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

Cpx/melt partition coefficients have been determined by ion probe for 24 trace elements at natural levels in an alkali basalt experimentally equilibrated at 1,380°C and 3 GPa. One goal was to intercompare Ds for both high-field-strength elements and rare earth elements (REE) in a single experiment. Relative to the REE spidergram, Hf and Ti show virtually no anomaly, whereas Zr exhibits a major negative anomaly. Other incompatible elements (Ba, K, Nb) fall in the range of published values, as do elements such as Sr, Y, Sc, Cr and V. Pb shows a value intermediate between La and Ce. Values for Be, Li and Ga are reported for the first time, and show that Be is as incompatible as the light REEs whereas Li and Ga are somewhat more compatible than the heavy REE.

Experimental cpx/melt partitioning of 24 trace elements

Mid-ocean ridge basalts (MORB) are a consequence of pressure-release melting beneath ocean ridges, and contain much information concerning melt formation, melt migration and heterogeneity within the upper mantle. MORB major element chemical systematics can be divided into global and local aspects, once they have been corrected for low pressure fractionation and interlaboratory biases. Regional average compositions for ridges unaffected by hot spots ("normal" ridges) can be used to define the global correlations among normalized Na20, FeO, TiO2 and Si02 contents, CaO/Al 203 ratios, axial depth and crustal thickness. Back-arc basins show similar correlations, but are offset to lower FeO and TiO2 contents. Some hot spots, such as the Azores and Galapagos, disrupt the systematics of nearby ridges and have the opposite relationships between FeO, Na 20 and depth over distances of 1000 km. Local variations in basalt chemistry from slowand fast-spreading ridges are distinct from one another. On slow-spreading ridges, correlations among the elements cross the global vector of variability at a high angle. On the fast-spreading East Pacific Rise (EPR), correlations among the elements are distinct from both global and slow-spreading compositional vectors, and involve two components of variation. Spreading rate does not control the global correlations, but influences the standard deviations of axial depth, crustal thickness, and MgO contents of basalts. Global correlations are not found in very incompatible trace elements, even for samples far from hot spots. Moderately compatible trace elements for normal ridges, however, correlate with the major elements. Trace element systematics are significantly different for the EPR and the mid-Atlantic Ridge (MAR). Normal portions of the MAR are very depleted in REE, with little variability; hot spots cause large long wavelength variations in REE abundances. Normal EPR basalts are significantly more enriched than MAR basalts from normal ridges, and still more enriched basalts can erupt sporadically along the entire length of the EPR. This leads to very different histograms of distribution for the data sets as a whole, and a very different distribution of chemistry along strike for the two ridges. Despite these differences, the mean Ce/Sm ratios from the two ridges are identical. Existing methods for calculating the major element compositions of mantle melts [Klein and Langmuir, 1987; McKenzie and Bickle, 1988; Niu and Batiza, 1991] are critically examined. New quantitative methods for mantle melting and high pressure fractionation are developed to evaluate the chemical consequences of melting and fractionation processes and mantle heterogeneity. The new methods rely on new equations for partition coefficients for the major elements between mantle minerals and melts. The melting calculations can be used to investigate the chemical compositions produced by small extents of melting or high pressures of melting that cannot yet be determined experimentally. Application of the new models to the observations described above leads to two major conclusions: (1) The global correlations for normal ridges are caused by variations in mantle temperature, as suggested by Klein and Langmuir [1987] and not by mantle heterogeneity. (2) Local variations are caused by melting processes, but are not yet quantitatively accounted for. On slower spreading ridges, local variations are controlled by the melting regime in the mantle. On the EPR, local variations are predominantly controlled by ubiquitous, small scale heterogeneites. Volatile content may be an important and as yet undetermined factor in affecting the observed variations in major elements. We propose a hypothesis, similar to one proposed by Allegre et al [1984] for isotopic data, to explain the differences between the Atlantic and Pacific local trends, and the trace element systematics of the two ocean basins, as consequences of spreading rate and a different distribution of enriched components from hot spots in the two ocean basins. In the Atlantic, the hot spot influence is in discrete areas, and produces clear depth and chemical anomalies. Ridge segments far from hot spots do not contain enriched

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Petrological systematics of mid-ocean ridge basalts: Constraints on melt generation beneath ocean ridges

MANY geochemical processes, such as crystallization of silicate magmas or planetary differentiation, require a knowledge of the way in which elements become partitioned between coexisting crystal and liquid phases1,2. But quantitative prediction of crystal/melt partition coefficients from thermodynamic principles has not previously been possible. By studying the partitioning of 15 elements between silicate minerals and their coexisting melts, we show here that the partitioning behaviour of any series of isovalent cations can be rationalized in terms of a simple model in which the size and elasticity of the crystal lattice sites play a critical role. We find that elasticity varies linearly with the formal charge of the cation. This model allows us to predict element partitioning behav-iour solely from the physical characteristics of the cation sites in the crystal.

Prediction of crystal–melt partition coefficients from elastic moduli

Trace element partition between two pyroxenes and the host lava

Neutron activation analysis of U, Th and K has been made on some possible mantle materials, mainly peridotite nodules from continental and oceanic areas. The paper first describes the analytical procedures of U and Th determinations. Results of analysis showed that oceanic nodules have more uniform concentrations of U, Th and K and Th/U, K/U ratios than continental nodules. Average values for 7 oceanic lherzolites are: (1.87±0.27)×10-8 gU/g, (5.48±0.87)×10-8 gTh/g, and (54.2±7.5)×10-6 gK/g, giving a rate of heat production, 26×10-16 cal/cm3·sec, which is about 70% of that for the average chondrite. There is no indication that oceanic lherzolites are more enriched in these elements than the continental ones. These results suggest that, from the thermal point of view, peridotite nodules may not be the representative constituent of the upper mantle, unless the oceanic mantle is capable of transferring heat exceedingly well. The average values of the ratios are Th/U=2.93±0.61, and K/U=(0.29±0.06)×104. The latter is significantly smaller than the crustal value (1×104), which is already smaller than the chondritic value (5×104).

Hiroshi Wakita

Papers

Trace element partition between two pyroxenes and the host lava

Uranium, thorium, and potassium contents of possible mantle materials.

Partition of uranium and thorium between augite and host lavas

Uranium and thorium contents in ultrabasic rocks

Neutron activation analysis of potassium in ultrabasic rocks