Marc M. Hirschmann

The pMELTS: A revision of MELTS for improved calculation of phase relations and major element partitioning related to partial melting of the mantle to 3 GPa

[1] We describe a newly calibrated model for the thermodynamic properties of magmatic silicate liquid. The new model, pMELTS, is based on MELTS [Ghiorso and Sack, 1995] but has a number of improvements aimed at increasing the accuracy of calculations of partial melting of spinel peridotite. The pMELTS algorithm uses models of the thermodynamic properties of minerals and the phase equilibrium algorithms of MELTS, but the model for silicate liquid differs from MELTS in the following ways: (1) The new algorithm is calibrated from an expanded set of mineral-liquid equilibrium constraints from 2439 experiments, 54% more than MELTS. (2) The new calibration includes mineral components not considered during calibration of MELTS and results in 11,394 individual mineral-liquid calibration constraints (110% more than MELTS). Of these, 4924 statements of equilibrium are from experiments conducted at elevated pressure (200% more than MELTS). (3) The pMELTS model employs an improved liquid equation of state based on a third-order Birch-Murnaghan equation, calibrated from high-pressure sink-float and shockwave experiments to 10 GPa. (4) The new model employs a revised set of end-member liquid components. The revised components were chosen to better span liquid composition-space. Thermodynamic properties of these components are optimized as part of the mineral-liquid calibration. Comparison of pMELTS to partial melting relations of spinel peridotite from experiments near 1 GPa indicates significant improvements relative to MELTS, but important outstanding problems remain. The pMELTS model accurately predicts oxide concentrations, including SiO2, for liquids from partial melting of MM3 peridotite at 1 GPa from near the solidus up to � 25% melting. Compared to experiments, the greatest discrepancy is for MgO, for which the calculations are between 1 and 4% high. Temperatures required to achieve a given melt fraction match those of the experiments near the solidus but are � 60� C high over much of the spinel lherzolite melting interval at this pressure. Much of this discrepancy can probably be attributed to overstabilization of clinopyroxene in pMELTS under these conditions. Comparison of pMELTS calculations to the crystallization and partial melting experiments of Falloon et al. [1999] shows excellent agreement but also suffers from exaggerated calculated stability of clinopyroxene. Finally, comparison of pMELTS

Alkalic magmas generated by partial melting of garnet pyroxenite

Many oceanic-island basalts (OIBs) with isotopic signatures of recycled crustal components are silica poor and strongly nepheline (ne) normative and therefore unlike the silicic liquids generated from partial melting of recycled mid-oceanic-ridge basalt (MORB). High-pressure partial-melting experiments on a garnet pyroxenite (MIX1G) at 2.0 and 2.5 GPa produce strongly ne-normative and silica-poor partial melts. The MIX1G solidus is located below 1350 and 1400 8C at 2 and 2.5 GPa, respectively, slightly cooler than the solidus of dry peridotite. Chemographic analysis suggests that natural garnet pyroxenite compositions straddle a thermal divide. Whereas partial melts of compositions on the silica-excess side of the divide (such as recycled MORB) are silica saturated, those from silica-deficient garnet pyroxenites can be alkalic and have similar- ities to low-silica OIB. Although the experimental partial melts are too rich in Al2O3 to be parental to highly undersaturated OIB suites, higher-pressure (4-5 GPa) partial melting of garnet pyrox- enite is expected to yield more appropriate parental liquids for OIB lavas. Silica-deficient garnet pyroxenite, which may originate by mixing of MORB with peridotite, or by recycling of other mafic lithologies, represents a plausible source of OIB that may resolve the apparent contradiction of strongly alkalic composition with iso- topic ratios characteristic of a recycled component.

