979 resultados para UNSATURATED-HYDROCARBONS
Resumo:
The variation of seawater level resulting from tidal fluctuations is usually neglected in regional groundwater flow studies. Although the tidal oscillation is damped near the shoreline, there is a quasi-steady-slate rise in the mean water-table position, which may have an influence on regional groundwater flow. In this paper the effects of tidal fluctuations on groundwater hydraulics are investigated using a variably saturated numerical model that includes the effects of a realistic mild beach slope, seepage face and the unsaturated zone. In particular the impact of these factors on the velocity field in the aquifer is assessed. Simulations show that the tidal fluctuation has substantial consequences for the local velocity field in the vicinity of the exit face, which affects the nearshore migration of contaminant in coastal aquifers. An overheight in the water table as a result of the tidal fluctuation is observed anti this has a significant effect on groundwater discharge to the sea when the landward boundary condition is a constant water level. The effect of beach slope is very significant and simplifying the problem by considering a vertical beach face causes serious errors in predicting the water-table position and the groundwater flux. For media with a high effective capillary fringe, the moisture retained above the water table is important in determining the effects of the tidal fluctuations. Copyright (C) 2001 John Wiley & Sons, Ltd.
Resumo:
Mesoporous Ti-substituted aluminophosphates (AlPOs) with a hexagonal, cubic and lamellar pore structure, characteristic of MCM-41, MCM-48, and MCM-50, respectively, were synthesized. The stability of these mesophases upon template removal was studied. The pore structures, surface properties, and local atom environments of Al, P, and Ti of the hexagonal and cubic Ti-containing mesoporous products were extensively characterized using X-ray diffraction, magic angle spinning nuclear magnetic resonance, AAS, XPS, ultraviolet–visible, and adsorption of nitrogen and water vapor techniques while the lamellar mesophase was not further characterized due to its very poor thermal stability. Ti-containing mesoporous AlPO materials show a reasonable thermal stability upon template removal, a hydrophilic surface property, and high porosity showing application potentials in catalytic oxidation of hydrocarbons.
Resumo:
The pore-opening size of MCM-41 is tailored to be in the microporous region using a chemical vapor deposition technique for selective tailoring. Although the pore opening is narrowed, the internal pore body of MCM-41 remains unchanged so the pore volume retains a substantial portion (80%) of its original value. The adsorption equilibrium of nitrogen and benzene in the modified MCM-41 shows a type I isotherm, which significantly improves the adsorption performance of MCM-41 for low-concentration volatile organic compounds. The adsorption kinetics of benzene in the modified MCM-41 is also studied.
Resumo:
Five kinetic models for adsorption of hydrocarbons on activated carbon are compared and investigated in this study. These models assume different mass transfer mechanisms within the porous carbon particle. They are: (a) dual pore and surface diffusion (MSD), (b) macropore, surface, and micropore diffusion (MSMD), (c) macropore, surface and finite mass exchange (FK), (d) finite mass exchange (LK), and (e) macropore, micropore diffusion (BM) models. These models are discriminated using the single component kinetic data of ethane and propane as well as the multicomponent kinetics data of their binary mixtures measured on two commercial activated carbon samples (Ajax and Norit) under various conditions. The adsorption energetic heterogeneity is considered for all models to account for the system. It is found that, in general, the models assuming diffusion flux of adsorbed phase along the particle scale give better description of the kinetic data.
