Diffusion Of Divalent Cations Research Articles

Transbilayer diffusion of divalent cations into liposomes mediated by lipidic particles of phosphatidate.

Liposomes formed from egg-yolk phosphatidylcholine:egg-yolk phosphatidate (molar ratio 2:1) containing pBR322 DNA and DNase I were induced to form, with divalent cations, bilayer/nonbilayer phase transitions of phosphatidate which allowed cation diffusion into liposomes; then cation diffusion was measured by the activation of the hydrolysis of DNase I on DNA. The formation of phosphatidate transitions on liposomes was demonstrated by freeze-fracture and 31P NMR, and a direct correlation between the formation of phosphatidate transitions and the transbilayer diffusion of cations was found: only Ca2+ and Mn2+, which induce phase transitions, were able to penetrate liposomes and triggered the DNase I activity; in addition, Ca2+ at higher concentrations (10 mM) caused fusion of liposomes, whereas Mn2+ did not, suggesting that transitions induced by Mn2+ participated only in the diffusion of this ion; furthermore, Mg2+ neither formed phase transitions nor triggered the enzymatic activity. The liposomes studied represent more dynamic structures that can form phosphatidate structures involved in both (1) the interchange of divalent cations with the surroundings, thereby modulating encapsulated enzymes, and (2) the fusion of lipid vesicles probably implicated in the enrichment of liposomal content in the early Precambian Earth.

Cation diffusion in aluminosilicate garnets: experimental determination in spessartine-almandine diffusion couples, evaluation of effective binary diffusion coefficients, and applications

We present new experimental data on diffusion of divalent cations in almandine-spessartine diffusion couples in graphite capsules in the P-T range of 14–35 kb, 1100–1200° C. The tracer diffusion coefficients of the major divalent cations, viz. Fe, Mg and Mn, retrieved from the multicomponent diffusion profiles, have been combined with earlier data from our laboratory at 29–43 kb, 1300–1480° C (Loomis et al. 1985) to derive expressions of the P-T dependence of the diffusion coefficients at fO2 approximately corresponding to that defined by equilibrium in the system graphite-O2. We review the conditions, discussed earlier by Cooper, under which the flux of a component in a multicomponent system becomes proportional to its concentration gradient (Fickian diffusion), as if the entire solvent matrix behaves as a single component, and also suggest a method of incorporating the thermodynamic effect on diffusion in the same spirit. Regardless of the magnitude or sign of the off-diagonal terms of the D matrix, it is always possible to define an effective binary diffusion coefficient (EBDC) of a component in a semi-infinite multicomponent diffusion-couple experiment such that it has the property of the Fickian diffusion coefficient, provided that there is no inflection on the diffusion profiles. It is shown that the success of Elphick et al. in fitting the experimental diffusion profiles of all components over a limited concentration range by a single diffusion coefficient is due to fortuitous similarity of the EBDCs of the components (Fe, Mg, Mn and Ca) in their diffusion couple experiments. In common metapelitic garnets showing compositional zoning, the EBDCs of the divalent cations do not differ from each other by more than a factor of 2.5. However, the EBDC of a component changes from core to rim by a factor of 3 to 12, depending on the composition. We suggest a method of volume averaging of the EBDC which should prove useful in approximate calculations of diffusion flux during relaxation of compositional zoning. The EBDC of Mn is found to reduce essentially to DMnMn, the main diagonal term of the D matrix, and consequently can be calculated quite easily. Evaluation of EBDC of Fe, Mg and Mn in garnets from a prograde Barrovian sequence did not reveal any significant dependence on the extent of relaxation of garnet. The diffusion data have been applied to calculate the cooling rate of natural biotite-garnet diffusion couple from eastern Finland and diffusional modification of growth zoning in garnet in early Proterozoic Wopmay orogen, Canada. The results are in good agreement with geochronological and other independent constraints.

Diffusion in single crystals of melilite: II. Cations

Diffusion coefficients of divalent cations, Ni, Co, Fe, Mn, Ca, Sr, and Ba, in synthetic åkermanite were determined by tracer-diffusion experiments. Diffusion coefficients of cation pairs, Al + Al-Mg + Si, Al + Al-Co + Si, and Mg-Co in melilite solid-solution systems, were determined by coupled annealing of synthetic melilites of endmember compositions. Cobalt tracer diffuses slower along the c- crystallographic axis than along the a- axis by a factor of about three, possibly due to the anisotropic sheet-like arrangement of oxygen ions parallel to the (001) plane which is perpendicular to the c- axis in the crystal structure of melilite. In the coupled diffusion experiments, the cation pairs interdiffuse complementary, as expected for conservation of material and ionic charge balance in the substitution. The tracer-diffusion coefficient of Co in åkermanite agrees well with that obtained by extrapolation of the inter-diffusion coefficient of Mg-Co cation pair to the composition of åkermanite 100-Co · åkermanite 0. This suggests the mechanism of tracer-diffusion of Co in åkermanite is essentially the same as in Mg-Co inter-diffusion. The inter-diffusion coefficients of cation pairs show a strong dependence on the endmember compositions, and can be correlated with the melting temperature or solidus curves in the phase diagrams. The observed trend in the inter-diffusion coefficient vs. melting temperature relations is similar to those observed for alloys and consistent with an empirical rule for self-diffusion coefficient-melting temperature relation. In the diffusion coefficient vs. ionic radius diagram for divalent cation diffusion in åkermanite, smooth curves were observed as in the case of olivine systems. However, the shapes of the curves were significantly different from those observed in olivine systems. The observed trend of diffusion coefficients with ionic radius can be explained on the basis of crystal structure-controlled diffusion in åkermanite. The observed results suggest that Mg diffusivity strongly depends on the chemical compositions of melilite solid-solution series: the estimated diffusivity of Mg in åkermanite is considerably larger than that of O, but is smaller than O in gehlenite.

