This study examines the whole-rock geochemistry and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) iron oxide chemistry of itabirite and related iron ore, as well as underlying phyllitic wall rock, of the Pau Branco iron ore deposit, Quadrilátero Ferrífero, Brazil. The phyllite and iron ore of Pau Branco extend from hypogene deep-seated into supergene weathered zones. The phyllitic sequence that underlies the itabirite-hosted iron ore along a sheared contact includes (from the bottom to top) carbonaceous and carbonate-, chlorite-, and Fe-rich zones, which likely reflect distal to proximal alteration halos. The Fe-rich phyllite and iron ore comprise a complex iron oxide mineralogy: (1) magnetite-martite is hosted in itabirite and related medium-grade iron ore and present as disseminated minerals in phyllite; (2) microplaty hematite replaces chlorite and carbonate in the phyllite; (3) granoblastic hematite is a recrystallization/precipitation product and the dominant iron oxide of the hard iron ore; (4) schistose specular hematite overgrows earlier iron oxides; and (5) goethite replaces earlier hematite and amphibole within the weathering horizon.
Whole-rock geochemistry and related mass balance calculations reveal that, unlike the itabirite-hosted iron ore, interpreted to be the result of a solely residual iron enrichment via depletion of most major oxides and trace elements, the iron enrichment of the phyllite is caused by addition of Fe2O3. The Fe2O3 is likely sourced from the overlying itabirite/iron ore and is mineralogically reflected in the replacement of carbonate and chlorite by hematite. The rare earth elements (REE) abundances of the different ore and phyllite zones reveal seawater-like REE signatures and Y/Ho ratios of the itabirite, hypogene and supergene iron ore, shale-atypical REE patterns in the unaltered phyllite, and Eu fractionation trends. This suggests a distinct input of hydrothermal fluids during the Fe enrichment of the phyllite. Locally, restricted Ce fractionation is attributed to distinct (e.g., Mn-rich) lithostratigraphic intercalations within the itabirite. Laser ablation-ICP-MS mineral chemistry of phyllite-hosted martite and microplaty hematite suggests a strong chemical inheritance by the host rock and precursor mineral. Positive Ce anomalies are restricted to phyllite- and itabirite-hosted martite only and, therefore, may reflect the highly oxidative conditions during martitization. At Pau Branco, the fluid-rock interaction affected not only the itabirite, but also the underlying phyllite, resulting in distinct alteration halos that extend beyond the itabirite toward the footwall. The significant chemical influence and importance of country-rock lithologies as a possible elemental source, for example, must be taken into account when interpreting whole-rock geochemical data and investigating an itabirite-/banded iron formation-hosted iron ore system.