The Effects of Metamorphism on Iron Mineralogy and the Iron Speciation Redox Proxy

As the most abundant transition metal in the Earth’s crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite’s identification depended on the extraction techniques utilized. The presence of diagenetic iron carbonates in many samples severely affected the proxy even at low grade, engendering an interpretation of ferruginous conditions in all lithologies, but particularly in carbonate-bearing rocks. Increasing metamorphic grades transformed iron in carbonates into iron in silicate minerals, which when combined with a slight increase in the amount of pyrrhotite, drove the proxy toward more oxic and more euxinic conditions. Broad-classes of metamorphic reactions (e.g. decarbonation, silicate formation) occurred at distinct temperatures-pressures in carbonates versus siliciclastics, and could be either abrupt between metamorphic facies or more gradual in nature. Notably, these analyses highlighted the importance of trace iron in phases like calcite, which otherwise might not be included in iron-focused research i.e. ore-system petrogenesis, metamorphic evolution, or normative calculations of mineral abundance. The observations show that iron is mobile and reactive during diagenesis and metamorphism, and these post-depositional processes can readily overprint primary redox information held by iron speciation. However, in principle, additional mineralogical and petrographic approaches can be combined with iron speciation data to help untangle many of these post-depositional processes and arrive at more accurate estimates of paleoenvironmental redox conditions and processes, even for metamorphosed samples

In situ Raman spectroscopy measurements of MgAl 2 O 4 spinel up to 1400 °C

abStract In-situ Raman measurements using a gated spectroscopy system revealed irreversible changes at 800-1000 °C in a natural red spinel (with 2 cation mol% Cr and 1 cation mol% Zn) and at 1100-1200 °C in a natural clear spinel (without Cr or Zn). Our observations of rapid broadening of a mode at 409 cm −1 and the appearance of two weak modes at 210 and 520 cm −1 at the transition temperature confirm the association of these features with cation disordering proposed by previous quench studies. Furthermore, we found that the frequencies of modes at 313 and 666 cm −1 change at the transition temperature. The discontinuous frequency decrease of the mode at 313 cm −1 and the increase in the frequency of the mode at 666 cm −1 can be explained by the entrance of heavier Al atoms into the tetrahedral sites and the entrance of lighter Mg atoms into the octahedral sites, respectively. Our study demonstrates that in-situ Raman spectroscopy is a powerful tool for studying cation disordering in spinel-structured minerals at high temperature

Mid-Proterozoic Ferruginous Conditions Reflect Postdepositional Processes

To evaluate the mechanics of mid‐Proterozoic environmental iron transport and deposition, we coupled microscale textural and bulk rock magnetic techniques to study the ~1.4‐Ga lower Belt group, Belt Supergroup, Montana and Idaho. We identified a pyrrhotite‐siderite isograd that marks metamorphic iron‐bearing mineral reactions beginning in subgreenschist facies samples. Even in the best‐preserved parts of the basin, secondary overprints were common including recrystallization of iron‐bearing sulfides, base metal sulfides, and nanophase pyrrhotite. Despite these overprints, a record of redox chemistry was preserved in the early diagenetic framboidal pyrite and detrital iron oxides including trace nanoscale magnetite that remained after sulfidization in anoxic and sulfidic sedimentary pore fluids. Based on these results, we interpret the Belt Basin as having oxic waters, at least in shallow‐water environments, with no indication of abundant ferrous iron in the water column; this is consistent with the cooccurrence of early eukaryotic fossils within the same strata

Iron mineralogy and redox conditions during deposition of the mid-Proterozoic Appekunny Formation, Belt Supergroup, Glacier National Park

The redox state of the mid-Proterozoic oceans, lakes, and atmospheres is still debated, but it is vital for understanding the emergence and rise of macroscopic organisms and eukaryotes. The Appekunny Formation, Belt Supergroup, Montana, contains some of these early macrofossils dated between 1.47 Ga and 1.40 Ga and provides a well-preserved record of paleoenvironmental conditions. We analyzed the iron chemistry and mineralogy in samples from Glacier National Park, Montana, by pairing bulk rock magnetic techniques with textural techniques, including light microscopy, scanning electron microscopy, and synchrotron-based X-ray absorption spectroscopy. Field observations of the Appekunny Formation combined with mineralogical information allowed revised correlations of stratigraphic members across the park. However, late diagenetic and/or metasomatic fluids affected primary iron phases, as evidenced by prevalent postdepositional phases including base-metal sulfides. On the west side of the park, pyrrhotite and chlorite rims formed during burial metamorphism in at least two recrystallization events. These complex postdepositional transformations could affect bulk proxies for paleoredox. By pairing bulk and textural techniques, we show primary records of redox chemistry were preserved in early diagenetic and often recrystallized framboidal pyrite, submicron magnetite grains interpreted to be detrital in origin, and red-bed laminae interpreted to record primary detrital oxides. Based on these observations, we hypothesize that the shallow waters of the mid-Proterozoic Belt Basin were similar to those in modern marine and lacustrine waters: fully oxygenated, with detrital reactive iron fluxes that mineralized pyrite during organic diagenesis in suboxic, anoxic, and sulfidic conditions in sedimentary pore waters