Chemical diffusion and crystalline nucleation during oxidation of ferrous iron-bearing magnesium aluminosilicate glass

Rutherford backscattering spectroscopy (RBS) and transmission electron microscopy (TEM) have been used to evaluate the mechanism and kinetics of oxidation of a Fe 2+-doped MgOAl 2O 3SiO 2 glass (with nominal composition along the enstatite-cordierite-liquid divariant) which was heat treated in air under the time and temperature ranges 10–150 h and 700–800°C, respectively. The results clearly demonstrate that oxidation occurs by a cation diffusion process: specifically, the divalent cations diffuse from the interior of the glass to the free surface where they subsequently react with environmental oxygen to form a two-phase, MgO(Mg, Fe) 3O 4 crystalline layer which covers the (divalent cation-depleted) glass. Oxidation of some Fe 2+ within the glass occurs via the inward flux of electron holes (a counterflux to the divalent cation diffusion required to maintain charge neutrality of the glass); this internal oxidation results in the fine-scale (∼ 1–5 nm), homogeneous nucleation of crystalline (Mg, Fe) 3O 4 within the divalent cation-depleted layer of the glass. Chemical diffusion of an oxygen species is thus demonstrated to be a slower, parallel kinetic process which is not required for oxidation to occur in this material. A first-order analysis of oxidation kinetics in the glass is presented.

Oxygen chemical diffusion in three basaltic liquids at elevated temperatures and pressures

The diffusivity of oxygen has been measured in three basaltic liquids from 1280 to 1450°C and 4 to 21 kilobars using a solid media piston-cylinder apparatus. The measurements were done by monitoring the reduction of ferric iron in previously oxidized spheres of basalt melt. The compositions studied were olivine nephelinite, alkali basalt, and 1921 Kilauea tholeiite. The isobaric temperature dependence of oxygen diffusivity is adequately described by Arrhenius relationships for the three liquids studied. Arrhenius activation energies were determined at 12 kilobars for olivine nephelinite (62± 6 kcal/mole) and tholeiite (51 ± 4 kcal/mole) and at 4, 12, and 20 kilobars for alkali basalt (70 ± 7, 86 ± 6, and 71 ± 14 kcal/mole, respectively). The Arrhenius parameters for the three compositions define a compensation law which is indistinguishable from those for oxygen diffusion in simple silicate melts (DUNN, 1982) and for divalent cation diffusion in basaltic melts ( Hofmann, 1980). These results suggest that the principal species contributing to the total diffusivity of oxygen is the oxide anion (O 2−). The isothermal pressure dependence of oxygen diffusion is complex and quite different from that observed for cationic diffusion in silicate melts. All three compositions show a sharp decrease in oxygen diffusivity at approximately the same pressure as the change in the liquidus phase from olivine to pyroxene, but otherwise the pressure dependence can be described by Arrhenius type equations. The equations yield negative activation volumes for the olivine nehpelinite and the alkali basalt. The activation volumes determined for the tholeiite are near zero at low pressure and positive at high pressure. A negative activation volume represents a decrease in the average size of the principal diffusing species. The results of this study are consistent with a melt model which includes both continuous changes in the relative proportions of the various anionic species in the melt with pressure and the occurrence of anionic disproportionation reactions within narrow pressure ranges.

Influence of divalent cations on potassium contracture duration in frog muscle fibres.

Single fibres or small fibre bundles were dissected from twitch muscles of frogs and washed in low Cl-solutions. Contractures were provoked by 122.5 mM K+. At room temperature (17-20 degrees C) the contracture duration was about 1.5 s in the absence of divalent cations and about 3 s in the presence of 2 mM Ca2+. Contractures were prolonged when Ca2+ was replaced by Ni2+ showing that inward Ca current was not the factor responsible for the contracture prolongation. K contracture duration was prolonged in the cold (3 degrees C) by a factor of about 4 in the presence of non-permeating divalent cations (Ni, Co), when 0.1 mM La3+ was applied together with 2 mM Ca2+, and in the virtual absence of divalent cations. The contractures were prolonged in the cold by a factor of 6 or more in the presence of permeant divalent cations (Ca, Sr, Ba, Mg, and Mn at 8 mM). Diffusion of divalent cations in the transverse tubules of the muscle fibres was shown to have a Q10 similar to that in free solution. It was concluded that inward current of divalent cations may shorten contracture duration by causing ionic depletion of the transverse tubules.

New models for impurity tracer diffusion in silver halides

Abstract A summary of results on diffusion of both anionic and cationic impurities in the silver halides is reported. The diffusion of bromide and iodide ions in silver chloride and of chloride and iodide ions in silver bromide are discussed in terms of two vacancy mechanisms. An interstitial-substitutional model is presented to explain the diffusion of divalent cations in silver halides. The effect of a chlorine atmosphere on the diffusion of gold ion in silver chloride is examined in terms of a deviation from stoichiometry.