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The Maranon Valley, located in the Eastern Cordillera of the northern Peruvian Andes, represents a 160-km-long section of the continental margin that was mainly active during the Paleozoic. A combination of whole rock geochemistry, and U-Pb, O and Hf isotope microanalysis of zircon on selected igneous rocks, reveals the timing and magmatic source variations along and across-strike of the Paleozoic proto-Andean margin. The igneous rocks exhibit a typical arc-related continental margin signature, with strong enrichment in LILE (e.g., Cs, Rb and Th), depletion of HFSE (e.g., Nb) and a negative Ti anomaly. The overlapping Hf-O isotopic compositions, together with similar inherited zircon ages, are consistent with the Lavasen Volcanics, the Esperanza Subvolcanic Complex and the Pataz Batholith sharing the same crustal source components, in about the same proportion. A genetic relationship is further supported by the strong depletion in Sr, Nb, Ta, Ti and Eu in the subvolcanic and volcanic rocks from the Esperanza Subvolcanic Complex and Lavasen Volcanics compared to the intrusive rocks from the Pataz Batholith, which is consistent with evolution of the erupted magmas by fractional crystallization. The new zircon U-Pb (LA-ICP-MS) age determinations, in combination with previously published geochronological data, suggest that the Pataz Batholith, the Esperanza Subvolcanic Complex and the Lavasen Volcanics were emplaced contemporaneously between ca. 342 Ma and 332 Ma. The new Mississippian U-Pb (zircon U-Pb LA-ICP-MS) age determination for the Lavador Pluton (336–332 Ma) and the Callangate-Enaben Pluton (341–337 Ma) suggest that magmatism was coeval with the emplacement of the Pataz Batholith. The Lavador Pluton is aligned with the main N-NW trend of the Pataz Batholith, and shares a similar range of Hf-O isotopic values (i.e., eHf (t) values from −5.3 to −1.3 and δ18O values from 6.4 to 7.1‰), and is therefore believed to represent a northern extension of the Pataz Batholith. The isotopic geochemistry and lithogeochemistry record in the Maranon Valley illustrates the regional scale tectonic switches that occurred during arc formation, from syn-collisional and compression in the Pataz-Parcoy district between ca. 342 Ma and 332 Ma, to post-collisional and extensional in the Montanitas district between ca. 332 Ma and 319 Ma. The delineation of the timing and location of tectonic regime switches in the Maranon Valley may provide a basis for future mineral exploration.

In the Pataz-Parcoy district, current mining activity is focused on the mesothermal quartz-carbonate-sulfide veins hosted by the Pataz batholith. Total gold production yielded approximately 8 Moz with grades in the mined ore shoots varying between 7 and 15 g/t Au, and locally reaching up to 120 g/t Au. High-grade ore shoots are extraordinarily enriched in sulfides, representing 10 to 20 modal vol% of the vein. Ore mineralogy is characterized by a complex paragenesis of pyrite, arsenopyrite, galena, sphalerite, chalcopyrite, and gold. Gold occurs mostly as electrum in equilibrium with base metals sulfides filling fractures of pyrite and arsenopyrite. A novel combination of secondary ion mass spectrometry, laser ablation inductively coupled plasma mass spectrometry, and electron probe microanalysis is used to track the compositional evolution of ore fluid(s) and to investigate the mineralization processes occurring in the Pataz-Parcoy district. Contrasting with the classical two-stage ore sequence previously proposed for the Pataz-Parcoy district, we suggest a revised paragenetic sequence, i.e., (1) deposition of pyrite core (PyI) with homogeneously distributed base metal sulfide inclusions, (2) progressive replacement of PyI by arsenian pyrite (PyII) and arsenopyrite associated with invisible gold deposition, and (3) deposition of sphalerite – galena ± chalcopyrite − electrum in fractured pyrite and arsenopyrite. We propose two models for the formation of base metal sulfide inclusions in PyI, i.e., (1) co-precipitation of base metal sulfide with PyI and later redistribution in cracks driven by partial As replacement of PyI to PyII and arsenopyrite and (2) preferential replacement of the PyI along crystallographic planes by percolation of the fluid responsible for base metal sulfide deposition in fractured pyrite and arsenopyrite.

