The Effect of Heat Treatment on the Crystallography and Mineral Magnetism of Pyrrhotite

Pyrrhotite (Fe1-xS, 0 ≤ x ≤ 0.125) is the second most common sulfide mineral after pyrite in the Earth's crust, and its properties are of interest to a wide variety of scientific disciplines, including electrical engineering, physical chemistry, planetary geology and meteoritics, and economic geology. The physical properties of pyrrhotite are highly dependent on slight variations in composition and the ordering of iron vacancies, resulting in a number of possible phases between the endmember compositions of FeS and Fe7S8­­. A common complication in studies on pyrrhotite is that different phases are frequently intergrown, making it difficult to isolate a natural single phase. This has led many researchers to rely on synthesis techniques, which produce a specific structure by using precise iron/sulfur ratios, heating protocols, and controlled cooling. One of the most common synthesis treatments used to create 4C pyrrhotite is an extended heating and annealing process, which is believed to allow the reordering of vacancies to a more thermodynamically stable, ordered state with elevated saturation magnetization. The process was first studied in detail by Schwarz and Vaughan (1972) who produced synthetic pyrrhotite at varying Fe/S ratios with annealing at either 700, 300, or 144°C. The most common method for producing 4C pyrrhotite is heating at 500°C for 24 hours under a vacuum followed by annealing at 250°C for 50 hours. While this technique has been broadly applied in diverse disciplines, there is debate about whether it produces ferrimagnetic, monoclinic 4C pyrrhotite or a different metastable disordered phase. We examined this process using a combination of rock magnetic, X-ray diffraction, and electron imaging techniques to study the effect of heating and annealing on a natural sample of pyrrhotite. Due to the lack of a Besnus transition in the annealed material, our data suggest that the increased magnetization we found following annealing, rather than being an increase in 4C ferrimagnetic pyrrhotite, was the preservation of a ferrimagnetic metastable phase which represents an intermediate to the original intergrown phases. Further work will examine the differences between heat treatments on synthetic and natural pyrrhotites.