Resumo:
1. The relative permeability of the native P2X receptor channel to monovalent and divalent inorganic and organic cations was determined from reversal potential measurements of ATP-evoked currents in parasympathetic neurones dissociated from rat submandibular ganglia using the dialysed whole-cell patch clamp technique. 2. The P2X receptor-channel exhibited weak selectivity among the alkali metals with a selectivity sequence of Na+ > Li+ > Cs+ > Rb+ > K+, and permeability ratios relative to Cs+ (P-X/P-Cs) ranging from 1. 11 to 0.86. 3. The selectivity for the divalent alkaline earth cations was also weak with the sequence Ca2+ > Sr2+ > Ba2+ > Mn2+ > Mg2+. ATP-evoked currents were strongly inhibited when the extracellular divalent cation concentration was increased. 4, The calculated permeability ratios of different ammonium cations are higher than those of the alkali metal cations. The permeability sequence obtained for the saturated organic cations is inversely correlated with the size of the cation. The unsaturated organic cations have a higher permeability than that predicted by molecular size. 5. Acidification to pH 6.2 increased the ATP-induced current amplitude twofold, whereas alkalization to 8.2 and 9.2 markedly reduced current amplitude. Cell dialysis with either anti-P2X(2) and/or anti-P2X(4) but not anti-P2X(1) antibodies attenuated the ATP-evoked current amplitude. Taken together, these data are consistent with homomeric and/or heteromeric P2X(2) and P2X(4) receptor subtypes expressed in rat submandibular neurones. 6. The permeability ratios for the series of monovalent organic cations, with the exception of unsaturated cations, were approximately related to the ionic size. The relative permeabilities of the monovalent inoganic and organic cations tested are similar to those reported previously for cloned rat P2X2 receptors expressed in mammalian cells.
Resumo:
The interaction between natural and sexual selection is central to many theories of how mate choice and reproductive isolation evolve, but their joint effect on the evolution of mate recognition has not, to my knowledge, been investigated in an evolutionary experiment. Natural and sexual selection were manipulated in interspecific hybrid populations of Drosophila to determine their effects on the evolution of a mate recognition system comprised of cuticular hydrocarbons (CHCs). The effect of natural selection in isolation indicated that CHCs were costly for males and females to produce. The effect of sexual selection in isolation indicated that females preferred males with a particular CHC composition. However, the interaction between natural and sexual selection had a greater effect on the evolution of the mate recognition system than either process in isolation. When natural and sexual selection were permitted to operate in combination, male CHCs became exaggerated to a greater extent than in the presence of sexual selection alone, and female CHCs evolved against the direction of natural selection. This experiment demonstrated that the interaction between natural and sexual selection is critical in determining the direction and magnitude of the evolutionary response of the mate recognition system.
Resumo:
The effect of gamma-radiation on a perfluoroalkoxy (PFA) resin was examined using solid-state high-speed magic angle spinning (MAS) F-19 NMR spectroscopy. Samples were prepared for analysis by subjecting them to gamma-radiation in the dose range 0.5-3 MGy at either 303, 473, or 573 K. New structures identified include new saturated chain ends, short and long branches, and unsaturated groups. The formation of branched structures was found to increase with increasing irradiation temperature; however, at all temperatures the radiation chemical yield (G value) of new chain ends was greater than the G value of long branch points, suggesting that chain scission is the net process.
Resumo:
Apart from very few families who have a direct cause from genetic mutation, causes of most Parkinson's disease (PD) remain unclear. Many allelic association studies on polymorphism of different candidate genes have been studied. Although these association studies do not imply a causal relationship, it does warrant further studies to elucidate the pathophysiologic significance. CYP1A1 polymorphisms have been reported to be associated with PD in a Japanese population sample. Since CYP1A1 transforms aromatic hydrocarbons into products that may be neurotoxic and perhaps lead to PD, we therefore undertook a study to look at the possible association of CYP1A1 polymorphism and PD in a Chinese population. Contrary to the Japanese result, we did not find any statistically significant difference between the PD group and the control group in our study with a bigger sample size.