The Effects of Metamorphism on Iron Mineralogy and the Iron Speciation Redox Proxy

As the most abundant transition metal in the Earth’s crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite’s identification depended on the extraction techniques utilized. The presence of diagenetic iron carbonates in many samples severely affected the proxy even at low grade, engendering an interpretation of ferruginous conditions in all lithologies, but particularly in carbonate-bearing rocks. Increasing metamorphic grades transformed iron in carbonates into iron in silicate minerals, which when combined with a slight increase in the amount of pyrrhotite, drove the proxy toward more oxic and more euxinic conditions. Broad-classes of metamorphic reactions (e.g. decarbonation, silicate formation) occurred at distinct temperatures-pressures in carbonates versus siliciclastics, and could be either abrupt between metamorphic facies or more gradual in nature. Notably, these analyses highlighted the importance of trace iron in phases like calcite, which otherwise might not be included in iron-focused research i.e. ore-system petrogenesis, metamorphic evolution, or normative calculations of mineral abundance. The observations show that iron is mobile and reactive during diagenesis and metamorphism, and these post-depositional processes can readily overprint primary redox information held by iron speciation. However, in principle, additional mineralogical and petrographic approaches can be combined with iron speciation data to help untangle many of these post-depositional processes and arrive at more accurate estimates of paleoenvironmental redox conditions and processes, even for metamorphosed samples

Gene Sequencing-Based Analysis of Microbial-Mat Morphotypes, Caicos Platform, British West Indies

Active carbonate platforms provide modern analogs to study microbial-mat development and taphonomy in the sedimentary record. Microbial-mat descriptions and classifications for tropical tidal-flat environments have focused predominantly on morphological observations. This is exemplified by flat and biscuit-shaped mats, where the mat morphotypes are postulated to reflect different Cyanobacteria communities as the main mat-building taxa. To compare the total microbial communities of these two mat types and test this Cyanobacteria hypothesis, we applied optical microscopy and gene sequencing methods using samples from a tidal algal marsh on Little Ambergris Cay, Turks and Caicos, B.W.I. With gene sequencing we find that total diversity and community composition differs significantly between morphotypes; the biscuit mat is more diverse than the flat mat. Microscopy results support that Cyanobacteria populations colonizing the surface layer of these two mat types are responsible for much of the mat's structural elements; however, genetic data find the Cyanobacteria population is indistinguishable between the two mat types. The recovered Cyanobacteria populations fall predominantly into three taxa: Scytonema, Halomicronema, and Crinalium. We propose that the morphology of these two mat types is not controlled by the Cyanobacteria, but instead reflects a time-integrated microbial response to environmental factors, where the microbial community becomes more diverse with time since environmental disturbance

A Late Cretaceous true polar wander oscillation

True polar wander (TPW), or planetary reorientation, is well documented for other planets and moons and for Earth at present day with satellites, but testing its prevalence in Earth’s past is complicated by simultaneous motions due to plate tectonics. Debate has surrounded the existence of Late Cretaceous TPW ca. 84 million years ago (Ma). Classic palaeomagnetic data from the Scaglia Rossa limestone of Italy are the primary argument against the existence of ca. 84 Ma TPW. Here we present a new high-resolution palaeomagnetic record from two overlapping stratigraphic sections in Italy that provides evidence for a ~12° TPW oscillation from 86 to 78 Ma. This observation represents the most recent large-scale TPW documented and challenges the notion that the spin axis has been largely stable over the past 100 million years

Mid-Proterozoic Ferruginous Conditions Reflect Postdepositional Processes

To evaluate the mechanics of mid‐Proterozoic environmental iron transport and deposition, we coupled microscale textural and bulk rock magnetic techniques to study the ~1.4‐Ga lower Belt group, Belt Supergroup, Montana and Idaho. We identified a pyrrhotite‐siderite isograd that marks metamorphic iron‐bearing mineral reactions beginning in subgreenschist facies samples. Even in the best‐preserved parts of the basin, secondary overprints were common including recrystallization of iron‐bearing sulfides, base metal sulfides, and nanophase pyrrhotite. Despite these overprints, a record of redox chemistry was preserved in the early diagenetic framboidal pyrite and detrital iron oxides including trace nanoscale magnetite that remained after sulfidization in anoxic and sulfidic sedimentary pore fluids. Based on these results, we interpret the Belt Basin as having oxic waters, at least in shallow‐water environments, with no indication of abundant ferrous iron in the water column; this is consistent with the cooccurrence of early eukaryotic fossils within the same strata