The Archean orogenic gold deposits exhibits common characteristics including coeval emplacement age often proposed to be associated with a single late tectonic gold mineralisation event. Although valid for a large majority of deposits in the Yilgarn Craton, this model does not account for certain atypical gold deposits. In the world-class Agnew District (Yilgarn Craton, Western Australia) structural and paragenetic relationships, combined with a compilation of geochronology and multiple sulfur isotopes, indicate that mineralisation developed during a two-stage process involving different fluid sources. The initial event dated at c. 2660 Ma is related to the onset of folding during Kalgoorlie Orogeny and presents characteristics compatible with magmatic intrusion related mineralisation. A second mineralisation event dated at c. 2630 Ma presents a mineral and metal inventory typical to Archean orogenic-like gold mineralisation, and developed at a later stage of the orogenesis. Measurements of δ34S and Δ33S from spatially constrained samples from the two temporally distinct mineralising events further ascertain contrasting fluid compositions and/or reservoirs. Combined with geochronological data obtained on the poly-magmatic Lawlers granitic complex, we argue for a protracted ore forming process. The first stage of mineralisation has a magmatic affinity and is followed by a second stage of mineralisation whereby Au-bearing hydrothermal solution incorporated an Archean sedimentary sulfur reservoir. We propose that the change in source reservoir for sulfur in hydrothermal fluids may reflect a regional change in tectonic regime from convergent to transcurrent motion, allowing fluids to be first sourced from mantle-derived magmas followed later by metamorphic fluids.

The evolution of a gold-bearing hydrothermal fluid from its source to the locus of gold deposition is complex as it experiences rapid changes in thermochemical conditions during ascent through the crust. Although it is well established that orogenic gold deposits are generated during time periods of abundant crustal growth and/or reworking, the source of fluid and the thermochemical processes that control gold precipitation remain poorly understood. In situ analyses of multiple sulfur isotopes offer a new window into the relationship between source reservoirs of Au-bearing fluids and the thermochemical processes that occur along their pathway to the final site of mineralisation. Whereas δ34S is able to track changes in the evolution of the thermodynamic conditions of ore-forming fluids, Δ33S is virtually indelible and can uniquely fingerprint an Archean sedimentary reservoir that has undergone mass independent fractionation of sulfur (MIF-S). We combine these two tracers (δ34S and Δ33S) to characterise a gold-bearing laminated quartz breccia ore zone and its sulfide-bearing alteration halo in the (+6 Moz Au) structurally-controlled Archean Waroonga deposit located in the Eastern Goldfields Superterrane of the Yilgarn Craton, Western Australia. Over 250 analyses of gold-associated sulfides yield a δ34S shift from what is interpreted as an early pre-mineralisation phase, with chalcopyrite-pyrrhotite (δ34S = +0.7‰ to +2.9‰) and arsenopyrite cores (δ34S = ∼−0.5‰), to a syn-mineralisation stage, reflected in Au-bearing arsenopyrite rims (δ34S = −7.6‰ to +1.5‰). This shift coincides with an unchanging Δ33S value (Δ33S = +0.3‰), both temporally throughout the Au-hosting hydrothermal sulfide paragenesis and spatially across the Au ore zone. These results indicate that sulfur is at least partially recycled from MIF-S-bearing Archean sediments. Further, the invariant nature of the observed MIF-S signature demonstrates that sulfur is derived from a homogeneous MIF-S-bearing fluid reservoir at depth, rather than being locally sourced at the site of Au precipitation. Finally, by constraining the MIF-S-bearing sulfur source to a fixed reservoir, we are able to display the thermochemical evolution of the ore fluid in δ34S space and capture the abrupt change in oxidation state that causes Au precipitation. Our results highlight the importance of constraining multiple sulfur isotopes in space and time in order to elucidate the source and evolution of any given Au-bearing fluid.