Resumo:
In order to study the effect of arsenic on DNA damage, Sprague-Dawley rats were dosed with sodium arsenite (10 mg/kg) with or without 800 mug of benzo(a)pyrene (BP) by intramammilary injection. The animals were sacrificed on day 1, 3, 5, 10 and 27 and the mammary gland tissues were collected for DNA adduct measurement using a P-32 post-labeling assay. Animals dosed with arsenic alone did not show any DNA adducts. DNA adduct levels in rats dosed with BP alone reached a maximum level by day 5, reducing to 13% of this level by day 27. Adduct levels in rats dosed with arsenic and BP also reached a maximum by day 5 but only 80% of the level observed in the BP group. However, 84% of this amount still remained by day 27. The First Nucleotide Change (FNC) technique was used for the screening of 115 samples of various tissues from mice that had been chronically exposed to sodium arsenate for over 2 years revealed that inorganic arsenic did not attack the two putative hotspots (codons 131 and 154) of the hOGG1 gene. These results support the hypothesis that arsenic exerts its biological activity through DNA repair inhibition. (C) 2002 Elsevier Science Ireland Ltd. All rights reserved.
Resumo:
The kinetics of single component adsorption on activated carbon is investigated here using a heterogeneous vacancy solution theory (VST) of adsorption. The adsorption isotherm is developed to account for the adsorbate non-ideality due to the size difference between the adsorbate molecule and the vacant site, while incorporating adsorbent heterogeneity through a pore-width-related potential energy. The transport process in the bidisperse carbon considers coupled mass transfer in both macropore and micropore phases simultaneously. Adsorbate diffusion in the micropore network is modeled through effective medium theory, thus considering pore network connectivity in the adsorbent, with the activation energy for adsorbate diffusion related to the adsorption energy, represented by the Steele 10-4-3 potential for carbons. Experimental data of five hydrocarbons, CO2 and SO2 on Ajax carbon at multiple temperatures, as well as three hydrocarbons on Norit carbon at three temperatures are first fitted by the heterogeneous VST model to obtain the isotherm parameters, followed by application of the kinetic model to uptake data on carbon particles of different sizes and geometry at various temperatures. For the hydrocarbons studied, the model can successfully correlate the experimental data for both adsorption equilibrium and kinetics. However, there is some deviation in the fit of the desorption kinetics for polar compounds such as CO2 and SO2, due to the inadequacy of the L-J potential model in this case. The significance of viscous transport in the micropores is also considered here and found to be negligible, consistent with recent molecular simulation studies. (C) 2002 Elsevier Science Ltd. All rights reserved.
Resumo:
A heterogeneous modified vacancy solution model of adsorption developed is evaluated. The new model considers the adsorption process through a mass-action law and is thermodynamically consistent, while maintaining the simplicity in calculation of multicomponent adsorption equilibria, as in the original vacancy solution theory. It incorporates the adsorbent heterogeneity through a pore-width-related potential energy, represented by Steele's 10-4-3 potential expression. The experimental data of various hydrocarbons, CO2 and SO2 on four different activated carbons - Ajax, Norit, Nuxit, and BPL - at multiple temperatures over a wide range of pressures were studied by the heterogeneous modified VST model to obtain the isotherm parameters and micropore-size distribution of carbons. The model successfully correlates the single-component adsorption equilibrium data for all compounds studied on various carbons. The fitting results for the vacancy occupancy parameter are consistent with the pressure change on different carbons, and the effect of pore heterogeneity is important in adsorption at elevated pressure. It predicts binary adsorption equilibria better than the IAST scheme, reflecting the significance of molecular size nonideality.
Resumo:
The role of PACs (primary adsorption centers) in the mesopore (i.e., transport) region of activated carbons during adsorption of polar species, such as water, is unclear. A classical model of three-dimensional adsorption on finite PACs is presented. The model is a preliminary, theoretical investigation into adsorption on mesopore PACs and is intended to give some insight into the energetic and physical processes at work. Work processes are developed to obtain isotherms and three-dimensional sorbate growth on PACs of varying size and energetic characteristics. The work processes allow two forms of adsorbed phase growth: densification at constant boundary and boundary growth at constant density. Relatively strong sorbate-sorbent interactions and strong surface tension favor adsorbed phase densification over boundary growth. Conversely, relatively weak sorbate-sorbent interactions and weak surface tension favor boundary growth over densification. If sorbate-sorbate interactions are strong compared to sorbate-sorbent interactions, condensation with hysteresis occurs. This can also give rise to delayed boundary growth, where all initial adsorption occurs in the monolayer only. The results indicate that adsorbed phase growth on PACs may be quite complex.
