Partitioning and Surficial Segregation of Trace Elements in Iron Oxides in Hydrothermal Fluid Systems

Partitioning experiments were done by hydrothermal synthesis of crystals containing trace elements (TEs) by internal sampling of fluid at the temperature of 450 °C and pressure of 1 kbar. The crystal phases obtained were magnetite, hematite, and Ni-spinel, which were studied using X-ray diffraction (XRD), X-ray electron probe microanalysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), atomic absorption spectrometry (AAS), and atomic force microscopy (AFM). The solutions from the sampler’s fluid probes were analysed by AAS for TEs included elements of the iron group plus aluminium. The highest co-crystallisation coefficients of TE and Fe between mineral and fluid (DTE/Fe) in magnetite were measured for V, Al, Ni and Cr (in decreasing order of n units in value), a lower value was observed for Co (2 × 10−1), and still lower values for Ti, Zn, and Mn (n × 10−2–10−3). In hematite, DTE/Fe values were highest for Al and V (order of n units in value), while lower values characterised Ti, Cr, and Co (n × 10−1–10−3), and the lowest values were exhibited by Cu, Mn, and Zn (n × 10−5). Copper was confirmed to be the most incompatible with all minerals studied; however, Cu had a high content on crystal surfaces. This surficial segregation contributes to the average TE concentration even when a thin layer of nonautonomous phase (NAP) is enriched in the element of interest. The accumulation of TEs on the surface of crystals increased bulk content 1–2 orders of magnitude above the content of structurally-bound elements even in coarse crystals. The inverse problem—evaluation of TE/Fe ratios in fluids involved in the formation of magnetite-containing deposits—revealed that the most abundant metals in fluids were Fe followed by Mn, Zn, and Cu, which comprised 10 to 30% of the total iron content.