Cosmochemistry of the rare earth elements: meteorite studies.

Data from experimental runs, coexisting phases in ultramafic rocks and phenocryst-matrix pairs in volcanic rocks have been used to compile a table of mineral-liquid distribution coefficients for Ti, Zr, Y, and Nb for basic, intermediate and acid melt compositions. These values have then been used to interpret variations of these elements, first in basalts and second, during fractional crystallization from basic to acid magmas. For basalts, petrogenetic modelling of Zr/Y, Zr/Ti, and Zr/Nb ratios, when used in conjunction with REE, Cr and isotopic variations, suggests that: (1) the increase in Zr/Y ratio from mid-ocean ridge to within plate basalts and the low Zr/Nb ratios of alkalic basalts are due to (fluid controlled) source heterogeneities; (2) the low Zr and Zr/Y ratio of volcanic arc basalts results from high degree of partial melting of a depleted source; and (3) the high Zr and similar Zr/Y ratio of basalts from fast spreading relative to slow spreading ridges results from open-system fractional crystallization. Modelling of fractionation trends in more evolved rocks using Y-Zr, Ti-Zr and Nb-Zr diagrams highlights in particular the change in crystallizing mafic phases from island arcs (clinopyroxene-dominated) to Andean-type arcs (amphibole±biotite-dominated). These methods can be applied to altered lavas of unknown affinities to provide additional information on their genesis and eruptive environment.

Petrogenetic implications of Ti, Zr, Y, and Nb variations in volcanic rocks

The parameters which control the behaviour of isovalent trace elements in magmatic and aqueous systems have been investigated by studying the distribution of yttrium, rare-earth elements (REEs), zirconium, and hafnium. If a geochemical system is characterized by CHArge-and-RAdius-Controlled (CHARAC) trace element behaviour, elements of similar charge and radius, such as the Y-Ho and Zr-Hf twin pairs, should display extremely coherent behaviour, and retain their respective chondritic ratio. Moreover, normalized patterns of REE(III) should be smooth functions of ionic radius and atomic number. Basic to intermediate igneous rocks show Y/Ho and Zr/Hf ratios which are close to the chondritic ratios, indicating CHARAC behaviour of these elements in pure silicate melts. In contrast, aqueous solutions and their precipitates show non-chondritic Y/Ho and Zr/Hf ratios. An important process that causes trace element fractionation in aqueous media is chemical complexation. The complexation behaviour of a trace element, however, does not exclusively depend on its ionic charge and radius, but is additionally controlled by its electron configuration and by the type of complexing ligand, since the latter two determine the character of the chemical bonding (covalent vs electrostatic) in the various complexes. Hence, in contrast to pure melt systems, aqueous systems are characterized by non-CHARAC trace element behaviour, and electron structure must be considered as an important additional parameter. Unlike other magmatic rocks, highly evolved magmas rich in components such as H2O, Li, B, F, P, and/or Cl often show non-chondritic Y/Ho and Zr/Hf ratios, and “irregular” REE patterns which are sub-divided into four concave-upward segments referred to as “tetrads”. The combination of non-chondritic Y/Ho and Zr/Hf ratios and lanthanide tetrad effect, which cannot be adequately modelled with current mineral/melt partition coefficients which are smooth functions of ionic radius, reveals that non-CHARAC trace element behaviour prevails in highly evolved magmatic systems. The behaviour of high field strength elements in this environment is distinctly different from that in basic to intermediate magmas (i.e. pure silicate melts), but closely resembles trace element behaviour in aqueous media. “Anomalous” behaviour of Y and REEs, and of Zr and Hf, which are hosted by different minerals, and the fact that these minerals show “anomalous” trace element distributions only if they crystallized from highly evolved magmas, indicate that non-CHARAC behaviour is a reflection of specific physicochemical properties of the magma. This supports models which suggest that high-silica magmatic systems which are rich in H2O, Li, B, F, P, and/or Cl, are transitional between pure silicate melts and hydrothermal fluids. In such a transitional system non-CHARAC behaviour of high field strength elements may be due to chemical complexation with a wide variety of ligands such as non-bridging oxygen, F, B, P, etc., leading to absolute and relative mineral/melt or mineral/aqueous-fluid partition coefficients that are extremely sensitive to the composition and structure of this magma. Hence, any petrogenetic modelling of such magmatic rocks, which utilizes partition coefficients that have not been determined for the specific igneous suite under investigation, may be questionable. But Y/Ho and Zr/Hf ratios provide information on whether or not the evolution of felsic igneous rocks can be quantitatively modelled: samples showing non-chondritic Y/Ho and Zr/Hf ratios or even the lanthanide tetrad effect should not be considered for modelling. However, the most important result of this study is that Y/Ho and Zr/Hf ratios may be used to verify whether Y, REEs, Zr, and Hf in rocks or minerals have been deposited from or modified by silicate melts or aqueous fluids.

Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect

Pb diffusion in zircon

Granitic plutonism is the principal agent of crustal differentiation, but linking granite emplacement to crust formation requires knowledge of the magmatic evolution, which is notoriously difficult to reconstruct from bulk rock compositions. We unlocked the plutonic archive through hafnium (Hf) and oxygen (O) isotope analysis of zoned zircon crystals from the classic hornblende-bearing (I-type) granites of eastern Australia. This granite type forms by the reworking of sedimentary materials by mantle-like magmas instead of by remelting ancient metamorphosed igneous rocks as widely believed. I-type magmatism thus drives the coupled growth and differentiation of continental crust.

https://science.sciencemag.org/content/sci/315/5814/980.full.pdf

Magmatic and Crustal Differentiation History of Granitic Rocks from Hf-O Isotopes in Zircon

Trace element partition between two pyroxenes and the host lava

Le diagramme coefficient de partage-rayon ionique (PC-IR) est presente pour les systemes tholeite a olivine, basalte alcalin a olivine, bronzite, augite, plagioclases, hornblende kaersutitique, et dacite a andesine et biotite. Le coefficient de partage d'un element est tres fortement dependant de la structure du cristal hote, de telle facon qu'a chaque site cationique de la structure correspond un pic d'allure parabolique sur le diagramme. Des ecarts a cette courbe reguliere sont observes pour des cations fortement stabilises dans un champ cristallin, particulierement les metaux de transition trivalents ainsi que les ions qui preferent une coordinance inhabituelle tel que le zinc. Les relations observees s'appliquent a tous les elements, qu'ils soient en trace ou majeurs. Il est suggere que l'effet de la structure des bains silicates pourrait etre le mieux mis en evidence par une etude systematique des anomalies des coefficients de partage de ces elements au comportement particulierement specifique mentionnes plus haut.

Crystal structure control in trace element partition between crystal and magma

Partition of trace elements between rock-forming minerals and the host volcanic rocks

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16) Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

Partition coefficient monovalent trace ions between liquids and either solid NaNO2 or KCl were determined. The isotropic elastic model of ionic crystals was used for calculating the energy change caused by the ionic substitutions. The observed values of partition coefficients in KCl good agreement with calculate values.

Hiroshi Nagasawa

Papers

Trace element partition between two pyroxenes and the host lava

Crystal structure control in trace element partition between crystal and magma

Partition of trace elements between rock-forming minerals and the host volcanic rocks

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

Trace Element Partition Coefficient in Ionic Crystals