Vincenzo Stagno

Evidence for a reducing Archean ambient mantle and its effects on the carbon cycle

Chemical reduction-oxidation mechanisms within mantle rocks link to the terrestrial carbon cycle by influencing the depth at which magmas can form, their composition, and ultimately the chemistry of gases released into the atmosphere. The oxidation state of the uppermost mantle has been widely accepted to be unchanged over the past 3800 m.y., based on the abundance of redox-sensitive elements in greenstone belt–associated samples of different ages. However, the redox signal in those rocks may have been obscured by their complex origins and emplacement on continental margins. In contrast, the source and processes occurring during decompression melting at spreading ridges are relatively well constrained. We retrieve primary redox conditions from metamorphosed mid-oceanic ridge basalts (MORBs) and picrites of various ages (ca. 3000–550 Ma), using V/Sc as a broad redox proxy. Average V/Sc values for Proterozoic suites (7.0 ± 1.4, 2σ, n = 6) are similar to those of modern MORB (6.8 ± 1.6), whereas Archean suites have lower V/Sc (5.2 ± 0.4, n = 5). The lower Archean V/Sc is interpreted to reflect both deeper melt extraction from the uppermost mantle, which becomes more reduced with depth, and an intrinsically lower redox state. The pressure-corrected oxygen fugacity (expressed relative to the fayalite-magnetite-quartz buffer, ΔFMQ, at 1 GPa) of Archean sample suites (ΔFMQ –1.19 ± 0.33, 2σ) is significantly lower than that of post-Archean sample suites, including MORB (ΔFMQ –0.26 ± 0.44). Our results imply that the reducing Archean atmosphere was in equilibrium with Earth’s mantle, and further suggest that magmatic gases crossed the threshold that allowed a build-up in atmospheric O2 levels ca. 3000 Ma, accompanied by the first “whiffs” of oxygen in sediments of that age.

Icosahedral AlCuFe quasicrystal at high pressure and temperature and its implications for the stability of icosahedrite.

The first natural-occurring quasicrystal, icosahedrite, was recently discovered in the Khatyrka meteorite, a new CV3 carbonaceous chondrite. Its finding raised fundamental questions regarding the effects of pressure and temperature on the kinetic and thermodynamic stability of the quasicrystal structure relative to possible isochemical crystalline or amorphous phases. Although several studies showed the stability at ambient temperature of synthetic icosahedral AlCuFe up to ~35 GPa, the simultaneous effect of temperature and pressure relevant for the formation of icosahedrite has been never investigated so far. Here we present in situ synchrotron X-ray diffraction experiments on synthetic icosahedral AlCuFe using multianvil device to explore possible temperature-induced phase transformations at pressures of 5 GPa and temperature up to 1773 K. Results show the structural stability of i-AlCuFe phase with a negligible effect of pressure on the volumetric thermal expansion properties. In addition, the structural analysis of the recovered sample excludes the transformation of AlCuFe quasicrystalline phase to possible approximant phases, which is in contrast with previous predictions at ambient pressure. Results from this study extend our knowledge on the stability of icosahedral AlCuFe at higher temperature and pressure than previously examined, and provide a new constraint on the stability of icosahedrite.

Quasicrystals at extreme conditions: The role of pressure in stabilizing icosahedral Al63Cu24Fe13 at high temperature

