Showing papers in "Contributions to Mineralogy and Petrology in 2012"

Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130°C and 2.2 GPa

Abstract: The following article presents constraints of the stability of Mg-rich (Mg/(Mg + Fe2+) > 0.5) calcic amphibole in both calc-alkaline and alkaline magmas, testing of previous thermobarometers, and formulation of new empirical equations that take into consideration a large amount of literature data (e.g. more than one thousand amphibole compositions among experimental and natural crystals). Particular care has been taken in choosing a large number of natural amphiboles and selecting quality experimental data from literature. The final database of experimental data, composed of 61 amphiboles synthesized in the ranges of 800–1,130°C and 130–2,200 MPa, indicates that amphibole crystallization occurs in a horn-like P–T stability field limited by two increasing curves (i.e. the thermal stability and an upper limit), which should start to bend back to higher pressures. Among calcic amphiboles, magnesiohornblendes and tschermakitic pargasites are only found in equilibrium with calc-alkaline melts and crystallize at relatively shallow conditions (P up to ~1 GPa). Kaersutite and pargasite are species almost exclusively found in alkaline igneous products, while magnesiohastingsite is equally distributed in calc-alkaline and alkaline rocks. The reliability of previous amphibole applications was checked using the selected experimental database. The results of this testing indicate that none of the previous thermobarometers can be successfully used to estimate the P, T and fO2 in a wide range of amphibole crystallization conditions. Multivariate least-square analyses of experimental amphibole compositions and physico-chemical parameters allowed us to achieve a new thermobarometric model that gives reasonably low uncertainties (T ± 23.5°C, P ± 11.5%, H2Omelt ± 0.78wt%) for calc-alkaline and alkaline magmas in a wide range of P–T conditions (up to 1,130°C and 2,200 MPa) and ∆NNO values (±0.37 log units) up to 500 MPa. The AK-[4]Al relation in amphibole can be readily used to distinguish crystals of calc-alkaline liquids from those of alkaline magmas. In addition, several chemometric equations allowing to estimate the anhydrous composition of the melts in equilibrium with amphiboles of calc-alkaline magmas were derived.

Experiments on liquid immiscibility along tholeiitic liquid lines of descent

Abstract: Crystallization experiments have been conducted on compositions along tholeiitic liquid lines of descent to define the compositional space for the development of silicate liquid immiscibility. Starting materials have 46–56 wt% SiO2, 11.7–17.7 wt% FeOtot, and Mg-number between 0.29 and 0.36. These melts fall on the basaltic trends relevant for Mull, Iceland, Snake River Plain lavas and for the Sept Iles layered intrusion, where large-scale liquid immiscibility has been recognized. At one atmosphere under anhydrous conditions, immiscibility develops below 1,000–1,020°C in all of these compositionally diverse lavas. Extreme iron enrichment is not necessary; immiscibility also develops during iron depletion and silica enrichment. Variations in melt composition control the development of silicate liquid immiscibility along the tholeiitic trend. Elevation of Na2O + K2O + P2O5 + TiO2 promotes the development of two immiscible liquids. Increasing melt CaO and Al2O3 stabilizes a single-liquid field. New data and published phase equilibria show that anhydrous, low-pressure fractional crystallization is the most favorable condition for unmixing during differentiation. Pressure inhibits immiscibility because it expands the stability field of high-Ca clinopyroxene, which reduces the proportion of plagioclase in the crystallizing assemblage, thus enhancing early iron depletion. Magma mixing between primitive basalt and Fe–Ti–P-rich ferrobasalts can serve to elevate phosphorous and alkali contents and thereby promote unmixing. Water might decrease the temperature and size of the two-liquid field, potentially shifting the binodal (solvus) below the liquidus, leading the system to evolve as a single-melt phase.

