Determination of Fe²⁺/Fe³⁺ Ratios of Magnetite using Different Methods: A Case Study from the Qimantag Metallogenic Belt

Abstract

Determination of Fe2+/Fe3+ ratios from metallogenic belts to explore controlling physical and chemical conditions of rock formation is of great significance. In order to explore magnetite Fe2+/Fe3+ ratios of the Qimantag metallogenic belt, part of the Eastern Kunlun orogenic belt in the northeastern margin of the Qinghai–Tibetan plateau, western Central Orogenic Belt of China, and overcome the limitation of the traditional electronic probe, five different measurement methods are proposed and their respective advantages and disadvantages evaluated, with the composition data of the magnetite obtained using electron probe microanalysis (EPMA). The direct oxygen measurement method has a significant impact on the determination results of FeO and Fe2O3, but the accuracy and uniformity of the results are low. The valence method (Flank method) based on the spectral intensity ratio of Lα to Lβ for iron is also unreliable for FeO and Fe2O3 measurements because it is difficult to establish a relationship between Lβ/Lα, the spectral intensity ratio, and the Fe2+/Fe3+ content ratio. In comparison, the charge difference method, the surplus‐oxygen method and the Mössbauer spectrum method are still the most favorable. Mössbauer spectroscopy, with its isomer movement particularly sensitive to the oxidation state of iron, yields results closer to 0.5, which is relatively reliable. Earlier magnetite deposits are located in intrusions or contact zones and formed by magmatic fluids with high Fe2+/Fe3+ ratios, whereas later magnetite deposits are farther away from intrusions and have low Fe2+/Fe3+ ratios. The transformation mechanism of hematite and magnetite in the Qimantage metallogenic belt is also studied. No large volume changes, such as pore filling and shrinkage fracture, were detected in the metallogenic belt, and the transformation mechanism is more similar to a reoxidation and reduction mechanism.