Partitioning of REE between calcite and carbonatitic melt containing P, S, Si at 900-650 °C and 100 MPa

Many carbonatites host deposits of REE and HFSE, and fractional crystallization might be a potentially powerful mechanism controlling magma enrichment by these metals to economically significant values. At present, information about the control of fractional crystallization by partition coefficients of ore-forming elements at magmatic stage is incomplete. Here we present an experimental study of REE partitioning between carbonatite melt and calcite in the system CaCO3-Na2CO3 with varying amounts of P2O5, F, Cl, SiO2, SO3 at 650–900°C and 100 MPa using cold-seal pressure vessels and LA-ICP-MS. The presence of phosphorus in the system generally increases the distribution coefficients but its effect decreases with increasing concentration. The influence of temperature is great: at 900 − 770°C DREE ≥1, while at lower temperatures the values are below unity. Silicon also promotes the fractionation of REE into calcite, while sulfur contributes to the retention of REE in the melt. Our results imply that calcite may impose significant control upon REE fractionation at the early stages of crystallization of carbonatite magma and can be a closest proxy for monitoring the REE content in initial melt.

PETROLOGY AND GEOCHEMISTRY OF INTRUSIVE ROCKS OF THE SINYUKHINSKOYE DEPOSIT (GORNY ALTAI)

New data on phase relationships, petrology and geochemistry of the Sinyukhinskoye rocks and dikes of the same deposit are presented. Five phases of rock intrusions formed in a homodromic-antidromic sequence are found. The Sinyukhinskoye rocks fall in the oxidized type. In the depth, a source of melting was garnet lherzolites, and, to a lesser extent, spinel lherzolites of an enriched mantle source of the lithospheric slab with a degree of partial melting from 0.2 to 0.4 and low pressure. The formation of intrusive rocks of the deposit took place in the post-collisional environment. The magmatite fluids of the massif and dikes were characterized by high partial pressures of such volatile components as H2O, Cl, F, CO2, which were the main carriers of metals. The rocks exhibit the tetrad effect of the W-type REE fractionation. The dependences of the values of the latter and the concentrations of copper and gold in igneous rocks and fluids were determined by different regimes of acidity and alkalinity of the medium. The deposit belongs to a complex family of ores of the copper-gold-skarn-porphyry type. In the Cheryomukhovaya Sopka and Chir areas, this is also confirmed by the presence of the copper-gold-porphyry type in the ore field, in addition to the gold-copperskarn mineralization.

Rare earth element geochemistry of sediments from the southern Okinawa Trough since 3 ka: Implications for river-sea processes and sediment source

The sediment sources in the southern Okinawa trough (SOT) are still controversial and few studies have focused on the effects of transport processes on the elemental composition of initial terrigenous materials. Here we present rare earth element (REE) and trace element data on siliciclastic sediments from 14C age-dated Core S3, which was collected from the SOT, to provide reliable evidence for illustrating the modified effects of marine environments on terrigenous sediments deposited at different stages and exposing changes in sediment source over the past 3 ka. Compared with bulk sediments, the siliciclastic sediments in S3 have more variable REE fractionation parameters and lower middle REE (MREE) contents. Our REE data indicate that during river-sea processes, MREE-enriched fractions such as Fe–Mn oxides and carbonate were added to the original terrigenous sediments before deposition, weakening the degree of REE fractionation in the initial sediments; thus, care should be taken when using REE data from bulk samples to decipher source changes. The temporal changes in sediment source in S3 can be broadly identified based on the REE fractionation parameters of the residual fractions, and the results are largely consistent with the findings obtained by heavy mineral examinations. Units 1 and 3 are dominated by reworked shelf sediments of Changjiang origin,while the proportion of Taiwan-derived sediment is notably higher in Units 2 and 4. The sediment flux of Taiwan origin in the SOT was much smaller than previously thought. Huanghe-derived sediments and volcanic materials did not contribute significantly to the late Holocene sedimentation in the SOT. The large variations in sediment sources in S3 were possibly caused by changes in transport patterns driven by time-dependent changes in oceanic currents.

Fractionation of Rare Earth Elements in Greisen and Hydrothermal Veins Related to A-Type Magmatism

This study focuses on concentrations and fractionation of rare earth elements (REE) in a variety of minerals and bulk materials of hydrothermal greisen and vein mineralization in Paleoproterozoic monzodiorite to granodiorite related to the intrusion of Mesoproterozoic alkali- and fluorine-rich granite. The greisen consists of coarse-grained quartz, muscovite, and fluorite, whereas the veins mainly contain quartz, calcite, epidote, chlorite, and fluorite in order of abundance. A temporal and thus genetic link between the granite and the greisen/veins is established via high spatial resolution in situ Rb-Sr dating, supported by several other isotopic signatures (δ34S, 87Sr/86Sr, δ18O, and δ13C). Fluid-inclusion microthermometry reveals that multiple pulses of moderately to highly saline aqueous to carbonic solutions caused greisenization and vein formation at temperatures above 200–250°C and up to 430°C at the early hydrothermal stage in the veins. Low calculated ∑REE concentration for bulk vein (15 ppm) compared to greisen (75 ppm), country rocks (173–224 ppm), and the intruding granite (320 ppm) points to overall low REE levels in the hydrothermal fluids emanating from the granite. This is explained by efficient REE retention in the granite via incorporation in accessory phosphates, zircon, and fluorite and unfavorable conditions for REE partitioning in fluids at the magmatic and early hydrothermal stages. A noteworthy feature is substantial heavy REE (HREE) enrichment of calcite in the vein system, in contrast to the relatively flat patterns of greisen calcite. The REE fractionation of the vein calcite is explained mainly by fractional crystallization, where the initially precipitated epidote in the veins preferentially incorporates most of the light REE (LREE) pool, leaving a residual fluid enriched in the HREE from which calcite precipitated. Fluorite occurs throughout the system and displays decreasing REE concentrations from granite towards greisen and veins and different fractionation patterns among all these three materials. Taken together, these features confirm efficient REE retention in the early stages of the system and minor control of the REE uptake by mineral-specific partitioning. REE-fractionation patterns and fluid-inclusion data suggest that chloride complexation dominated REE transport during greisenization, whereas carbonate complexation contributed to the HREE enrichment in vein calcite.