The beginnings of hydrous mantle wedge melting

Abstract: This study presents new phase equilibrium data on primitive mantle peridotite (0.33 wt% Na2O, 0.03 wt% K2O) in the presence of excess H2O (14.5 wt% H2O) from 740 to 1,200°C at 3.2–6 GPa. Based on textural and chemical evidence, we find that the H2O-saturated peridotite solidus remains isothermal between 800 and 820°C at 3–6 GPa. We identify both quenched solute from the H2O-rich fluid phase and quenched silicate melt in supersolidus experiments. Chlorite is stable on and above the H2O-saturated solidus from 2 to 3.6 GPa, and chlorite peridotite melting experiments (containing ~6 wt% chlorite) show that melting occurs at the chlorite-out boundary over this pressure range, which is within 20°C of the H2O-saturated melting curve. Chlorite can therefore provide sufficient H2O upon breakdown to trigger dehydration melting in the mantle wedge or perpetuate ongoing H2O-saturated melting. Constraints from recent geodynamic models of hot subduction zones like Cascadia suggest that significantly more H2O is fluxed from the subducting slab near 100 km depth than can be bound in a layer of chloritized peridotite ~ 1 km thick at the base of the mantle wedge. Therefore, the dehydration of serpentinized mantle in the subducted lithosphere supplies free H2O to trigger melting at the H2O-saturated solidus in the lowermost mantle wedge. Alternatively, in cool subduction zones like the Northern Marianas, a layer of chloritized peridotite up to 1.5 km thick could contain all the H2O fluxed from the slab every million years near 100 km depth, which suggests that the dominant form of melting below arcs in cool subduction zones is chlorite dehydration melting. Slab P–T paths from recent geodynamic models also allow for melts of subducted sediment, oceanic crust, and/or sediment diapirs to interact with hydrous mantle melts within the mantle wedge at intermediate to hot subduction zones.

Amphibole stability in primitive arc magmas: effects of temperature, H 2 O content, and oxygen fugacity

Abstract: The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO2, 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200–800 MPa, temperature range of 915–1,070 °C, and oxygen fugacities varying from the nickel–nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO2, 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515–533; 2003) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H2O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H2O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H2O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H2O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975–1,025 °C. With increasing H2O pressure ( $${P}_{\text {H}_2{\rm O}}$$ ), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and $$f_{\text {O}_2}$$ : $$ P_{\text{H}_{2}{\rm O}}({\rm MPa})=\left[{\frac{{\rm Mg\#}}{52.7}}-0.014 * \Updelta {\rm NNO}\right]^{15.12} $$ This barometer gives a minimum $${P}_{\text{H}_{2}{\rm O}}$$ recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H2O pressures (500–900 MPa) and high pre-eruptive magmatic H2O contents (10–14 wt% H2O) are indicated for the primitive end members of magma mixing that are preserved in the Shasta lavas. We also use these new experimental data to explore and evaluate the empirical hornblende barometer of Larocque and Canil (2010).

Redox-controlled iron isotope fractionation during magmatic differentiation: An example from the Red Hill intrusion, S. Tasmania

Abstract: This study presents accurate and precise iron isotopic data for 16 co-magmatic rocks and 6 pyroxene–magnetite pairs from the classic, tholeiitic Red Hill sill in southern Tasmania. The intrusion exhibits a vertical continuum of compositions created by in situ fractional crystallisation of a single injection of magma in a closed igneous system and, as such, constitutes a natural laboratory amenable to determining the causes of Fe isotope fractionation in magmatic rocks. Early fractionation of pyroxenes and plagioclase, under conditions closed to oxygen exchange, gives rise to an iron enrichment trend and an increase in \( f_{{{\text{O}}_{2} }} \) of the melt relative to the Fayalite–Magnetite–Quartz (FMQ) buffer. Enrichment in Fe3+/ΣFemelt is mirrored by δ57Fe, where VIFe2+-bearing pyroxenes partition 57Fe-depleted iron, defining an equilibrium pyroxene-melt fractionation factor of \( \Updelta^{57} {\text{Fe}}_{{{\text{px}} - {\text{melt}}}} \le - 0.25\,\permille \times 10^{6} /T^{2} \). Upon magnetite saturation, the \( f_{{{\text{O}}_{2} }} \) and δ57Fe of the melt fall, commensurate with the sequestration of the oxidised, 57Fe-enriched iron into magnetite, quantified as \( \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{melt}}}} = + 0.20\,\permille \times 10^{6} /T^{2} \). Pyroxene–magnetite pairs reveal an equilibrium fractionation factor of \( \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{px}}}} \approx + 0.30\,\permille \) at 900–1,000 °C. Iron isotopes in differentiated magmas suggest that they may act as an indicator of their oxidation state and tectonic setting.

Isotopic variations in S-type granites: an inheritance from a heterogeneous source?