Resumo:
Field populations of Drosophila serrata display reproductive character displacement in cuticular hydrocarbons (CHCs) when sympatric with Drosophila birchii. We have previously shown that the naturally occurring pattern of reproductive character displacement can be experimentally replicated by exposing field allopatric populations of D. serrata to experimental sympatry with D. birchii. Here, we tested whether the repeated evolution of reproductive character displacement in natural and experimental populations was a consequence of genetic constraints on the evolution of CHCs. The genetic variance-covariance (G) matrices for CHCs were determined for populations of D. serrata that had evolved in either the presence or absence of D. birchii under field and experimental conditions. Natural selection on mate recognition under both field and experimental sympatric conditions increased the genetic variance in CHCs consistent with a response to selection based on rare alleles. A close association between G eigenstructure and the eigenstructure of the phenotypic divergence (D) matrix in natural and experimental populations suggested that G matrix eigenstructure may have determined the direction in which reproductive character displacement evolved during the reinforcement of mate recognition.
Resumo:
A suite of allenic hydrocarbons, previously unknown as a molecular class from insects, has been characterized from several Australian melolonthine scarab beetles. The allenes are represented by the formula CH3(CH2)nCH=.=CH(CH2)(7)CH3 with n being 11-15, 17 and 19, and thus, all have Delta(9,10)-unsaturation. These structures have been confirmed by syntheses and comparisons of spectral and chromatographic properties with those of the natural components. The enantiomers of (+/-)-Delta(9,10)-tricosadiene and Delta(9,10)-pentacosadiene were separable on a modified beta-cyclodextrin column (gas chromatography), and the natural Delta(9,10)-tricosadiene (n = 11) and Delta(9,10)-pentacosadiene (n = 13) were shown to be of >85% ee. Syntheses of nonracemic allenes of known predominating chirality were acquired using both organotin chemistry and sulfonylhydrazine intermediates, and comparisons then demonstrated that the natural allenes were predominantly (R)-configured.
Resumo:
The dissected carcass composition and fatty acid profiles of intermuscular fat from 110 male goat kids from six genotypes i.e. Boer x Angora (BA), Boer x Feral (BF), Boer x Saanen (BS), Feral x Feral (1717), Saanen x Angora (SA) and Saanen x Feral (SF) and two slaughter weight groups i.e. Capretto and Chevon (liveweight at slaughter 14-22 and 30-35 kg, respectively) were compared. Carcass tissue distribution for various genotypes was: muscle (63-66%), fat (10-13%) and bone (21-24%). Genotype significantly (P < 0.05) influenced the carcass composition; BA and FF carcasses had significantly higher muscle to bone ratio, while carcasses from BS kids were leaner compared to other genotypes. However, the two slaughter weight groups did not differ significantly (P > 0.05) in terms of carcass composition, when compared at the same carcass weight. In the present study, significant (P < 0.01) correlations were observed between percentage of muscle, fat and bone in most of the primal cuts and that in the carcass side. The main saturated fatty acids (SFAs) identified were palmitic (16:0) and stearic acid (18:0), while oleic acid (18: 1, omega9) was the main unsaturated fatty acid (UFA) in the intermuscular fat from goat kids. There were significant (P < 0.05) differences between genotypes in the proportions of individual fatty acids. Adipose tissue from BS kids had significantly higher UFAs (mainly oleic acid) and thus had a significantly lower melting point compared to other genotypes. There were significantly higher proportions of palmitic acid (35%) in the adipose tissue from Capretto kids compared to that from Chevon kids (22%). The concentration of UFAs increased in the adipose tissue from Capretto to Chevon carcasses. (C) 2003 Elsevier Science B.V. All rights reserved.