Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf, Australia

Abstract

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia. Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (⩽5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ∼5 times seawater and extremely elevated I/Cl ratios of ∼11,500 times seawater. The first two fluids have 40Ar/36Ar of 300–400 and greater than air saturated water 36Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest 40Ar/36Ar ratio of up to 1500 and a depleted 36Ar concentration. Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H2S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and 36Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct 40Ar/36Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.