Diana Zivak

Phosphorites of the Georgina Basin (northern Australia) are an established economic source of phosphate and have recently been recognized to be a potential source of rare earth elements (REE). Previous bulk‐rock geochemistry work focused on the eastern margin of the basin revealed that phosphorites from the southern region have significantly higher (up to 0.5%) REE contents than equivalent prospects further to the north. In this study, we examine the origin of REE enrichment in the Georgina Basin phosphorites using an integrated geochemical, petrographic, mineralogical, and isotopic (Sm‐Nd and Sr) approach. The trace element geochemistry of primary phosphate minerals is consistent with a seawater origin for the REEs in phosphorites, with minimal input from the underlying basement rocks. Variations in total REE concentrations are controlled largely by the seawater composition, depositional environment, and the texture of the phosphorite (grainstone vs. mudstone phosphorite). Grainstone phosphorite yields on average higher concentrations of REEs compared to the mudstone phosphorite, likely due to the higher surface‐to‐mass ratio of the grainstone phosphorite resulting in the uptake of higher concentrations of REEs during coastal reworking. The formation of the low‐REE northern and central deposits took place during early transgression in oxidized, shallow supratidal to subtidal platformal environments. During the subsequent main transgressive event, fault‐controlled topography in the southern domain allowed phosphogenesis along basement highs to be facilitated along a redox boundary, where more saline and REE‐rich deep anoxic bottom waters, along with Fe‐cycling and bacterial mediation played a major role in the enrichment of REEs in the southern phosphorites.

Detrital zircon grains preserved within clasts and the matrix of a basal diamictite sequence directly overlying the Carrapateena IOCG deposit in the Gawler Craton, South Australia are shown here to preserve U–Pb ages and geochemical signatures that can be related to underlying mineralisation. The zircon geochemical signature is characterised by elevated heavy rare-earth element fractionation values (Gd_N/Yb_N ≥ 0.15) and high Eu ratios (Eu/Eu* ≥ 0.6). This geochemical signature has previously been recognised within zircon derived from within the Carrapateena orebody and can be used to distinguish zircon associated with IOCG mineralisation from background zircon preserved within stratigraphically equivalent regionally unaltered and altered samples. The results demonstrate that zircon chemistry is preserved through processes of weathering, erosion, transport, and incorporation into cover sequence materials and, therefore, may be dispersed within the cover sequence, effectively increasing the geochemical footprint of the IOCG mineralisation. The zircon geochemical criteria have potential to be applied to whole-rock geochemical data for the cover sequence diamictite in the Carrapateena area; however, this requires understanding of the presence of minerals that may influence the HREE fractionation (Gd_N/Yb_N) and/or Eu/Eu* results (e.g., xenotime, feldspar).

The chemistry of hydrothermal monazite from the Carrapateena and Prominent Hill iron oxide-copper-gold (IOCG) deposits in the IOCG-rich Gawler Craton, South Australia, is used here to define geochemical criteria for IOCG exploration in the Gawler Craton as follows: Monazite associated with IOCG mineralisation: La + Ce > 63 wt% (where La > 22.5 wt% and Ce > 37 wt%), Y and/or Th < 1 wt% and Nd < 12.5 wt%; Intermediate composition monazite (between background and ore-related compositions): 45 wt% < La + Ce < 63 wt%, Y and/or Th < 1 wt%. Intermediate monazite compositions preserving Nd > 12.5 wt% are considered indicative of Carrapateena-style mineralisation; Background compositions: La + Ce < 45 wt% or Y or Th > 1 wt%. Mineralisation-related monazite compositions are recognised within monazite hosted within cover sequence materials that directly overly IOCG mineralisation at Carrapateena. Similar observations have been made at Prominent Hill. Recognition of these signatures within cover sequence materials demonstrates that the geochemical signatures can survive processes of weathering, erosion, transport and redeposition into younger cover sequence materials that overlie older, mineralised basement rocks. The monazite geochemical signatures therefore have the potential to be dispersed within the cover sequence, effectively increasing the geochemical footprint of mineralisation.

Zircon from spatially and temporally distinct igneous rock units across the Gawler Craton, Australia, show subtle differences in trace and rare earth element ratios. These igneous suites range in composition from granite, rhyolite to gabbro and originate from the ca 2450 Ma Sleaford Complex, the ca 1850 Ma Donington Suite, the ca 1633–1608 Ma St Peter Suite, the ca 1595–1587 Ma Gawler Range Volcanics and the ca 1595–1575 Ma Hiltaba Suite granites. The geochemical characterisation of zircon is carried out on relatively unaltered samples in order to establish primary signatures and to understand the processes controlling the geochemical signatures of the igneous suites. A range of zircon morphologies and internal textures that are preserved in these igneous suites infer the geological history of the host rock, including metamorphism and multiple episodes of zircon saturation suggesting a complex magma evolution. Despite differences in whole-rock geochemistry between igneous suites, zircon largely overlaps geochemically. However, subtle differences in Th/U, U/Hf and (Nb + Ta)/P ratios are evident between the Donington Suite, Gawler Range Volcanics and Hiltaba Suite. This is likely due to the tectonic setting, composition of the crystallising magma and timing of zircon crystallisation in the magma evolution. The subtle geochemical differences in zircon show the potential of using these ratios to aid in provenance studies with large populations of zircon that are of similar age. However, as the dataset is limited and focused only on unaltered samples, further work needs to be undertaken to look at the altered counterparts of these igneous suites.

A first pass workflow for placing cover sequence materials into four broad lithological groups using A–CNK–FM (Al₂O₃–CaO + Na₂O + K₂O–Fe₂O₃+MgO) and A–CN–K (Al₂O₃–CaO + Na₂O–K₂O) ternary diagrams in conjunction with the SiO₂ vs Al₂O₃, Fe₂O₃ and CaO plus the Ca versus Sr XY diagrams has been derived from lithological logging and laboratory whole-rock geochemistry of 2346 samples. These lithological groups include siliciclastics (quartz sands and clays), weathered material, carbonate lithologies (marine limestone, pedogenic carbonate and compositions intermediate between the two end members) and ferruginous lithologies (including ferricrete and ferruginous sediments). Depositional, weathering and groundwater processes influence sample geochemistry during or after the formation of the material and will influence where the sample will plot on the geochemical diagrams used in this study. Geochemical data for discrete lithologies targeted during sampling (e.g. carbonate lithologies) clusters on diagrams used in the geochemical workflow, whereas data from targeted stratigraphic horizons (e.g. basement–cover interface) are more variable. The ability to characterise rock types that are texturally defined using the geochemical workflow is limited. For instance, the geochemistry of diamictite/conglomerate samples is dependent on the matrix versus clast content and composition as well as the source rock and catchment area. This workflow has the potential to be applied in a mineral exploration environment for rapid interpretation of real-time geochemical (e.g. portable XRF) data to gain an understanding of background geochemistry and geochemical signatures that may be related to underlying mineralisation.