Germanium chemistry and MC-ICPMS isotopic measurements of Fe–Ni, Zn alloys and silicate matrices: Insights into deep Earth processes

Abstract

Chemical separation and isotopic measurement of germanium using hexapole-collision cell-MC-ICPMS were developed in various Fe–Ni, ZnS and silicates matrices in order to investigate the potentiality of Ge as an isotopic tracer of planetary differentiation and rock-forming processes. Analytical procedures are described for the critical step of silicate dissolution in HF+HNO3 medium, as well as for Ge chemical purification using a single cationic-exchange resin step for Fe–Ni and ZnS matrices, and two anionic and cationic resin steps for silicate matrices. Germanium isotopic measurements using MC-ICPMS were performed with appropriate Ar+H fluxes in the collision cell to eliminate argide interferences on Ge masses. Three methods of mass bias correction, including sample standard bracketing, external Ga mass bias correction using the exponential law, and the empirical “regression method”, give similar results and demonstrate the use of Ga as an appropriate element for mass bias correction of Ge. Results are presented as delta values with respect to JMC Ge standard, and NIST3120a Ge standard for comparison. We show a long-term 2SD reproducibility of less than 0.24‰ on the δ74Ge.These analytical methods have been applied to Fe-meteorites, sphalerite (ZnS) deposits, and geostandard silicates ranging from ultramafic to basaltic to granitic compositions, and to an iron formation composition. Fe-meteorites and terrestrial silicate samples display small variations of δ74GeJMC=+1.77±0.22‰ and +0.89±0.16‰ (2SD reproducibility), respectively. This contrasts with the large variations seen in low-temperature rocks, such as the ZnS ores (δ74GeJMC=−0.37 to −1.69‰), and banded iron formations (IF-G Isua, δ74GeJMC=+1.38‰). A slight δ74GeJMC–NBO/T negative tendency in silicate samples indicates that polymerisation of silicate melt would control the small Ge isotope fractionation among mantle silicates.A comparison of δ74Ge values of iron meteorites and Earth silicate mantle opens new perspectives in deep Earth processes. On the basis of theoretical metal-silicate isotopic equilibrium processes, the low δ74Ge of silicate Earth cannot reconcile one-stage process of core–mantle segregation. It is proposed that the δ74Ge(JMC) value of silicate earth samples of +0.89±0.16‰ (or δ74Ge(NIST3120a)=+0.53‰) represents the composition of the accessible Earth modern mantle. The δ74Ge of the silicate mantle in equilibrium with the core at time of core formation would be distinct to that of the present mantle in result of distinct thermodynamic parameters, e.g. fO2, pressure, inducing changes in coordination and valence state of Ge in the silicate crystallographic structure. In addition, the light isotopic composition of the Earth's mantle could result from reverse diffusive processes induced by an increase in oxidation state at the end of core formation. This would have some implications on core formation modelling and the use of Ge isotopes for tracing the origin of deep mantle plumes.