Melting in the Earth's deep upper mantle caused by carbon dioxide

The onset of partial melting beneath mid-ocean ridges governs the cycling of highly incompatible elements from the mantle to the crust, the flux of key volatiles (such as CO2, He and Ar) and the rheological properties of the upper mantle. Geophysical observations indicate that melting beneath ridges begins at depths approaching 300 km, but the cause of this melting has remained unclear. Here we determine the solidus of carbonated peridotite from 3 to 10 GPa and demonstrate that melting beneath ridges may occur at depths up to 330 km, producing 0.03–0.3% carbonatite liquid. We argue that these melts promote recrystallization and realignment of the mineral matrix, which may explain the geophysical observations. Extraction of incipient carbonatite melts from deep within the oceanic mantle produces an abundant source of metasomatic fluids and a vast mantle residue depleted in highly incompatible elements and fractionated in key parent-daughter elements. We infer that carbon, helium, argon and highly incompatible heat-producing elements (such as uranium, thorium and potassium) are efficiently scavenged from depths of ∼200–330 km in the upper mantle.

High-pressure partial melting of garnet pyroxenite: Possible mafic lithologies in the source of ocean island basalts

Abstract Many ocean island basalts (OIB) that have isotopic ratios indicative of recycled crustal components in their source are silica-undersaturated and unlike silicic liquids produced from partial melting of recycled mid-ocean ridge basalt (MORB). However, experiments on a silica-deficient garnet pyroxenite, MIX1G, at 2.0–2.5 GPa show that some pyroxenite partial melts are strongly silica-undersaturated [M.M. Hirschmann et al., Geology 31 (2003) 481–484]. These low-pressure liquids are plausible parents of alkalic OIB, except that they are too aluminous. We present new partial melting experiments on MIX1G between 3.0 and 7.5 GPa. Partial melts at 5.0 GPa have low SiO 2 ( 2 O 3 ( 12 wt%) at moderate MgO (12–16 wt%), and are more similar to primitive OIB compositions than lower-pressure liquids of MIX1G or experimental partial melts of anhydrous or carbonated peridotite. Solidus temperatures at 5.0 and 7.5 GPa are 1625 and 1825°C, respectively, which are less than 50°C cooler than the anhydrous peridotite solidus. The liquidus temperature at 5.0 GPa is 1725°C, indicating a narrow melting interval (∼100°C). These melting relations suggest that OIB magmas can be produced by partial melting of a silica-deficient pyroxenite similar to MIX1G if its melting residue contains significant garnet and lacks olivine. Such silica-deficient pyroxenites could be produced by interaction between recycled subducted oceanic crust and mantle peridotite or could be remnants of ancient oceanic lower crust or delaminated lower continental crust. If such compositions are present in plumes ascending with potential temperatures of 1550°C, they will begin to melt at about 5.0 GPa and produce appropriate partial melts. However, such hot plumes may also generate partial melts of peridotite, which could dilute the pyroxenite-derived partial melts.

High-resolution records of the late Paleocene thermal maximum and circum-Caribbean volcanism: Is there a causal link?

Two recently drilled Caribbean sites contain expanded sedimentary records of the late Paleocene thermal maximum, a dramatic global warming event that occurred at ca. 55 Ma. The records document significant environmental changes, including deep-water oxygen deficiency and a mass extinction of deep-sea fauna, intertwined with evidence for a major episode of explosive volcanism. We postulate that this volcanism initiated a reordering of ocean circulation that resulted in rapid global warming and dramatic changes in the Earth’s environment.

