Sedimentary exhalative (SEDEX) Zn-Pb-sulfide mineralization first occurred on a large scale during the late Paleoproterozoic. Metal sulfides in most Proterozoic deposits have yielded broad ranges of predominantly positive δ 34 S values traditionally attributed to bacterial sulfate reduction. Heavy isotopic signatures are often ascribed to fractionation within closed or partly closed local reservoirs isolated from the global ocean by rifting before, during, and after the formation of Rodinia. Although such conditions likely played a central role, we argue here that the first appearance of significant SEDEX mineralization during the Proterozoic and the isotopic properties of those deposits are also strongly coupled to temporal evolution of the amount of sulfate in seawater. The ubiquity of 34 S-enriched sulfide in ore bodies and shales and the widespread stratigraphic patterns of rapid δ 34 S variability expressed in both sulfate and sulfide data are among the principal evidence for global seawater sulfate that was increasing during the Proterozoic but remained substantially lower than today. Because sulfate is produced mostly through weathering of the continents in the presence of oxygen, low Proterozoic concentrations imply that levels of atmospheric oxygen fell between the abundances of the Phanerozoic and the deficiencies of the Archean, which are also indicated by the Precambrian sulfur isotope record. Given the limited availability of atmospheric oxygen, deep-water anoxia may have persisted well into the Proterozoic in the presence of a growing sulfate reservoir, which promoted prevalent euxinia. Collectively, these observations suggest that the mid-Proterozoic maximum in SEDEX mineralization and the absence of Archean deposits reflect a critical threshold in the accumulation of oceanic sulfate and thus sulfide within anoxic bottom waters and pore fluids—conditions that favored both the production and preservation of sulfide mineralization at or just below the seafloor. Consistent with these evolving global conditions, the appearance of voluminous SEDEX mineralization ca. 1800 Ma coincides generally with the disappearance of banded iron formations—marking the transition from an early iron-dominated ocean to one more strongly influenced by sulfide availability. In further agreement with this conceptual model, Proterozoic SEDEX deposits in northern Australian formed from relatively oxidized fluids that required reduced conditions at the site of mineralization. By contrast, the generally more oxygenated Phanerozoic ocean may have only locally and intermittently favored the formation and preservation of exhalative mineralization, and most Phanerozoic deposits formed from reduced fluids that carried some sulfide to the site of ore precipitation.

Abstract In terms of zinc, lead, and silver metal endowment, the Proterozoic sedimentary basins of northern Australia rank number one in the world. The Mt. Isa-McArthur basin system hosts five supergiant, stratiform, sedimentary rock-hosted Zn-Pb-Ag deposits (McArthur River, Century, Mt. Isa, Hilton, and George Fisher) and one supergiant strata-bound Ag-Pb-Zn deposit (Cannington). These superbasins consist of units deposited during three nested cycles of deposition and exhumation that occurred in the period from 1800 to 1580 Ma. The cycles took place in response to far -field extension and subsidence associated with a major northward-dipping subduction zone in central Australia. All major stratiform zinc-dominant deposits occur within rocks of the sag phase of the youngest Isa superbasin, which was deposited between 1670 and 1580 Ma. The strata-bound silver- and lead-rich Cannington deposit is hosted by highgrade metamorphosed clastic sedimentary rocks that are temporal correlatives of the basal extensional phase of the Isa superbasin. It exhibits distinct differences from the stratiform zinc-dominant deposits but shows similarities with Broken Hill-type deposits. The major stratiform Zn-Pb-Ag deposits exhibit many similar geological and geochemical features that include: (1) location close to regionally extensive normal and strike-slip synsedimentary faults, (2) organic-rich black shale and siltstone host rocks, (3) laminated, bedding-parallel synsedimentary sulfide minerals, (4) stacked ore lenses separated by pyritic and Fe-Mn carbonate-bearing siltstones, (5) lateral zonation exhibiting an increasing Zn/Pb ratio away from the feeder fault, (6) vertical zonation exhibiting decreasing Zn/Pb ratio upstratigraphy, (7) an extensive strata-bound halo of iron- and manganese-rich alteration in the sedimentary rocks surrounding and along strike from ore, (8) a broad range of δ 34 S values for sulfide minerals, from about 0 to 20 per mil, with pyrite exhibiting a greater spread than base metal sulfides, and (9) lead isotope ratios that indicate derivation of lead from intrabasinal sources with interpreted lead model ages being similar to the measured zircon U-Pb ages of the host rocks. These common features demonstrate that the stratiform Zn-Pb-Ag ores formed approximately contemporaneously with sedimentation and/or diagenesis. The exact timing of mineralization relative to these processes