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.

A quantification of the effect of diagenesis on the paleoredox record in mid-Proterozoic sedimentary rocks

Iron speciation in ancient sedimentary rocks is widely used to reconstruct oceanic redox conditions over geological time, specifically to assess the extent of oxic, euxinic (anoxic containing sulfide), and ferruginous (anoxic containing iron) conditions. We explore how post-depositional sedimentary processes can skew particular geochemical signals in the rock record. One such process is when aqueous sulfide—including that produced in the sediment column—reacts with sedimentary iron, converting non-sulfide, highly reactive iron minerals to iron-sulfide minerals; this can lead to increased preservation of iron as pyrite and an overestimation of seafloor euxinia. We show that sedimentary rocks with higher (>5 wt%) total iron content are more buffered to this effect and thus are a more reliable indicator of true water-column euxinia. When considering this effect in the geological past, we estimate that true euxinia in the mid-Proterozoic may have been as much as fourfold less than previously thought—more in line with other recent paleoredox proxies not based on iron minerals. Marine iron and sulfate concentrations were more equivalent in Proterozoic–Neoproterozoic oceans, suggesting this time period was particularly susceptible to this post-depositional alteration, explaining the extent of euxinia suggested for this geological interval.

Effect of Ferric Ions on Sulfidization Flotation of Oxidize Digenite Fine Particles and Their Significance

Digenite fine particles are easily oxidized and ferric ions (Fe3+) commonly exist in the flotation pulp of digenite. This study investigated the effect of Fe3+ on the sulfidization flotation of oxidized digenite fine particles using sodium butyl xanthate (SBX) as a collector. The results of microflotation experiments show that the flotation rate and recovery of oxidized digenite fine particles can be improved by adding Na2S and SBX, whereas the existence of large amounts of Fe3+ is not beneficial for the sulfidization flotation of digenite. The results of Fe3+ adsorption, zeta potential, and contact angle measurements indicate that Fe3+ can be adsorbed on the digenite surface mainly in the form of Fe(OH)3, which hinders the adsorption of SBX and significantly reduces the surface hydrophobicity of digenite. X-ray photoelectron spectroscopy analysis further suggests that the poor surface hydrophobicity of digenite in the presence of Fe3+ is due to the production of large amounts of hydrophilic iron and copper oxides/hydroxides on the surface. Furthermore, optical microscopy analysis shows that these hydrophilic species effectively disperse digenite fine particles in the pulp, which eventually leads to the poor floatability of digenite. Therefore, it is necessary to reduce the amount of Fe3+ present in the pulp and adsorbed on digenite surface before sulfidization to realize effective separation of oxidized digenite fine particles and iron sulfide minerals.

Bistability in the redox chemistry of sediments and oceans

For most of Earth’s history, the ocean’s interior was pervasively anoxic and showed occasional shifts in ocean redox chemistry between iron-buffered and sulfide-buffered states. These redox transitions are most often explained by large changes in external inputs, such as a strongly altered delivery of iron and sulfate to the ocean, or major shifts in marine productivity. Here, we propose that redox shifts can also arise from small perturbations that are amplified by nonlinear positive feedbacks within the internal iron and sulfur cycling of the ocean. Combining observational evidence with biogeochemical modeling, we show that both sedimentary and aquatic systems display intrinsic iron–sulfur bistability, which is tightly linked to the formation of reduced iron–sulfide minerals. The possibility of tipping points in the redox state of sediments and oceans, which allow large and nonreversible geochemical shifts to arise from relatively small changes in organic carbon input, has important implications for the interpretation of the geological rock record and the causes and consequences of major evolutionary transitions in the history of Earth’s biosphere.

Greigite (Fe3S4) is thermodynamically stable: Implications for its terrestrial and planetary occurrence

Iron sulfide minerals are widespread on Earth and likely in planetary bodies in and beyond our solar system. Using measured enthalpies of formation for three magnetic iron sulfide phases: bulk and nanophase Fe3S4spinel (greigite), and its high-pressure monoclinic phase, we show that greigite is a stable phase in the Fe–S phase diagram at ambient temperature. The thermodynamic stability and low surface energy of greigite supports the common occurrence of fine-grained Fe3S4in many anoxic terrestrial settings. The high-pressure monoclinic phase, thermodynamically metastable below about 3 GPa, shows a calculated negative P-T slope for its formation from the spinel. The stability of these three phases suggests their potential existence on Mercury and their magnetism may contribute to its present magnetic field.

Magnetic properties of sedimentary smythite (Fe9S11)

<p>Smythite (Fe<sub>9</sub>S<sub>11</sub>) is an occasionally reported magnetic iron sulphide mineral that occurs in varied geological settings and co-occurs commonly with other magnetic iron sulphide minerals. Determining the magnetic properties of smythite is important to understand its geological distribution and paleomagnetic and environmental magnetic significance. We have identified sedimentary smythite from three locations in Taiwan (one terrestrial and two marine), which suggest that smythite forms in methanic diagenetic environments into which sulfide has been reintroduced. We report the magnetic properties of our purest smythite sample and compare them with those of other magnetic iron sulfide minerals. The magnetization of smythite is controlled by multi-axial anisotropy, with magnetic easy axes that lie within the crystallographic basal plane. Smythite has stable magnetic properties with no low-temperature magnetic transition. The magnetic properties of smythite at elevated temperatures are dominated by thermal alteration, which precludes Curie temperature determination. Hysteresis and coercivity properties of stable single domain smythite are similar to those of greigite at, and below, room temperature. In contrast to greigite, and similar to pyrrhotite polytypes, smythite crystals occur as hexagonal plates. This morphological contrast facilitates discrimination of smythite from greigite in electron microscope observations, but it does not assist discrimination from pyrrhotite. Similar magnetic and morphological properties between smythite and other magnetic iron sulfides means that diagnostic mineralogical analyses (e.g., X-ray diffraction) are needed to identify these minerals. Further work is needed to obtain pure samples to develop a comprehensive domain state dependent magnetic property framework for smythite.</p>

A theoretical study of adsorption on iron sulfides towards nanoparticle modeling

The adsorption properties of two iron sulfide minerals (mackinawite and pyrite) and zero-valent iron with respect to two small polar molecules (H2O and H2S) and trichloroethylene (TCE) were modeled.