are not very interesting at ambient temperature, while by increasing the temperature up to 80 °C, these properties become more favorable for electrochemical applications, as shown by the calculated Walden products: w = ση–1 (mS cm–1 Pa–1 s–1) (7 < w < 16 at 25 °C and 513 < w < 649 at 80 °C). This “superionicity” behavior of selected DESs used as electrolytes explains their good cycling ability, which was determined herein by cyclic voltammetry and galvanostic charge–discharge methods, with high capacities up to 380 F g–1 at elevated voltage and temperature, i.e., ΔE = 2.8 V and 80 °C for the LiTFSI–MAc mixture at xLi = 0.25, for example. The electrochemical resistances ESR (equivalent series resistance) and EDR (equivalent diffusion resistance) evaluated using electrochemical impedance spectroscopy (EIS) measurements clearly demonstrate that according to the nature of anion, the mechanism of ions adsorption can be described by pure double-layer adsorption at the specific surface or by the insertion of desolvated ions into the ultramicropores of the activated carbon material. The insertion of lithium ions is observed by the presence of two reversible peaks in the CVs when the operating voltage exceeds 2 V. Finally, the efficiency and capacitance of symmetric AC/AC systems were then evaluated to show the imbalance carbon electrodes caused by important lithium insertion at the negative and by the saturation of the positive by anions, both mechanisms prevent in fact the system to be operational. Considering the promising properties, especially their cost, hazard, and risks of these DESs series, their introduction as safer electrolytes could represent an important challenge for the realization of environmentally friendly EDLCs operating at high temperature.