We present microanalyses of secondary phyllosilicates in altered ferroan metaperidotite, containing approximately equal amounts of end-members serpentine ((Mg,Fe2+)3Si2O5(OH)4) and hisingerite (□Fe3+2Si2O5(OH)4·nH2O). These analyses suggest that all intermediate compositions can exist stably, a proposal that was heretofore impossible because phyllosilicate with the compositions reported here have not been previously observed. In samples from the Duluth Complex (Minnesota, USA) containing igneous olivine Fa36–44, a continuous range in phyllosilicate compositions is associated with hydrothermal Mg extraction from the system and consequent relative enrichments in Fe2+, Fe3+ (hisingerite), Si, and Mn. Altered ferroan–olivine-bearing samples from the Laramie Complex (Wyoming, USA) show a compositional variability of secondary FeMg–phyllosilicate (e.g., Mg–hisingerite) that is discontinuous and likely the result of differing igneous olivine compositions and local equilibration during alteration. Together, these examples demonstrate that the products of serpentinization of ferroan peridotite include phyllosilicate with iron contents proportionally larger than the reactant olivine, in contrast to the common observation of Mg-enriched serpentine in “traditional” alpine and seafloor serpentinites. To augment and contextualize our analyses, we additionally compiled greenalite and hisingerite analyses from the literature. These data show that greenalite in metamorphosed banded iron formation contains progressively more octahedral-site vacancies (larger apfu of Si) in higher XFe samples, a consequence of both increased hisingerite substitution and structure modulation (sheet inversions). Some high-Si greenalite remains ferroan and seems to be a structural analogue of the highly modulated sheet silicate caryopilite. Using a thermodynamic model of hydrothermal alteration in the Fe–silicate system, we show that the formation of secondary hydrothermal olivine and serpentine–hisingerite solid solutions after primary olivine may be attributed to appropriate values of thermodynamic parameters such as elevated a S i O 2 ( a q ) and decreased a H 2 ( a q ) at low temperatures (~200 °C). Importantly, recent observations of Martian rocks have indicated that they are evolved magmatically like the ferroan peridotites analyzed here, which, in turn, suggests that the processes and phyllosilicate assemblages recorded here are more directly relevant to those occurring on Mars than are traditional terrestrial serpentinites.
Photoferrotrophy, deposition of banded iron formations, and methane production in Archean oceans
