Kinetic and equilibrium Fe isotope fractionation between aqueous Fe (II) and Fe (III)
Geochimica et Cosmochimica Acta, 2003•Elsevier
Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species
measured over a range of chloride concentrations (0, 11, 110 mM Cl−) and at two
temperatures (0 and 22° C) indicate that Fe isotope fractionation is a function of temperature,
but independent of chloride contents over the range studied. Using 57Fe-enriched tracer
experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or
a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at …
measured over a range of chloride concentrations (0, 11, 110 mM Cl−) and at two
temperatures (0 and 22° C) indicate that Fe isotope fractionation is a function of temperature,
but independent of chloride contents over the range studied. Using 57Fe-enriched tracer
experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or
a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at …
Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl−) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using 57Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60–80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl− (∼10 mM HNO3) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl− solutions. The average measured equilibrium isotope fractionations, ΔFe(III)-Fe(II), in 0, 11, and 111 mM Cl− solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured ΔFe(III)-Fe(II) fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl− solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: 10 3 ln α Fe(III)-Fe(II) = [0.334 ± 0.032]*10 6T 2 − 0.88 ± 0.38 where the isotopic fractionation is independent of Cl− contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl− contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation.
Elsevier
以上显示的是最相近的搜索结果。 查看全部搜索结果