Abstract: Inherited zircons from S-type granites provide exceptionally good insight into the isotopic heterogeneity of their sources. Zircons from four samples (one granite, two granodiorites, one granodioritic enclave) of Pan-African S-type granite of the Cape Granite Suite (c. 540 Ma) have been the subject of a laser LA-ICP-MS zircon U/Pb study to determine emplacement ages and inheritance. Zircons from three of these samples (2 granodiorites and 1 granodioritic enclave) were also analysed for Hf isotopes by LA-MC-ICP-MS. Ages of inherited cores range from 1,200 to 570 Ma and show Hafnium isotope values (eHf,t) for the crystallisation age (t) of the different cores that range from −14.1 to +9.1. Magmatic zircons and magmatic overgrowth with concordant spot ages between ca. 525 and ca. 555 Ma show a similar range of eHf,t, between −8.6 and +1.5, whilst eHf values calculated at 540 Ma (eHf,540) for inherited cores range from −15.2 to +1.7. Thus, our results show that the time evolved eHf arrays of the inherited cores overlap closely with the eHf range displayed by the magmatic rims at the time of crystallisation of the pluton. These similarities imply a genetic relationship between magmatic and inherited zircons. Within the inherited cores, four main peak ages can be identified. This, coupled with their large Hf isotopic range, emphasises that the source of the granite is highly heterogeneous. The combination of the U/Pb zircon ages ranges and Hf isotope data implies that: (1) The source of S-type granite consists of crustal material recording several regional events between 1,200 and 600 Ma. This material records the recycling of a much older crust derived from depleted mantle between 1.14 and 2.02 Ga. (2) The homogenisation of Hf isotopic variation in the magma acquired through dissolution of the entrained zircon, via mechanical mixing and/or diffusion between within the granite was particularly inefficient. (3) This evidence argues for the assembly of the pluton through many relatively small magma batches that undergo rapid cooling from their intrusion temperature (ca. 850°C) to background magma chamber temperature that is low enough to ensure that much of the magmatic zircon crystallised rapidly (>80% by 700°C). (4) There is no evidence for the addition of mantle-derived material in the genesis of S-type Cape Granite Suite, where the most mafic granodiorites are strongly peraluminous, relatively low in CaO and K2O rich. Interpreted more widely, these findings imply that S-type granites inherit their isotopic characteristic from the source. Source heterogeneity transfers to the granite magma via the genesis of discrete magma batches. The information documented from the S-type CGS zircons has been recorded because the individual batches of magma crystallised the bulk of their magmatic zircon prior to mechanical or diffusional magma homogenisation. This is favoured by zirconium saturation in the magma shortly after emplacement, by partial dissolution of the entrained zircon fraction, as well as by the intrusion of volumetrically subordinate magma batches into a relatively cool pluton. Consequently, evidence recorded within inherited cores will most likely be best preserved in S-type granite plutons intruded at shallow depths. Other studies that have documented similar eHf arrays in magmatic zircons have interpreted these to reflect mixing between crustal- and mantle-derived magmas. This study indicates that such arrays may be wholly source inherited, reflecting mixing of a range of crustal materials of different ages and original isotopic signatures.

Distribution of REE between clinopyroxene and basaltic melt along a mantle adiabat: effects of major element composition, water, and temperature

Abstract: The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D 0, r 0 and E) as functions of pressure, temperature, and compositions of cpx and melt. D 0 is found to positively correlate with Al in tetrahedral site (Al T ) and Mg in the M2 site (MgM2) of cpx and negatively correlate with temperature and water content in the melt. r 0 is negatively correlated with Al in M1 site (AlM1) and MgM2 in cpx. And E is positively correlated with r 0. During adiabatic melting of spinel lherzolite, temperature, Al T , and MgM2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.

A case for hornblende dominated fractionation of arc magmas: the Chelan Complex (Washington Cascades)

Abstract: Amphibole fractionation in the deep roots of subduction-related magmatic arcs is a fundamental process for the generation of the continental crust. Field relations and geochemical data of exposed lower crustal igneous rocks can be used to better constrain these processes. The Chelan Complex in the western U.S. forms the lowest level of a 40-km thick exposed crustal section of the North Cascades and is composed of olivine websterite, pyroxenite, hornblendite, and dominantly by hornblende gabbro and tonalite. Magmatic breccias, comb layers and intrusive contacts suggest that the Chelan Complex was build by igneous processes. Phase equilibria, textural observations and mineral chemistry yield emplacement pressures of ∼1.0 GPa followed by isobaric cooling to 700°C. The widespread occurrence of idiomorphic hornblende and interstitial plagioclase together with the lack of Eu anomalies in bulk rock compositions indicate that the differentiation is largely dominated by amphibole. Major and trace element modeling constrained by field observations and bulk chemistry demonstrate that peraluminous tonalite could be derived by removing successively 3% of olivine websterite, 12% of pyroxene hornblendite, 33% of pyroxene hornblendite, 19% of gabbros, 15% of diorite and 2% tonalite. Peraluminous tonalite with high Sr/Y that are worldwide associated with active margin settings can be derived from a parental basaltic melt by crystal fractionation at high pressure provided that amphibole dominates the fractionation process. Crustal assimilation during fractionation is thus not required to generate peraluminous tonalite.

