The application of S isotopes and S/Se ratios in determining ore-forming processes of magmatic Ni-Cu-PGE sulfide deposits: A cautionary case study from the northern Bushveld Complex

The application of S/Se ratios and S isotopes in the study of magmatic Ni-Cu-PGE sulfide deposits has long been used to trace the source of S and to constrain the role of crustal contamination in triggering sulfide saturation. However, both S/Se ratios and S isotopes are subject to syn- and post-magmatic processes that may alter their initial signatures. We present in situ mineral et signatures and S/Se ratios combined with bulk S/Se ratios to investigate and assess their utility in constraining ore-forming processes and the source of S within magmatic sulfide deposits. Magmatic Ni-Cu-PGE sulfide mineralization in the Grasvally Norite-Pyroxenite-Anorthosite (GNPA) member, northern Bushveld Complex was used as a case study based on well-defined constraints of sulfide paragenesis and local S isotope signatures. A crustal et component is evident in the most primary sulfide assemblage regardless of footwall lithology, and is inferred that the parental magma(s) of the GNPA member was crustally contaminated and sulfide saturated at the time of emplacement. However, S/Se ratios of both the primary and in particular secondary sulfide assemblages record values within or below the mantle range, rather than high crustal S/Se ratios. In addition, there is a wide range of S/Se ratio for each sulfide mineral within individual assemblages that is not necessarily consistent with the bulk ratio. The initial crustal S/Se ratio is interpreted to have been significantly modified by syn-magmatic lowering of S/Se ratio by sulfide dissolution, and post-magmatic lowering of the S/Se ratio from hydrothermal S-loss, which also increases the PGE tenor of the sulfides. Trace element signatures and variations in Th/Yb and Nb/Th ratios support both an early pre-emplacement contamination event as seen by the S isotopes and S/Se ratios, but also a second contamination event resulting from the interaction of the GNPA magma with the local footwall country rocks at the time of emplacement; though this did not add any additional S. We are able to present an integrated emplacement and contamination model for the northern limb of the Bushveld Complex. Although the multitude of processes that affect variations in the delta S-34 signature and in particular S/Se ratio may be problematic in interpreting ore genesis, they can reveal a wealth of additional detail on a number of processes involved in the genetic history of a Ni-Cu-PGE deposit in addition to crustal contamination. However, a prerequisite for being able to do this is to utilize other independent petrological and mineralogical techniques that provide constraints on both the timing and effect of various ore-forming and modifying processes. Utilizing both bulk and in situ methods in concert to determine the S/Se ratio allows for the assessment of multiple sulfide populations, the partitioning behaviour of Se during sulfide liquid fractionation and also the effects of low temperature fluid alteration. In comparison, S isotopes are relatively more robust and represent a more reliable indicator of the role of crustal S contamination. The addition of trace element data to the above makes for an incredibly powerful approach in assessing the role of crustal contamination in magmatic sulfide systems. (C) 2015 The Authors. Published by Elsevier B.V.