Fluid Evolution and Scheelite Precipitation Mechanism of the Large-Scale Shangfang Quartz-Vein-Type Tungsten Deposit, South China: Constraints from Rare Earth Element(REE) Behaviour during Fluid/Rock Interaction

Unlike classic skarn-type scheelite deposits directly acquiring sufficient Ca2+ from surrounding limestones, all of the scheelite orebodies of the Shangfang tungsten(W) deposit occur mainly in amphibolite, and this provides a new perspective on the mineralization mechanism of W deposits. The ability of hydrothermal scheelite(CaWO4) to bind REE3+ in their Ca2+ crystal lattices makes it a useful mineral for tracing fluid-rock interactions in hydrothermal mineralization systems. In this study, the REE compositions of scheelite and some silicate minerals were measured systematically in-situ by laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) to assess the extent of fluid-rock interactions for the Late Mesozoic quartz-vein-type Shangfang W deposits. According to the variations in CaO and REE among scheelite and silicate minerals, the amphibole and actinolite in amphibolite may be able to release large amounts of Ca2+ and REE3+ into the ore-forming fluids during chlorite alteration, which is critical for scheelite precipitation. Furthermore, an improved batch crystallization model was adopted for simulating the process of scheelite precipitation and fluid evolution. The results of both the in-situ measurements and model calculations demonstrate that the precipitation of early-stage scheelite with medium rare-earth elements(MREE)-rich and [Eu/Eu*]N<1. The early-stage scheelite would consume more MREE than LREE and HREE of fluid, which will gradually produce residual fluids with strong MREE-depletion and [Eu/Eu*]N>1. Even though the partition coefficient of REE is constant, the later-stage scheelite will also inherit a certain degree of MREE-depletion and [Eu/Eu*]N future from the residual fluids. As a common mineral, sheelite forms in various types of hydrothermal ore deposits(e.g., tungsten and gold deposits). Hence, the improved batch crystallization model is also possible for obtaining detailed information regarding fluid evolution for other types of hydrothermal deposits. The results from model calculations also illustrate that the Eu anomalies of scheelite are not an effective index correlated to oxygen fugacity of fluids but rather are dominantly controlled by the continuous precipitation of scheelite.