The Effect of Alkalis on the Silica Content of Mantle-Derived Melts

A large body of experimental evidence shows that at low and moderate pressure (<1.5 GPa), alkali-rich silicate liquids coexisting with Mg-rich olivine and orthopyroxene are richer in silica than typical basalts. This phenomenon is caused by the tendency of alkali ions to reduce the number of Si-O-Si linkages in the melt, which translates to negative deviations from ideality for mixing between alkalis and silica and which requires increases in alkalis to be accompanied by increases in silica for liquids in equilibrium with mantle peridotite. P_2O_5 and TiO_2 have an effect opposite to alkalis, and when these elements are also enriched in the liquid, the high silica contents caused by alkali-enrichment may be reduced or eliminated. The effect of alkalis on the silica content of melts equilibrated with magnesian olivine and orthopyroxene is reduced at higher pressure, such that silica enrichments in alkali-rich melts will be small if the equilibration pressure is greater than ∼1.5 GPa. This pressure effect is largely the result of decreases with pressure in the extent of polymerization for all olivine + orthopyroxene-saturated liquids. As pressure increases and liquids in equilibrium with olivine and orthopyroxene become less polymerized, proportionally fewer alkalis break up highly polymerized (Q^4) silica tetrahedra, and, therefore, alkalis have less effect on the activity coefficient of silica. Secondarily, the observed changes with pressure may also be related to changes in the energetics of alkali-silica interactions. Because equilibration of alkali-rich melts with mantle peridotite only produces high silica at low and moderate pressures, small degree partial melts of anhydrous peridotite formed during adiabatic upwelling will not typically be silica-rich. However, if liquids rich in alkalis, perhaps formed by selective leaching of Na_2O and K_2O from peridotite during upward percolation, equilibrate with the mantle at depths <1.5 GPa, they will become silica-rich. Such silica-rich liquids, now preserved as glass inclusions in spinel peridotite xenoliths, are probably restricted to the shallowest part of the mantle (<45 km).

Carbon-dioxide-rich silicate melt in the Earth's upper mantle.

The onset of melting in the Earth’s upper mantle influences the thermal evolution of the planet, fluxes of key volatiles to the exosphere, and geochemical and geophysical properties of the mantle. Although carbonatitic melt could be stable 250 km or less beneath mid-oceanic ridges, owing to the small fraction (∼0.03 wt%) its effects on the mantle properties are unclear. Geophysical measurements, however, suggest that melts of greater volume may be present at ∼200 km (refs 3–5) but large melt fractions are thought to be restricted to shallower depths. Here we present experiments on carbonated peridotites over 2–5 GPa that constrain the location and the slope of the onset of silicate melting in the mantle. We find that the pressure–temperature slope of carbonated silicate melting is steeper than the solidus of volatile-free peridotite and that silicate melting of dry peridotite + CO2 beneath ridges commences at ∼180 km. Accounting for the effect of 50–200 p.p.m. H2O on freezing point depression, the onset of silicate melting for a sub-ridge mantle with ∼100 p.p.m. CO2 becomes as deep as ∼220–300 km. We suggest that, on a global scale, carbonated silicate melt generation at a redox front ∼250–200 km deep, with destabilization of metal and majorite in the upwelling mantle, explains the oceanic low-velocity zone and the electrical conductivity structure of the mantle. In locally oxidized domains, deeper carbonated silicate melt may contribute to the seismic X-discontinuity. Furthermore, our results, along with the electrical conductivity of molten carbonated peridotite and that of the oceanic upper mantle, suggest that mantle at depth is CO2-rich but H2O-poor. Finally, carbonated silicate melts restrict the stability of carbonatite in the Earth’s deep upper mantle, and the inventory of carbon, H2O and other highly incompatible elements at ridges becomes controlled by the flux of the former.

