Rare earth element fractionation in magmatic Ca-rich garnets

Igneous garnets have the potential to strongly fractionate rare earth elements (REE). Yet informations on partition coefficients are very scant, and criteria for distinguishing between hydrothermal and magmatic garnets are ambiguous. To fill this gap, we present trace element and isotopic data for two types of Ca-rich garnets from phonolites (Mt. Somma-Vesuvius). Both Ca-garnet populations are different in their style and dynamics of fractionation: one population is progressively strongly depleted in HREE from core to rim, reflecting REE fractionation in the host phonolite via earlier-crystallized garnets. Such examples for extreme changes in HREE in garnets are only known for hydrothermal grandites by REE-bearing fluids. The second garnet population is homogeneous and formed in a closed system. Near-flat patterns between Sm and Lu confirm experimental data indicating lower D(Sm)/D(Lu) for Ca-rich garnets than for e.g. pyrope-rich garnets. It follows: D ^Grt/PhMelt for La = 0.5, Sm = 48 and Yb = 110.     

Carbonate- and silicate-rich globules in the kimberlitic rocks of northwestern Tarim large igneous province,NW China: Evidence for carbonated mantle source

We report carbonate- and silicate-rich globules and andradite from the Wajilitage kimberlitic rocks in the northwestern Tarim large igneous province, NW China. The carbonate-rich globules vary in size from 1 to 3 mm, and most have ellipsoidal or round shape, and are composed of nearly pure calcite. The silicate-rich globules are elliptical to round in shape and are typically larger than the carbonate-rich globules ranging from 2 to several centimeters in diameter. They are characterized by clear reaction rims and contain several silicate minerals such as garnet, diopside and phlogopite. The silicate-rich globules, reported here for the first time, are suggested to be related to the origin of andradite within the kimberlitic rocks. Our results show that calcite in the carbonate-rich globules has a high X_Ca (>0.97) and is characterized by extremely high concentrations of the total rare earth elements (up to 1500 ppm), enrichment in Sr (8521–10,645 ppm) and LREE, and remarkable depletion in Nd, Ta, Zr, Hf and Ti. The calcite in the silicate-rich globules is geochemically similar to those in the carbonate-rich globules except the lower trace element contents. Garnet is dominantly andradite (And_{59.56–92.32}Grs_5.67–36.03Pyr_0.36–4.61Spe_0–0.33) and is enriched in light rare earth elements (LREEs) and relatively depleted in Rb, Ba, Th, Pb, Sr, Zr and Hf. Phlogopite in the silicate-rich globules has a high Mg^# ranging from 0.93 to 0.97. The composition of the diopside is Wo_{45.82–51.39}En_{39.81–49.09}Fs_0.88–0.95 with a high Mg^# ranging from 0.88 to 0.95. Diopside in the silicate-rich globules has low total rare earth element (REE) contents (14–31 ppm) and shows middle REE- (Eu to Gd), slight light REE- and heavy REE-enrichment with elevated Zr, Hf and Sr contents and a negative Nb anomaly in the normalized diagram. The matrix of the kimberlitic rocks are silica undersaturated (27.92–29.31 wt.% SiO₂) with low Al₂O₃ (4.51–5.15 wt.%) and high CaO (17.29–17.77 wt.%) contents. The samples are characterized by incompatible element enrichment with high (La/Yb)_N values (41–58) and remarkable negative anomalies in HFSEs (e.g. Ta, Zr, Hf). Our new data suggest that the carbonate-rich globule most likely crystallized at high-temperature and does not represent immiscible liquids, whereas the silicate-rich globules are related to carbonate-rich deuteric hydrothermal fluids during the later-stage of melt evolution. The fluids reacted with the surrounding silicate melts resulting in the formation of skarn minerals such as phlogopite, diopside and andradite. The presence of the carbonate-bearing globules indicates that the Wajilitage kimberlitic rocks are carbonate-rich and most likely derived from an enriched mantle with abundant carbonate. We correlate the carbonated mantle to metasomatism by the migration of deep-seated fluids (carbonate-rich) in response to the impingement of the early Permian mantle plume.     

Pressure–volume–temperature equation of state of andradite and grossular, by high-pressure and -temperature powder diffraction

 The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for andradite K ₀=158.0(±1.5) GPa, (dK/dT )₀=−0.020(3) GPa K⁻¹ and α₀=31.6(2) 10⁻⁶ K⁻¹, and for grossular K ₀=168.2(±1.7) GPa, (dK/dT)₀=−0.016(3) GPa K⁻¹ and α₀=27.8(2) 10⁻⁶ K⁻¹. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out. Received: 7 July 2000 / Accepted: 20 October 2000