Experimental determination of F and Cl partitioning between lherzolite and basaltic melt

Abstract: We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D Cpx/melt > D Opx/melt > D Grt/melt > D Ol/melt > D Plag/melt, and D mineral/melt is larger than D Cl mineral/melt Four other major results were brought to light (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity (3) F and Cl partition coefficients correlate with the Young’s modulus (E 0) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D 0 M 1, D 0 M 2, r 0 M1 , r 0 M2 , E 0 M1 and E 0 M2

Electrical conductivity of orthopyroxene and plagioclase in the lower crust

Abstract: The electrical conductivities of lower crustal orthopyroxene and plagioclase, as well as their dependence on water content, were measured at 6–12 kbar and 300–1,000°C on both natural and pre-annealed samples prepared from fresh mafic xenolith granulites. The complex impedance was determined in an end-loaded piston cylinder apparatus by a Solarton-1260 Impedance/Gain Phase analyzer in the frequency range of 0.1–106 Hz. The spectra usually show an arc over the whole frequency range at low temperature and an arc plus a tail in the high and low frequency range, respectively, at high temperature. The arc is due to conduction in the sample interior, while the tails are probably due to electrode effects. Different conduction mechanisms have been identified under dry and hydrous conditions. For the dry orthopyroxene, the activation enthalpy is ~105 kJ/mol, and the conduction is likely due to small polarons, e.g., electrons hopping between Fe2+ and Fe3+. For the dry plagioclase, the activation enthalpy is ~161 kJ/mol, and the conduction may be related to the mobility of Na+. For the hydrous samples, the activation enthalpy is ~81 kJ/mol for orthopyroxene and ~77 kJ/mol for plagioclase, and the electrical conductivity is markedly enhanced, probably due to proton conduction. For each mineral, the conductivity increases with increasing water content, with an exponent of ~1, and the activation enthalpies are nearly independent of water content. Combining these data with our previous work on the conductivity of lower crustal clinopyroxene, the bulk conductivity of lower crustal granulites is modeled, which is usually >~10−4 S/m in the range of 600–1,000°C. We suggest that the high electrical conductivity in most regions of the lower crust, especially where it consists mostly of granulites, can be explained by the main constitutive minerals, particularly if they contain some water. Contributions from other highly conducting materials such as hydrous fluids, melts, or graphite films are not strictly necessary to explain the observed conductivities.

U–Pb geochronology of two discrete Ordovician high-pressure metamorphic events in the Seve Nappe Complex, Scandinavian Caledonides

Abstract: U–Pb geochronology for eclogites in two different areas of the Seve Nappe Complex (SNC) in Sweden confirms previous indications of discrete Ordovician high-pressure events affecting various parts of the complex In Norrbotten, just north of the Arctic circle, eclogites from the Tsakkok and Vaimok Lenses yield identical metamorphic zircon ages of 482 ± 1 Ma Titanite in a metagabbro from the Vaimok Lens retains an older age of 607 ± 2 Ma, which may date a protolith coeval with mafic dikes in the overlying Sarek Lens; high-U zircon cores in one of the eclogites also indicate a similar age Farther south, in Jamtland, the Tjeliken eclogite yields a significantly younger metamorphic age of 446 ± 1 Ma Although they support the age discrepancy between the Norrbotten and Jamtland eclogites, the U–Pb ages of both eclogite suites are ca 20 my younger than previously reported Sm–Nd ages The latter may either represent early prograde growth or be spuriously too old due to isotopic disequilibrium The SNC has traditionally been taken to represent the outermost margin of Baltica, linking the Early Caledonian eclogite–forming events to subduction of Baltica below an offshore arc Alternatively, the coincidence of these eclogite-forming events with orogenic phases recorded on the Laurentian margin may point to an origin from other regions of the Iapetus Ocean

Formation of ferrian chromite in podiform chromitites from the Golyamo Kamenyane serpentinite, Eastern Rhodopes, SE Bulgaria: a two-stage process

