Tin transport and cassiterite precipitation from hydrothermal fluids

Cassiterite(SnO_(2))is the main ore mineral of tin in magmatic-hydrothermal tin deposits,but tin transport and precipitation mechanisms from hydrothermal fluids remain poorly understood.We critically evalu-ated aqueous tin speciation in hydrothermal fluids from extensive experimental data and thermody-namic modeling.Sn(II)chloride complexes in hydrothermal fluids exist mainly as SnCl^(+),SnCl_(2)(aq),and SnCl_(3).The revised Helgeson-Kirkham-Flowers model parameters of these three tin species and two tin ions(Sn^(4+) and Sn^(2+))were derived from the correlation algorithms among these parameters,and the standard molar properties of cassiterite were optimized to be internally consistent with the available thermodynamic dataset.These thermodynamic parameters,together with the available equilibrium con-stant equation of Sn(IV)chloride complexes,could reproduce the available solubility data of cassiterite in acidic solutions at 400-700℃under oxygen fugacity(f_(o2))levels buffered by hematite-magnetite(HM)or nickel-nickel oxide(NNO).These comparisons allow modeling chemical systems of SnO_(2)-NaCl-HCI-H_(2)O(liquid phase)to examine tin transport and cassiterite precipitation mechanisms under tin-mineralizing conditions:300--500℃,50-150 MPa,2 molal NaCI,and fo。levels from QFM(quartz-fayalite-magnetite)to HM.Sn(I)chloride complexes are commonly interpreted to dominate in aqueous tin speciation under f_(o2)=NNO,but our modeling results indicate that considerable contents of Sn(IV)chloride complexes also exist in those reduced fluids with high HCI contents,consistent with recent in situ high-temperature experiments and molecular dynamic simulations.The Sn(I)/Sn(IV)ratios in fluids depends onfo,temperature,and HCl contents.A considerable amount of Sn(IV)possibly exist in an early mineralization stage even under f_(o2)=NNO;if so,redox reactions are unnecessary to precipitate cassiterite from these mineralizing fluids.We find that even if the f_(o2) levels are constant,simple cooling can alter mineralizing fluids to be more oxidized(e.g.,from QFM to HM)and cause cassiterite precipitation,indicating that oxidizing agents are not necessary as previously thought.This explains why cassiterite can precipitate in host rocks(e.g.,sandstone or quartzite)that do not provide oxidizing agents.A simple rise in f_(o2),levels and pH neutralization(e.g.,greisenization)also cause cassiterite precipitation.Cassiterite solubility in oxidized acidic hydrothermal fluids(NNO<f_(o2),<HM)is high enough to account for the tin contents of fluid inclusions from typical tin deposits,but the mineralization potential of oxdized fluids is inferior to reduced fluids(f_(o2),≤NNO)under the same conditions.