Metal mobilization and precipitation in a Sn-W skarn system, Gejiu Sn district, China

Abstract

In the Gejiu Sn-Cu polymetallic district, skarns with or without mineralization developed both at the contact zones between a granitic intrusion and carbonate-rich wall rocks and within carbonate-rich wall rocks. We analyzed the chemical and Sr, Nd, Pb, Li, and B isotopic compositions of mineralogically different zones in two hand specimens, i.e., a banded carbonate and a distal skarn with distinct reaction zones, to interpret chemical and isotopic variation in terms of (i) temporal compositional changes of skarn-forming fluids and (ii) reaction-induced exchange between fluids and carbonate wall rocks. The banded carbonates have seen little fluid-mediated exchange and therefore the compositions of the various bands reflect a two-component system of carbonates and detrital silicates. The compositional range of the banded carbonates represents the compositional heterogeneity of the protoliths of the distal skarn that experienced a pronounced impact by metasomatic fluids. The studied distal skarn is characterized by the vein-like aquifer (Zone I), reaction zones (Zone II and Zone III), and the carbonate aquitard (Zone IV). As evident from the distal skarn, the chemical and isotopic compositions of skarn-forming fluids change over time due to (i) processes in the fluid sources, (ii) variable contributions of different fluid sources, and (iii) reaction-induced exchange with the rocks bordering the aquifer, leading to selective addition or removal of elements from the fluid. During early interaction between aquifer fluids and its wall-rocks, the aquitard is partially consumed and the chemical and isotopic signature of the newly-formed minerals in the reaction zone represent a mixture of material derived from either fluids or wall rock. Once formed, the reaction zones largely protected the aquitard from further interaction with fluids. The Sr-budget of zones I to IV is dominated by Sr derived from the carbonate aquitard and redistributed during the consumption of older reaction zones. The Pb, Li, and B budgets of zones I to III are dominated by materials derived from the fluids. In contrast, the Nd isotopic compositions in zones II to III fall between the values of the carbonate aquitard and the aquifer. The ore elements occur in different zones, i.e., (i) scheelite, sphalerite, pyrite, and chalcopyrite precipitate in the aquifer and (ii) Sn substitutes in calc-silicates at the reaction front between zones II and III and is present in late fractures in Zone III. Thus, ore elements may have been transported by different skarn-forming fluids. The chemical and isotopic signatures of reaction zones do neither strictly reflect the nature of the reactive fluid nor reflect simple bulk mixing between fluid and wall rock, as (i) reaction-induced volume decrease may allow later fluids to infiltrate into earlier reaction zones, (ii) the fluid may be depleted in elements that have been scavenged from the fluid before, (iii) some elements having low compatibility in minerals of the reaction zones may have strongly partitioned into the fluid and are lost from the system. Although reaction zoning provides information about the nature of the reactive fluids, the mineralogically-controlled selective behavior of trace elements, i.e., most ore elements, does not allow to use the ore element content in skarn as a vector to mineralization.