Abstract Icosahedrite, the first natural quasicrystal with composition Al63Cu24Fe13, was discovered in several grains of the Khatyrka meteorite, a CV3 carbonaceous chondrite. The presence of icosahedrite associated with high-pressure phases like ahrensite and stishovite indicates formation at high pressures and temperatures due to an impact-induced shock. Previous experimental studies on the stability of synthetic icosahedral AlCuFe have either been limited to ambient pressure, for which they indicate incongruent melting at ~1123 K, or limited to room-temperature, for which they indicate structural stability up to about 35 GPa. These data are insufficient to experimentally constrain the formation and stability of icosahedrite under the conditions of high pressure and temperature that formed the Khatyrka meteorite. Here we present the results of room-temperature, high-pressure diamond-anvil cells measurements of the compressional behavior of synthetic icosahedrite up to ~50 GPa. High P-T experiments were also carried out using both laser-heated diamond-anvil cells combined with in situ synchrotron X‑ray diffraction (at ~42 GPa) and multi-anvil apparatus (at 21 GPa) to investigate the structural evolution and crystallization of possible coexisting phases. The results demonstrate that the quasiperiodic order of icosahedrite is retained over the P-T range explored. We find that pressure acts to stabilize the icosahedral symmetry at temperatures much higher than previously reported. Direct solidification of AlCuFe quasicrystals from an unusual Al-Cu-rich melt is possible but it is limited to a narrow temperature range. Alternatively, quasicrystals may form after crystallization through solidsolid reactions of Al-rich phases. In either case, our results show that quasicrystals can preserve their structure even after hypervelocity impacts spanning a broad range of pressures and temperatures.

Evaluating the Role of Seagrass in Cenozoic CO2 Variations

Marine seagrass angiosperms play an important role in carbon sequestration, removing carbon dioxide from the atmosphere and binding it as organic matter. Carbon is stored in the plants themselves, but also in the sediments both in inorganic and organic forms. The inorganic component is represented by carbonates produced by calcareous organisms living as epiphytes on seagrass leaves and rhizomes. In this paper, we find that the rate of seagrass epiphyte production (leaves and rhizomes), averages 400 g m-2 yr-1, as result of seagrass sampling at seven localities along the Mediterranean coasts, and related laboratory analysis. Seagrasses have appeared in the Late Cretaceous, becoming a place of remarkable carbonate production and C sequestration during the whole Cenozoic era. Here, we explore the potential contribution of seagrass as C sink on the atmospheric CO2 decrease by measuring changes in seagrass extent, which is directly associated with variations in the global coastal length associated with plate tectonics. We claim that global seagrass distribution significantly affected the atmospheric composition, particularly at the Eocene-Oligocene boundary, when the CO2 concentration fell to 400 ppm, i.e. the approximate value of current atmospheric CO2.

High-pressure experimental verification of rutile-ilmenite oxybarometer: Implications for the redox state of the subduction zone

The more oxidized mantle peridotites above subducting slabs than stable continental areas have been attributed to the infiltration of some oxidizing fluids released from the subducting slabs. However, knowledge for the redox states of the slabs itself is very limited. Until now, few oxybarometers can be directly used to constrain the redox states of the subducting slabs. The rutile-ilmenite oxybarometer was proposed and successfully applied to constrain the oxygen fugacity of mantle assemblages. However, its application to rocks equilibrated at crustal P-T conditions has been hampered by some uncertainties in an early solid solution model of ilmenite. With a newly-released solid solution model for the ilmenite, we have conducted high-P experiments (at 3 and 5 GPa, and 900–1300°C) to test the accuracy of this oxybarometer. The experiments were performed with their oxygen fugacities controlled by the CCO buffer (i.e., C+O2=CO2). We demonstrated that the oxygen fugacities calculated for our high-P experimental products by using the rutile-ilmenite oxybarometer were in excellent agreement with the fO2 dictated by the CCO buffer, suggesting a wide applicability of this oxybarometer to crust rocks. As examples, the rutile-ilmenite oxybarometer has been used to constrain the oxygen fugacities of some metamorphic rocks such as eclogite, granulite and amphibolite usually observed from the subduction zones.

Response: Commentary: Evaluating the Role of Seagrass in Cenozoic CO2 Variations

Dipartimento Scienze della Terra, Università Roma La Sapienza, Rome, Italy, 2 Istituto di Geologia Ambientale e Geoingegneria (CNR), Sez. Sapienza, Dipartimento Scienze della Terra, Università Roma La Sapienza, Rome, Italy, Càtedra Guillem Colom Casasnovas, Universitat de les Illes Balears, Palma de Mallorca, Spain, 4 Laboratorio de Zoología, Departament de Biologia, Universitat de les Illes Balears, Palma de Mallorca, Spain