The role of volatile exsolution and sub-solidus fluid/rock interactions in producing high Fe/Fe ratios in siliceous igneous rocks

Highly differentiated igneous rocks can, in some cases, have ⁵⁶Fe/⁵⁴Fe ratios that are significantly higher than those of mafic- to intermediate-composition igneous rocks. Iron isotope compositions were obtained for bulk rock, magnetite, and Fe silicates from well-characterized suites of granitic and volcanic rocks that span a wide range in major- and trace-element contents. Sample suites studied include granitoids from Questa, N.M. (Latir volcanic field) and the Tuolumne Intrusive Series (Sierra Nevada batholith), and volcanic rocks from Coso, Katmai, Bishop Tuff, Grizzly Peak Tuff, Seguam Island, and Puyehue volcano. The rocks range from granodiorite to high-silica granite and basalt to high-silica rhyolite. The highest δ⁵⁶Fe values (up to +0.31‰) are generally restricted to rocks that have high Rb (>100 ppm), Th (>∼15 ppm) and SiO₂ (>70 wt.%) but low Fe (<2 wt.% total Fe as Fe₂O₃) contents. Magnetite separated from these rocks has high δ⁵⁶Fe values, whereas Fe silicates have δ⁵⁶Fe values close to zero. Although in principle crystal fractionation might explain the high δ⁵⁶Fe values, trace-element ratios in high-δ⁵⁶Fe igneous rocks indicate that crystal fractionation is an unlikely explanation. The highest δ⁵⁶Fe values occur in volcanic and plutonic rocks that contain independent evidence for fluid exsolution, including sub-chondritic Zr/Hf ratios, suggesting that loss of a low-δ⁵⁶Fe ferrous chloride fluid is the most likely explanation for the high δ⁵⁶Fe values in the bulk rocks. Based on magnetite solubility in chloride solutions and predicted Fe isotope fractionations among Fe silicates, magnetite, and ferrous chloride fluids, the increase in δ⁵⁶Fe values of bulk rocks may be explained by isotopic exchange between magnetite and , which predicts an increase in the δ⁵⁶Fe values of magnetite upon fluid exsolution. This model is consistent with the δ⁵⁶Fe values measured in this study for bulk rocks, as well as magnetite and Fe silicates. Our results suggest that fluid exsolution from siliceous hydrous magmas, which sometimes produce porphyry-style Cu, Mo, or Cu-Au mineralization, may be traced using Fe isotopes.     

Polymetamorphism in high‐T metamorphic rocks: An example from the central Appalachians

Contact metamorphism associated with mafic intrusives is one of several mechanisms that has been invoked to produce extensive high‐temperature (HT) metamorphism and associated partial melting of the crust. Indisputable evidence for polymetamorphism in these settings can be difficult to decipher because both melt loss and retrogression (i.e. rehydration) can erase or obscure the records of earlier HT metamorphism by modifying HT mineral parageneses and compositions. Here, a combination of detailed field and petrographical observations, inverse mineral thermometry, and thermodynamic forward modelling is used to delineate the polymetamorphic history of migmatites from the Smith River Allochthon (SRA) in the central Appalachians. Bulk rock geochemical data suggest that some metapelitic samples lost a significant amount of melt during interpreted contact metamorphism with the Rich Acres gabbro, resulting in a residual bulk composition (<50 wt% SiO₂, ~30 wt% Al₂O₃). Garnet cores (Grt1) in SiO₂‐depleted samples are interpreted to grow during this HT contact metamorphism, with Fe‐Ti oxide thermometry on spinel inclusions in Grt1, cordierite–garnet thermometry, and thermodynamic forward modelling constraining peak P–T conditions during contact heating of the migmatites to ~800ºC and ～0.5 GPa. This is associated with an inferred peak assemblage prior to melt loss of crd+kfs+pl+grt+bt+spl (mag+usp+hc)+ilm+sil+qtz+melt. Garnet in SiO₂‐depleted samples has a distinct high‐Ca rim (Grt2), which appears to record a younger metamorphic event. A combination of substantial melt loss and later rehydration appears to be a major control on the ability of SiO₂‐depleted samples to faithfully record evidence for this polymetamorphism. The tectonic implications of this younger metamorphic event are not entirely clear, but it appears to record renewed burial and heating of the SRA sometime after the Taconic orogeny, which may be related to either the neo‐Acadian or Alleghanian orogenies.     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

Electric and magnetic drift of non-adiabatic ions in the Earth's geomagnetic tail current sheet

It has been shown recently that non-adiabatic particles in the Earth's magnetotail drift across the tail roughly as predicted for adiabatic particles with 90° pitch angles. In this paper we show that this result implies the existence of an approximate invariant of the motion. Adding the effect of convection associated electric fields, we can then obtain the approximate bounce averaged motion of non-adiabatic particles in the magnetotail. Thus the particle motion and energization due to combined magnetic and electric drifts in the magnetotail are easily predicted.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction

Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced ⁵⁶Fe/⁵⁴Fe ratios for Fe(II)_aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)_aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)_aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO₃) and ca. +0.9‰ for Ca-substituted siderite (Ca_0.15Fe_0.85CO₃) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have ⁵⁶Fe/⁵⁴Fe ratios that are up to 1‰ lower than Fe(II)_aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)_aq.The relative order of δ⁵⁶Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)_aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ⁵⁶Fe >0‰, the calculated δ⁵⁶Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ⁵⁶Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ⁵⁶Fe values. Based on this experimental study, formation of low-δ⁵⁶Fe Fe(II)_aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.