With growing interest in the application of in situ multiple sulfur isotope analysis to a variety of mineral systems, we report here the development of a suite of sulfur isotope standards for distribution relevant to magmatic, magmatic-hydrothermal, and hydrothermal ore systems. These materials include Sierra pyrite (FeS2), Nifty-b chalcopyrite (CuFeS2), Alexo pyrrhotite (Fe(1 − x)S), and VMSO pentlandite ((Fe,Ni)9S8) that have been chemically characterized by electron microprobe analysis, isotopically characterized for δ33S, δ34S, and δ36S by fluorination gas-source mass spectrometry, and tested for homogeneity at the micro-scale by secondary ion mass spectrometry. Beam-sample interaction as a function of crystallographic orientation is determined to have no effect on δ34S and Δ33S isotopic measurements of pentlandite. These new findings provided the basis for a case study on the genesis of the Long-Victor nickel-sulfide deposit located in the world class Kambalda nickel camp in the southern Kalgoorlie Terrane of Western Australia. Results demonstrate that precise multiple sulfur isotope analyses from magmatic pentlandite, pyrrhotite and chalcopyrite can better constrain genetic models related to ore-forming processes. Data indicate that pentlandite, pyrrhotite and chalcopyrite are in isotopic equilibrium and display similar Δ33S values + 0.2‰. This isotopic equilibrium unequivocally fingerprints the isotopic signature of the magmatic assemblage. The three sulfide phases show slightly variable δ34S values (δ34Schalcopyrite = 2.9 ± 0.3‰, δ34Spentlandite = 3.1 ± 0.2‰, and δ34Spyrrhotite = 3.9 ± 0.5‰), which are indicative of natural fractionation. Careful in situ multiple sulfur isotope analysis of multiple sulfide phases is able to capture the subtle isotopic variability of the magmatic sulfide assemblage, which may help resolve the nature of the ore-forming process. Hence, this SIMS-based approach discriminates the magmatic sulfur isotope signature from that recorded in metamorphic- and alteration-related sulfides, which may not be resolved during bulk rock fluorination analysis. The results indicate that, unlike the giant dunite-hosted komatiite systems that thermo-mechanically assimilated volcanogenic massive sulfides proximal to vents and display negative Δ33S values, the Kambalda ores formed in relatively distal environments assimilating abyssal sulfidic shales.

In the Norseman–Wiluna belt, Yilgarn Craton, the Agnew–Mt. White district is the host of many gold deposits. Located in the hinge of the regional Lawlers anticline, the Turret gold deposit is structurally controlled by the Table Hill shear zone that transects the Agnew Ultramafic unit. Geochemistry, coupled with petrographic data, allowed the delineation of the paragenetic sequence associated with gold mineralisation and include (1) a pervasive talc-carbonate alteration assemblage, (2) a pre-mineralisation stage associated with pervasive arsenopyrite + chalcopyrite + pyrrhotite + pyrite alteration, followed by (3) a late deformation event along a dilatational segment of the main Table Hill shear zone, leading to the formation of a breccia hosting a Cu–Bi–Mo–Au (± Ag ± Zn ± Te ± W) metal assemblage. The presence of Au–Ag–Cu alloys, native bismuth, chalcopyrite and other Bi–Te–S phases in the mineralisation stage suggest that gold may have been scavenged from the hydrothermal fluids by composite Bi–Te–Cu–Au–Ag–S liquids or melts. Using this mineral paragenetic sequence, together with mineralogical re-equilibration textures observed, we show that the gold deposition at Turret occurred over a temperature range approximately between c. 350 and 270 °C. This temperature range, together with the structural control and typical mesothermal alteration pattern including carbonate–chlorite alteration, shows that the Turret deposit shares common characteristics with the orogenic gold deposit class. However, the metal association of Cu, Au, Bi, and Mo, the quartz-poor, and high copper-sulphide content (up to 15 %) are characteristics that depart from the typical orogenic gold deposit mineralogy. Through comparison with similar deposits in the Yilgarn Craton and worldwide, we propose that the Turret deposit represents an example of a porphyry-derived Au–Cu–Bi–Mo deposit.