Pyrite Framboid Formation Chemistry

Pyrite forms mainly through two routes: (1) the reaction between FeS species and polysulfides, and (2) the reaction of FeS species and H2S. Both of these reactions produce framboidal pyrite, and the mechanisms have been confirmed both kinetically and through the use of isotopic tracers. Aqueous Fe2+ does not appear to react directly with aqueous polysulfide species to produce pyrite, and the S-S bond in aqueous S2(-II) is normally split by aqueous Fe2+ to produce aqueous FeS and sulfur. The FeS moiety involved in pyrite formation may be provided by aqueous FeS or =FeS groups on solid surfaces. The reaction with surface =FeS occurs with any iron mineral in a sulfidic environment, including the relatively scarce iron sulfide minerals, mackinawite and greigite, nanoparticulate FeS, and pyrite itself. The reaction with surface =FeS sites on pyrite is a major route for pyrite crystal growth. The extreme insolubility of pyrite is one of the fundamental reasons for its particular involvement in framboid formation as well as for the ubiquity of framboids.

Introduction

Framboids are microscopic subspherical clusters of equant and equidimensional microcrystals. They overwhelmingly consist of the mineral pyrite, cubic FeS2. There are about 1030 framboids on Earth and they are forming at a rate of about 1014 per second. They may be the most abundant mineral texture on Earth. Framboids are especially concentrated in sediments, although they are also to be found in the water column and in high temperature systems. The oldest framboids are possibly 2.9 Ga and they are found in all geologic periods from that time. The first framboids were described in 1885 from a peat bog, and the term framboid was coined in 1935. They have fascinated researchers ever since, not least because a substantial fraction of them display astonishing regular microarchitectures where their constituent microcrystals are geometrically ordered. Understanding of the nature of framboids has paralleled technological advances in microscopy, structural and chemical analyses, and computing. The sulfur in sedimentary framboids is almost exclusively sourced from sulfate-reducing bacteria, and the idea that framboids were fossil microorganisms was first propounded in 1923. Subsequently, the limited distribution of organic matter in framboids, its absence in hydrothermal framboids, and inorganic framboid syntheses showed that organisms were not necessary for framboid formation.

Nucleation of Framboids

Framboid microcrystals, which are intrinsically similar in size and habit within any individual framboid, must have all nucleated and grown at the same time. The formation of many thousands of equidimensional and equimorphic microcrystals in framboids is the fundamental evidence for burst nucleation. This is conventionally described by the LaMer model, which is characterized by (1) a lag phase before nucleation becomes significant; (2) burst nucleation where the rate of nucleation increases exponentially and may be completed in seconds; and (3) a short growth phase where nucleation becomes again insignificant. The growth phase is limited by the diffusion of Fe and S in stagnant, diffusion limited environments. By contrast, individual pyrite crystals evidence isolated nucleation and unlimited growth in advecting systems. The reaction with surface =FeS provided by sulfidized iron oxyhydroxides may a major route for producing individual pyrite crystals, rather than framboids, especially in sediments. Framboid formation by the nucleation of pyrite in solution can be described by classical nucleation theory (CNT), which leads to results consistent with observed critical supersaturation ranges, critical nucleus radius, and surface energies.

Framboid Sizes

Framboid size-frequency plots show log-normal distributions with a geometric mean diameter of 6.0 μ‎m and with 95% of framboids ranging between 2.9 and 12.3 μ‎m. The largest framboids may be 250 μ‎m in diameter, although spherical aggregates of framboids, known as polyframboids, may range up to 900 μ‎m in diameter. Various spherical clusters of nanoparticles have been described which are less than 0.2 μ‎m in diameter. These do not form a continuum with framboids. There is no evidence for any significant change in framboid diameters with geologic time, and the differences in mean sizes between hydrothermal and sedimentary framboids do not, at present, appear to be statistically significant. By contrast, it appears that the mean diameters of framboids from non-marine sediments are significantly larger (7.6 μ‎m) than marine framboids (5.7 μ‎m). There is some evidence that framboids formed in the water column are smaller than those formed in sediments, but the non-critical use of this possible difference as a proxy for paleoenvironmental reconstructions is not robust. So-called microframboids and nanoframboids are discrete entities which are distinct from framboids. They are nanoparticle clusters and are not produced by the same processes as those involved in framboid formation, nor do they behave in the same way. They are more akin to atomic clusters, which form similar constructs.

Framboid Mineralogy

Framboids are dominantly made of pyrite. The limiting factors for other minerals forming framboids include the requirements of crystal habit, solubility, and natural abundances of the constituent elements for framboid formation. Detailed examination of reports of non-pyritic framboids reveal microcrystalline material within and associated with framboids (e.g., greigite) and sub-spherical crystalline aggregates (e.g., marcasite, chalcocite-digenite, magnetite). Framboids are sometimes observed replaced by other minerals. Pyrite framboids are often formed during the earliest stages of sedimentation or mineralization and therefore are subject to further reactions with later fluids. Minerals such as copper, cobalt, zinc, and lead sulfides often display framboidal forms that have replaced original pyrite framboids. Likewise, oxidation of pyrite under some conditions can produce iron (oxyhydr)oxide and iron sulfate framboids.