An analysis of variations in isentropic melt productivity

The amount of melt generated per unit pressure drop during adiabatic upwelling, the isentropic melt productivity, cannot be determined directly from experiments and is commonly assumed to be constant or to decrease as melting progresses. From analysis of one– and two–component systems and from calculations based on a thermodynamic model of peridotite partial melting, we show that productivity for reversible adiabatic (i.e. isentropic) depressurization melting is never constant; rather, productivity tends to increase as melting proceeds. Even in a one–component system with a univariant solid–liquid boundary, the 1/T dependence of (∂S/∂T)P and the downward curvature of the solidus (due to greater compressibility of liquids relative to minerals) lead to increased productivity with increasing melt fraction during batch fusion (and even for fractional fusion in some cases). Similarly, for multicomponent systems, downward curvature of contours of equal melt fraction between the solidus and the liquidus contributes to an increase in productivity as melting proceeds. In multicomponent systems, there is also a lever–rule relationship between productivity and the compositions of coexisting liquid and residue such that productivity is inversely related to the compositional distance between coexisting bulk solid and liquid. For most geologically relevant cases, this quantity decreases during progressive melting, again contributing to an increase in productivity with increasing melting. These results all suggest that the increases in productivity with increasing melt fraction (punctuated by drops in productivity upon exhaustion of each phase from the residue) predicted by thermodynamic modelling of melting of typical mantle peridotites using MELTS are neither artifacts nor unique properties of the model, but rather general consequences of adiabatic melting of upwelling mantle.

Aluminum coordination and the densification of high-pressure aluminosilicate glasses

Abstract To better understand the relationship between atomic-scale structures and densities of aluminosilicate glasses and liquids, we used 27Al MAS NMR to determine the speciation of aluminum ions in K3AlSi3O9, Na3AlSi3O9, and Ca3Al2Si6O18 glasses quenched from melts at 3 to 10 GPa. These data are a first approximation of high-pressure melt structure and illustrate the effects of the type of modifier cation. High field strength modifier cations (e.g., Ca) clearly induce more high-coordinated Al than lower field strength cations (e.g., Na and K). Measured glass densities show that, especially with rapid decompression, a significant portion of the total densification observed in-situ in melts is retained on return to ambient temperature and pressure. Observed increases in Al coordination are well correlated with decreased volume, which suggests that this structural change is a major part of the mechanism for recovered densification of high-pressure melts. Additionally, 23Na MAS NMR, combined with the 27Al MAS spectra and density determinations, reveal that other changes, such as the compression of modifier cation sites and/or decreased network bond angles, must also be significant, especially at low pressure.

Length scales of mantle heterogeneities and their relationship to ocean island basalt geochemistry

The upper mantle is widely considered to be heterogeneous, possibly comprising a “marble-cake” mixture of heterogeneous domains in a relatively well-mixed matrix. The extent to which such domains are capable of producing and expelling melts with characteristic geochemical signatures upon partial melting, rather than equilibrating diffusively with surrounding peridotite, is a critical question for the origin of ocean island basalts (OIB) and mantle heterogeneity, but is poorly constrained. Central to this problem is the characteristic length scale of heterogeneous domains. If radiogenic osmium signatures in OIB are derived from discrete domains, then sub-linear correlations between Os isotopes and other geochemical indices, suggesting melt-melt mixing, may be used to constrain the length scales of these domains. These constraints arise because partial melts of geochemically distinct domains must segregate from their sources without significant equilibration with surrounding peridotite. Segregation of partial melts from such domains in upwelling mantle is promoted by compaction of the domain mineral matrix, and must occur faster than diffusive equilibration between the domain and its surroundings. Our calculations show that the diffusive equilibration time depends on the ratios of partition and diffusion coefficients of the partial melt and surrounding peridotite. Comparison of time scales between diffusion and melt segregation shows that segregation is more rapid than diffusive equilibration for Os, Sr, Pb, and Nd isotopes if the body widths are greater than tens of centimeter to several meters, depending on the aspect ratio of the bodies, on the melt fraction at which melt becomes interconnected in the bodies, and on the diffusivity in the solid. However, because Fe-Mg exchange occurs significantly more rapidly than equilibration of these isotopes under solid-state and partially molten conditions, it is possible that some domains can produce melts with Fe/Mg ratios reflecting that of the surrounding mantle but retaining isotopic signatures of heterogeneous domains. Although more refined estimates on the rates of, and controls on, Os mobility are needed, our preliminary analysis shows that heterogeneous domains large enough to remain compositionally distinct in the mantle (as solids) for ∼109 yr in a marble-cake mantle, can produce and expel partial melts faster than they equilibrate with surrounding peridotite.