Tourmaline-rich rocks are widespread minor lithologies within the Early Proterozoic Willyama Supergroup in the Broken Hill district, Australia. Tourmaline concentrations occur in strata-bound and local stratiform tourmalinites, clastic metasedimentary rocks, quartz-gahnite lode rocks, stratiform Pb-Zn-Ag sulfide ores, garnet quartzites, strata-bound scheelite deposits, quartz-tourmaline nodules, discordant quartz veins, and granitic pegmatites. Most of the tourmaline-rich rocks are within the Broken Hill Group that hosts the main Pb-Zn-Ag ores.At the Globe mine along the northeast end of the main lodes, tourmalinites are closely associated with Pb-Zn-Ag mineralization and in places are interbedded with Mn-rich garnet quartzites. Galena and other ore minerals occur locally in the cores of recrystallized tourmaline grains in these tourmalinites, indicating that tourmaline and sulfides were present together prior to deformation and high-grade metamorphism. Electron microprobe analyses of tourmalines intergrown with Fe sulfides at the Globe mine show Mg-rich compositions relative to tourmalines in sulfide-free assemblages from the same area, suggesting early (premetamorphic) introduction of boron and Mg enrichment of tourmaline by sulfide-silicate reactions during metamorphism.Combined field and geochemical data indicate that the district tourmalinites represent normal clastic sediments that were metasomatically altered by boron-rich hydrothermal fluids at or below the sediment-water interface. Whole-rock chemical analyses of 33 tourmaline-rich rocks show linear trends of data for major and trace elements that closely resemble the trends observed for unmineralized elastic metasedimentary rocks of the district. Average Fe/Al, Mg/Al, Na/Al, and Ti/Al molar ratios of the tourmaline-rich rocks and clastic metasediments are very similar; the average K/Al molar ratio of the tourmaline-rich rocks is significantly lower than that of the clastic metasediments, reflecting the loss of K during tourmalinite formation. Chondrite-normalized patterns of rare earth elements (REE) in the quartz-rich tourmalinites are generally similar to those of the clastic metasediments, except for minor depletions of light REE; local positive and negative Ce anomalies suggest tourmalinite formation in the presence of seawater or a seawater-derived pore fluid. The geochemical data imply relative immobility of Al, Ti, Cr, and heavy REE during hydrothermal alteration and later metamorphism. Boron isotope analyses of 52 tourmaline separates show a total range of delta 11 B values from -26.8 to -17.0 per mil. Fine-grained, euhedral, nonpoikilitic tourmalines from tourmalinites in the andalusite-muscovite zone in the northern part of the district (e.g., Black Prince mine) have delta 11 B values from -21 to -17 per mil, whereas coarse granoblastic and poikilo-blastic tourmalines from the sillimanite and two-pyroxene granulite zones in the southern part of the district (e.g., Globe mine) have delta 11 B values of-24 to -19 per mil. Tourmalines in strongly retrogressed tourmalinites have delta 11 B values from about -27 to -20 per mil. The observed variations in delta 11 B are consistent with prograde and retrograde metamorphic fractionation of boron isotopes, in which the fluid phase is preferentially enriched in the heavier isotope ( 11 B). Premetamorphic hydrothermal fluids that deposited the Black Prince tourmalinites had delta 11 B values of-8 to -5 per mil at 200 degrees to 300 degrees C, suggesting a boron source from nonmarine evaporite borates.Tourmalinites in the Broken Hill district apparently formed by the same submarine hydrothermal processes as the main Pb-Zn-Ag lodes and the siliceous ferromanganese protoliths of the garnet quartzites. In our model, the hydrothermal system(s) acquired abundant boron by leaching evaporitic borates within the Thackaringa Group, the stratigraphic sequence that underlies the Broken Hill Group and most of the tourmaline concentrations. We suggest that evaporites of the Thackaringa Group provided a source of readily extractable boron for formation of the tourmalinites and also the source of the fluoride, sulfur, and perhaps the carbonate in the main lodes; such evaporites may have been critical for increased metal chloride complexing and transport necessary for deposition of the high-grade Pb-Zn-Ag ores. The Broken Hill deposit may have formed contemporaneously with the Mount Isa and McArthur River Pb-Zn-Ag deposits in similar evaporite-bearing sequences during widespread Early Proterozoic continental rifting.

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