Abstract: The Golyamo Kamenyane serpentinite is a portion of a metaophiolite, located in the Upper High-Grade Unit of the metamorphic basement of the Eastern Rhodope Metamorphic Complex, SE Bulgaria. It consists of metaharzburgite and metadunite hosting layers of metagabbro and some chromitite bodies. All these lithologies were affected by ultrahigh-pressure (UHP) metamorphism and subsequent retrograde evolution during exhumation. Chromite from chromitites can be classified into four textural groups: (1) partly altered chromite, (2) porous chromite, (3) homogeneous chromite and (4) zoned chromite. Partly altered chromite shows unaltered, Al-rich cores with unit cell size of 8.255 A and Cr# [Cr/(Cr + Al) atomic ratio] = 0.52–0.60, Mg# [Mg/(Mg + Fe2+) atomic ratio] = 0.65–0.70 and Fe3+/(Fe3+ + Fe2+) = 0.20–0.30, surrounded by porous chromite, with a cell size of 8.325 A, Fe3+/(Fe3+ + Fe2+) < 0.20 and values of Cr# and Mg# evolving from 0.60 to 0.91 and 0.65–0.44, respectively, from core to rim. The chemical composition of porous chromite varies within the following ranges: Cr# = 0.93–0.96, Mg# = 0.48–0.35 and Fe3+/(Fe3+ + Fe2+) = 0.22–0.53. Its unit cell size is very constant (8.350 A). Most pores in porous and partly altered chromite are filled with chlorite, which also occurs between chromite grains. Homogeneous chromite has Fe3+/(Fe3+ + Fe2+) = 0.55–0.66, Cr# = 0.96–0.99, Mg# = 0.32–0.19 and a cell size of 8.385 A. The cores of zoned chromite are similar to those of partially altered chromite, but the rims are identical to homogeneous chromite. Although chlorite predominates in the silicate matrix of homogeneous and zoned chromite, it coexists with some antigorite, talc and magnesiohornblende. Mineral data and thermodynamic modeling allow interpretation of the alteration patterns of chromite as the consequence of a two-stage process developed during retrograde metamorphic evolution coeval with fluid infiltration. During the first stage, chromite reacts in the presence of fluid with olivine to produce chlorite and Cr- and Fe2+-rich residual chromite (ferrous chromite) at ~700 to ~450 °C. This dissolution–precipitation reaction involves continuous chromite mass loss resulting in the development of a porous texture. This stage takes place progressively on cooling under water-saturated and reducing conditions. The second stage mainly consists of the formation of homogeneous chromite with ferrian chromite composition by the addition of magnetite to the porous ferrous chromite during a late oxidizing hydrothermal event.

A parameterized model for REE distribution between low-Ca pyroxene and basaltic melts with applications to REE partitioning in low-Ca pyroxene along a mantle adiabat and during pyroxenite-derived melt and peridotite interaction

Abstract: Low-Ca pyroxenes play an important role in mantle melting, melt-rock reaction, and magma differentiation processes. In order to better understand REE fractionation during adiabatic mantle melting and pyroxenite-derived melt and peridotite interaction, we developed a parameterized model for REE partitioning between low-Ca pyroxene and basaltic melts. Our parameterization is based on the lattice strain model and a compilation of published experimental data, supplemented by a new set of trace element partitioning experiments for low-Ca pyroxenes produced by pyroxenite-derived melt and peridotite interaction. To test the validity of the assumptions and simplifications used in the model development, we compared model-derived partition coefficients with measured partition coefficients for REE between orthopyroxene and clinopyroxene in well-equilibrated peridotite xenoliths. REE partition coefficients in low-Ca pyroxene correlate negatively with temperature and positively with both calcium content on the M2 site and aluminum content on the tetrahedral site of pyroxene. The strong competing effect between temperature and major element compositions of low-Ca pyroxene results in very small variations in REE partition coefficients in orthopyroxene during adiabatic mantle melting when diopside is in the residue. REE partition coefficients in orthopyroxene can be treated as constants at a given mantle potential temperature during decompression melting of lherzolite and diopside-bearing harzburgite. In the absence of diopside, partition coefficients of light REE in orthopyroxene vary significantly, and such variations should be taken into consideration in geochemical modeling of REE fractionation in clinopyroxene-free harzburgite. Application of the parameterized model to low-Ca pyroxenes produced by reaction between pyroxenite-derived melt and peridotite revealed large variations in the calculated REE partition coefficients in the low-Ca pyroxenes. Temperature and composition of starting pyroxenite must be considered when selecting REE partition coefficients for pyroxenite-derived melt and peridotite interaction.