varies from deposit to deposit. However metamorphic overprints in some deposits (e.g., Mt. Isa, Hilton, Dugald River, Lady Loretta) have lead to recrystallization of sulfide minerals, making it difficult to interpret primary paragenetic relationships and absolute timing of mineralization. Mount Isa is the only northern Australian stratiform Zn-Pb-Ag deposit that has spatially associated highgrade copper mineralization. Textural and isotopic data for the stratiform Zn-Pb-Ag deposits suggest there is a spread of ore depositional processes from synsedimentary exhalative to syndiagenetic replacement. At McArthur River, for example, the highgrade laminated ores principally formed by synsedimentary exhalative processes. However, there is good evidence that the lower grade ores at the margins of the deposit formed at shallow depth in the organic-rich muds by syndiagenetic replacement and open-space fill. At Century, on the other hand, the textual and lead isotope evidence indicate the major mineralization probably formed by syndiagenetic replacement about 20 m.y. after sedimentation. At Mt. Isa, Hilton, and George Fisher, overprinting metamorphism precludes determination of the precise timing of ore deposition relative to sedimentation and diagenesis, but recent studies at the least metamorphosed George Fisher deposit suggest that syndiagenetic replacement was likely dominant. The lack of footwall stringer zones or hydrothermal vent complexes in the Zn-Pb-Ag deposits, coupled with the lateral and vertical Pb-Zn metal zonation, suggest the ores are of the vent-distal type, forming at some lateral distance from the hydrothermal vent or feeder fault. The laterally extensive strata-bound Fe-Mn car bonate halos indicate significant hydrothermal fluid volumes that have interacted with the sea-floor and sub-sea-floor sediments. These halos provide an important vector for exploration. Basin-scale, fluid-flow modeling has emphasized the importance of (1) early rift phase volcanic and volcaniclastic rocks as potential deep sources for metals, (2) clastic units at the top of the rift package that act as aquifers for basin-wide hy drothermal fluid flow, (3) evaporitic units that lead to high fluid salinity, which enhances metal transport, (4) thick packages of fine-grained dolomites and siltstones in the overlying sag phase sequence, which act as a seal over the fluid-rich reservoir rocks (rift clastics), and (5) deeply penetrating faults that provide the fluid conduit from the fluid reservoir and metal source area, located deep in the sedimentary basin, to the organic-rich trap rocks at the top of the section. Fluids were oxidized, low- to moderate-temperature (100°–250°C), near-neutral pH brines, with sulfate reduction in organic-bearing trap sites being the principal cause of zinc- and lead-bearing sulfide deposition.

Abstract Volcanogenic massive sulfide deposits in Australia exhibit a range in average gold content from 0.2 to 4.75 ppm Au, with an overall mean of 1.6 ppm. The Mount Morgan Cu-Au deposit in eastern Queensland has been the major producer (237.5 metric tons of gold), followed by the deposits in the Mount Read Volcanics of western Tasmania (Rosebery, Hercules, Que River, Hellyer, and Mount Lyell) which together have a premining resource of 156.3 metric tons of gold. Two distinct spatial and mineralogical associations of gold mineralization have been defined for the eastern Australian volcanogenic massive sulfide deposits: (1) a gold-zinc association (with lead, silver, and barite), which typically occurs throughout the massive and layered ores with gold and barite concentrated toward the stratigraphic hanging wall of the deposit (e.g., Rosebery, Que River, and Hellyer), and (2) a gold-copper association, which typically occurs in the footwall stringer and lower massive zones of some deposits, particularly those with a high Cu/Zn ratio (e.g., Mount Chalmers, Mount Morgan, and Mount Lyell). This biparite gold association observed in the eastern Australian deposits is also displayed in other volcanogenic massive sulfide provinces, such as the kuroko district (Japan) and the Canadian Archean. Thermodynamic studies on the controls of gold transport and deposition indicate that the two gold associations described above may relate directly to the gold-transporting mechanism. The footwall gold-copper association reflects gold transport as the AuCl 2 complex by high-temperature (>300°C), low pH (<4.5), moderate to high f O2 , and high-salinity fluids (>seawater). The hanging-wall gold-zinc association reflects gold transport as the Au(HS) − 2 complex by lower temperature (150°-300°C), moderate pH (4.5-6), and moderate f o2 fluids. A process of gold refining where cooling hydrothermal solutions leach gold (plus zinc and lead) from the lower parts of the sulfide body and reprecipitate the gold at the top of the body, and which is associated with dropping temperature and increasing SO 4 /H 2 S ratio, is proposed as the mechanism which leads to gold enrichment at the top of zinc-rich deposits. This process is common in barite-rich Paleozoic deposits but less common in Archean deposits, due to lower SO 4 /H 2 S fluid ratios in the latter.