Metasomatic High Field Strength Element, Tin, and Base Metal Enrichment Processes in Lithium Pegmatites from Southeast Ireland

2020 ◽  
Author(s):  
David Kaeter ◽  
Renata Barros ◽  
Julian F. Menuge

Abstract Compared to average crustal abundances, high field strength elements (HFSEs) including Zr, Nb, Hf, Ta, and U are commonly enriched in rare element pegmatites. Albite-spodumene pegmatites may show economic grades of these elements, along with Sn, primarily in oxide minerals. Processes leading to enrichment and precipitation of HFSEs in these rocks are not well understood. Here, we characterize the textures and geochemistry of minerals of HFSEs, tin, and base metals in the Leinster albite-spodumene pegmatites. We use these data to infer processes for enrichment and precipitation of these metals during pegmatite crystallization, especially subsolidus processes. The Leinster albite-spodumene pegmatites are located within the East Carlow deformation zone on the eastern flank of the Caledonian S-type Leinster batholith, southeast Ireland. The final crystallization stages of these pegmatites are characterized by autometasomatism and hydrothermal overprint leading to in situ greisenization and precipitation of massive, commonly replacive, albitites. Cassiterite and HFSE minerals (columbite-tantalite and zircon) crystallized predominantly during these late stages. Crystals of HFSE minerals that precipitated during the early magmatic stages commonly exhibit evidence of resorption and additional growth during later stages. Others, such as microlite and uraninite, only crystallized during metasomatism or from hydrothermal fluids. Base metal sulfides are among the last precipitates from these fluids. We present a detailed paragenetic sequence for the Leinster albite-spodumene pegmatites and show that late-stage aqueous fluids transported HFSEs, especially after all the melt had crystallized. Tantalum enrichment seems to have been controlled by processes affecting the entire crystallizing medium, as opposed to fractional crystallization of columbite-tantalite. The textures and parageneses described in the present and our previous work are well explained by element partitioning between coexisting liquids with characteristics similar to those described in published melt-melt-fluid immiscibility models for rare element pegmatites but do not exclude other models for early-stage pegmatite evolution. The chemical and textural features of columbite-tantalite and cassiterite in the Leinster albite-spodumene pegmatites are seen in similar rare element pegmatites and rare metal granites elsewhere, suggesting wide applicability of the processes interpreted for Leinster. Late-stage processes of the type that affected the lithium pegmatites at Leinster may either enhance or reduce economic potential: ore metal tenor may be increased because late-stage columbite-tantalite is generally richer in Ta, and/or ore metals may be lost from pegmatites to country rocks. Lithium pegmatites, including the ones at Leinster, are commonly associated spatially with Sn-W veins and greisens and share some geochemical and textural features, such as evidence of widespread albitization. We propose that lithium pegmatites are transitional products regarding the interrelated dimensions time, temperature, and depth in S-type granite-related Li-Sn-W mineralizing systems.

2020 ◽  
Vol 105 (7) ◽  
pp. 1078-1087
Author(s):  
Alysha G. McNeil ◽  
Robert L. Linnen ◽  
Roberta L. Flemming ◽  
Mostafa Fayek

Abstract Niobium and tantalum, rare metals and high field strength elements (HFSEs) that are essential to modern technologies, are concentrated among others in lithium-cesium-tantalum (LCT) pegmatites and rare metal granites. The most important hosts for Nb-Ta in these types of deposits are the columbite group minerals (columbite-tantalite), but at some ore deposits significant Ta is also contained in wodginite, microlite, and tapiolite. Previous solubility experiments of HFSE minerals have been limited to high temperatures because of the slow diffusivities of HFSEs in granitic melts. An experiment protocol is described herein that allows HFSE mineral solubilities to be determined at lower temperatures, more in line with the estimated solidus temperatures of LCT pegmatites and rare metal granites. This is achieved through the interaction of a melt that is enriched in high field strength elements (e.g., P and Nb or Ta) with a fluid enriched in a fluid-mobile element (FME, e.g., Mn). A starting glass enriched in a slow diffusing HFSE was synthesized, and HFSE mineral saturation is obtained via the diffusion of a FME into the melt via interaction with a fluid. This interaction can occur at much lower temperatures in reasonable experimental durations than for experiments that require diffusion of niobium and tantalum. The solubility product of columbite-(Mn) from the fluid-melt interaction experiment in a highly fluxed granitic melt at 700 °C is the same as those from dissolution and crystallization (reversal) experiments at the same P-T conditions. Thus, both methods produce reliable measurements of mineral solubility, and the differences in the metal concentrations in the quenched melts indicates that the solubility of columbite-(Mn) follows Henry's Law. Results show that columbite-(Mn) saturation can be reached at geologically reasonable concentrations of niobium in melts and manganese in hydrothermal fluids. This experimental protocol also allows the investigation of HFSE mineral crystallization by fluid-melt interactions in rare-metal pegmatites. Magmatic origins for columbite group minerals are well constrained, but hydrothermal Nb-Ta mineralization has also been proposed for pegmatite-hosted deposits such as Tanco, Greenbushes, and granite-hosted deposits such as Cínovec/Zinnwald, Dajishan, and Yichun. This study shows that columbite-(Mn), lithiophilite, and a Ca-Ta oxide mineral (that is likely microlite) crystallized from experiments in fluid-melt systems at temperatures as low as 650 °C at 200 MPa. It is important to note that HFSE minerals that crystallize from fluid-melt interactions texturally occur as euhedral crystals as phenocrysts in glass, i.e., are purely magmatic textures. Therefore, crystallization of HFSE minerals from fluid-melt interactions in rare metal granites and pegmatite deposits may be more widespread than previously recognized. This is significant because the formation of these deposits may require magmatic-hydrothermal interaction to explain the textures present in deposits worldwide, rather than always being the result of a single melt or fluid phase.


Author(s):  
L Scheef ◽  
M Daamen ◽  
U Fehse ◽  
MW Landsberg ◽  
DO Granath ◽  
...  

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