Tracing the evolution and distribution of F and Cl in plutonic systems from volatile-bearing minerals: a case study from the Liujiawa pluton (Dabie orogen, China)

Abstract: Fluorine and chlorine play an important role in magmatic differentiation, hydrothermal alteration, and related mineralization processes, but tracing their evolution in magmatic and especially plutonic systems is not an easy task. The F and Cl in melts can be estimated from F and Cl concentrations in minerals, provided that partitioning between minerals and melts are constrained. Based on available partitioning models between mineral/melt, mineral/fluid, and melt/fluid, a set of equations has been derived to determine F and Cl concentrations in melts from the compositions of amphibole, biotite, and apatite. The new calculation procedure has been applied to a plutonic system, the Liujiawa pluton, eastern Dabie orogen (China). Cl and F concentrations in amphiboles, biotites, and apatites from different rock types (gabbronorite, two-pyroxene diorite, clinopyroxene diorite, and hornblende gabbro) have been determined by electron microprobe. Most amphiboles show a negative correlation between log(Cl/OH) and Mg-number and a positive correlation between log(F/OH) and A-site occupation. Biotites from the gabbronorite and two-pyroxene diorite show a slight positive correlation between log(Cl/OH) and Mg, which is however not the case for the clinopyroxene diorite. Apatites from all the samples are rich in F and show negative correlations between Cl and F concentrations. In our case study, we demonstrate that the Cl concentration in melt remains approximately constant at 1,000–2,000 ppm over the major crystallization interval, but decreases strongly at near solidus temperatures as a result of fluid exsolution. The F concentration in melt remains nearly constant at ca. 2,000–3,000 ppm at high temperatures as well as near solidus conditions, indicating that it is not largely affected by fluid exsolution because of its strongly preferred incorporation into melt. Interestingly, the evolution of Cl and F concentrations in melt with magmatic differentiation is similar to that determined in volcanic systems, suggesting that the evolution of Cl and F in melts during crystallization and late magmatic stages at depth (plutonic systems) is similar to that observed in volcanic systems during decompression and degassing.

Coexisting serpentine and quartz from carbonate-bearing serpentinized peridotite in the Samail Ophiolite, Oman

Abstract: Tectonically exposed mantle peridotite in the Oman Ophiolite is variably serpentinized and carbonated. Networks of young carbonate veins are prevalent in highly serpentinized peridotite, particularly near low-temperature alkaline springs emanating from the peridotite. An unusual feature in some samples is the coexistence of serpentine and quartz, which is not commonly observed in serpentinites. This assemblage is unstable with respect to serpentine + talc or talc + quartz under most conditions. Serpentine in the carbonated serpentinites in this study is more iron rich than in most serpentinites reported in previous studies, and samples with co-existing quartz contain the most iron-rich serpentines. Calculations of thermodynamic equilibria in the MgO–SiO2–H2O–CO2 system suggest that serpentine + quartz may be a stable assemblage at low temperatures (e.g., <~15–50 °C) and is stabilized to higher temperatures by preferential cation substitutions in serpentine over talc. Based on these calculations, serpentine + quartz assemblages could result from serpentinization at near-surface temperatures. Clumped isotope thermometry of carbonate veins yields temperatures within error of the observed temperatures in Oman groundwater for all samples analyzed, while the δ18O of water calculated to be in equilibrium with carbonate precipitated at those temperatures is within error of the observed isotopic composition of Oman groundwater for the majority of samples analyzed. As groundwater geochemistry suggests that carbonate precipitation and serpentinization occur concomitantly, this indicates that both hydration and carbonation of peridotite are able to produce extensive alteration at the relatively low temperatures of the near-surface weathering environment.

Fulgurite Morphology: A Classification Scheme and Clues to Formation

Abstract: Fulgurites are natural glasses formed by cloud-to-ground lightning. Several different morphologies of fulgurites have been reported in previous studies, including sand fulgurites, rock fulgurites, and clay fulgurites. Herein, we examine sand, clay, and caliche fulgurites and demonstrate that these differ systematically in their morphology. We further use morphological features to constrain properties of fulgurite-forming lightning strikes. We classify fulgurites into four types of morphologies with an additional minor type. Type I fulgurites are sand fulgurites consisting of thin, glass walls; type II fulgurites are clay fulgurites, consisting of thick, melt rich walls; type III fulgurites are caliche fulgurites, consisting of thick, glass poor walls; and type IV fulgurites are rock fulgurites, consisting of glasses with walls consisting of surrounding, unmelted rock. Fulgurite morphology shows that the energy of fulgurite-forming strikes is between 1 and 30 MJ/m of fulgurite formed, suggests heating rates in the order of 1,000 K/s, and lightning channel thicknesses of about 1 mm diameter. Lightning generates mixtures of at least two components in most fulgurites: an SiO2 glass identified as lechatelierite and a groundmass of more varied composition. In addition to these four primary types, a fifth type—droplet fulgurites—is morphologically dissimilar from the other types, but is compositionally related to the type II or IV fulgurites. Additionally, two fulgurites, both from York County, Pennsylvania, USA, showed the reduction of iron to iron metal with an assortment of Fe–Ti and Si–P compounds with stoichiometry that ranges from nearly pure Fe metal to FeSi. These metal silicides include stoichiometric Fe3Si, Fe2Si, and Fe5Si3, and possibly Fe8Si3 and Fe7Si3, and provide a terrestrial source for these phases, which are typically associated with extraterrestrial material.

Decoding near-concordant U–Pb zircon ages spanning several hundred million years: recrystallisation, metamictisation or diffusion?

Abstract: In situ isotopic (U–Pb, Lu–Hf) and trace element analyses of zircon populations in six samples of the intrusive Mawson Charnockite, east Antarctica, emphasise complex zircon behaviour during very high-grade metamorphism. The combination of geochemical data sets is used to distinguish xenocrysts and identify a population of primary igneous zircon in situations where U–Pb data spread close to concordia over a few hundred Myr. The population is filtered to exclude grains with: (1) U–Pb ages >2% discordant, (2) anomalous trace element-content (Th, U, Y, REE) and (3) outlying Hf-isotopic values. Rare metamorphic-type grains were also excluded. Upon filtering the population, minimum emplacement ages for each sample were determined using the oldest grain(s). This approach improves upon age determinations in complex data sets that use weighted mean or isochron methods. Our results suggest that the Mawson Charnockite was emplaced episodically at c. 1145–1140 Ma, c. 1080–1050 Ma and c. 985–960 Ma. Core-outer core-rim and core-rim textures were identified but are not correlated with U–Pb ages. We establish that recrystallisation (mainly of zircon rims) must have occurred shortly following igneous crystallisation and that metamictisation/cracking is a Paleozoic to Recent event. Therefore, intra-zircon diffusion in a high-T, high-strain environment during Meso-Neoproterozoic orogenesis is inferred to have caused the extensive U–Pb isotopic disturbance. Charnockitic magmatism prior to c. 1,000 Ma has not previously been recorded in the Mawson region and indicates that orogenesis may have commenced c. 150 Myr earlier than previously thought. Correlations with similar aged rocks in adjacent regions have implications for supercontinent reconstructions.

U-Pb zircon dating, geochemical and Sr-Nd-Hf isotopic compositions of Early Indosinian intrusive rocks in West Qinling, central China: petrogenesis and tectonic implications

Abstract: The Qinling–Dabie–Sulu orogenic belt is the junction between the North and South China blocks, which resulted from the final amalgamation of China continents during the Indosinian. Indosinian granitoids are widespread in the Qinling orogen, and their geneses can thus constrain the evolution of China continent. We carried out a combined U–Pb zircon dating and geochemical study for the Shuangpengxi granodiorite pluton and the Xiekeng diorite–granodiorite pluton in the middle part of the West Qinling orogen. U–Pb zircon dating shows that the magma crystallization ages of 242 ± 3 Ma for the Shuangpengxi pluton and ~244–242 Ma for the Xiekeng pluton. Geochemical and Sr–Nd–Hf isotopic compositions reveal that the magma of the Shuangpengxi granodiorite was derived from partial melting of crustal materials. The Xiekeng diorites can be divided into high-Al diorite and high-Mg diorite. Both of them resulted from partial melting of enriched lithospheric mantle, but their mantle source had been modified by previous slab-derived melt. The high-Al diorite was formed by fractional crystallization of olivine, pyroxene and/or preferential accumulation of plagioclase, and the high-Mg diorite was formed by fractional crystallization of olivine and/or preferential accumulation of pyroxene. The Xiekeng granodioritic porphyry was formed by mixing of crust-derived and mantle-derived melts. We propose that the Early Indosinian magmatism resulted from break-off of subducted oceanic slab after collision. The slab break-off model can well explain the linear distribution of the Early Indosinian plutons and rapid crustal uplift during the Middle Triassic in the West Qinling.

Evolution of silicic magmas in the Kos-Nisyros volcanic center, Greece: a petrological cycle associated with caldera collapse

Abstract: Multiple eruptions of silicic magma (dacite and rhyolites) occurred over the last ~3 My in the Kos-Nisyros volcanic center (eastern Aegean sea). During this period, magmas have changed from hornblende-biotite-rich units with low eruption temperatures (≤750–800°C; Kefalos and Kos dacites and rhyolites) to hotter, pyroxene-bearing units (>800–850°C; Nisyros rhyodacites) and are transitioning back to cooler magmas (Yali rhyolites). New whole-rock compositions, mineral chemistry, and zircon Hf isotopes show that these three types of silicic magmas followed the same differentiation trend: they all evolved by crystal fractionation and minor crustal assimilation (AFC) from parents with intermediate compositions characterized by high Sr/Y and low Nb content, following a wet, high oxygen fugacity liquid line of descent typical of subduction zones. As the transition between the Kos-Kefalos and Nisyros-type magmas occurred immediately and abruptly after the major caldera collapse in the area (the 161 ka Kos Plateau Tuff; KPT), we suggest that the efficient emptying of the magma chamber during the KPT drew out most of the eruptible, volatile-charged magma and partly solidified the unerupted mush zone in the upper crust due to rapid unloading, decompression, and coincident crystallization. Subsequently, the system reestablished a shallow silicic production zone from more mafic parents, recharged from the mid to lower crust. The first silicic eruptions evolving from these parents after the caldera collapse (Nisyros units) were hotter (up to >100°C) than the caldera-forming event and erupted from reservoirs characterized by different mineral proportions (more plagioclase and less amphibole). We interpret such a change as a reflection of slightly drier conditions in the magmatic column after the caldera collapse due to the decompression event. With time, the upper crustal intermediate mush progressively transitioned into the cold-wet state that prevailed during the Kefalos-Kos stage. The recent eruptions of the high-SiO2 rhyolite on Yali Island, which are low temperature and hydrous phases (sanidine, quartz, biotite), suggest that another large, potentially explosive magma chamber is presently building under the Kos-Nisyros volcanic center.

Magma accumulation rates and thermal histories of plutons of the Sierra Nevada batholith, CA

Abstract: Zircon U–Pb geochronology results indicate that the John Muir Intrusive Suite of the central Sierra Nevada batholith, California, was assembled over a period of at least 12 Ma between 96 and 84 Ma. Bulk mineral thermochronology (U–Pb zircon and titanite, 40Ar/39Ar hornblende and biotite) of rocks from multiple plutons comprising the Muir suite indicates rapid cooling through titanite and hornblende closure following intrusion and subsequent slow cooling through biotite closure. Assembly of intrusive suites in the Sierra Nevada and elsewhere over millions of years favors growth by incremental intrusion. Estimated long-term pluton assembly rates for the John Muir Intrusive Suite are on the order of 0.001 km3 a−1 which is inconsistent with the rapid magma fluxes that are necessary to form large-volume magma chambers capable of producing caldera-forming eruptions. If large shallow crustal magma chambers do not typically develop during assembly of large zoned intrusive suites, it is doubtful that the intrusive suites represent cumulates left behind following caldera-forming eruptions.

Peralkaline magma evolution and the tephra record in the Ethiopian Rift

Abstract: The 3.119 ± 0.010 Ma Chefe Donsa phreatomagmatic deposits on the shoulder of the Ethiopian Rift mark the northern termination of the Silti-Debre Zeyit Fault Zone, a linear zone of focused extension within the modern Ethiopian Rift. These peralkaline pumice fragments and glass shards span a wide range of glass compositions but have a restricted phenocryst assemblage dominated by unzoned sanidine. Glass shards found within the ash occupy a far more limited compositional range (75–76 wt% SiO2) in comparison with the pumice (64–75 wt% SiO2), which is rarely mingled. Thermodynamic modeling shows that liquids broadly similar to the least evolved glass composition can be achieved with 50–60 % fractionation of moderately crustally contaminated basalt. Inconsistencies between modeled solutions and the observed values of CaO and P2O5 highlight the important role of fluorine in stabilizing fluor-apatite and the limitations of current thermodynamic models largely resulting from the scarce experimental data available for the role of fluorine in igneous phase stability. On the basis of limited feldspar heterogeneity and crystal content of pumice at Chefe Donsa, and the difficulties of extracting small volumes of Si-rich melt in classical fractional crystallization models, we suggest a two-step polybaric process: (1) basaltic magma ponds at mid-upper-crustal depths and fractionates to form a crystal/magma mush. Once this mush has reached 50–60 % crystallinity, the interstitial liquid may be extracted from the rigid crystal framework. The trachytic magma extracted at this step is equivalent to the most primitive pumice analyzed at Chefe Donsa. (2) The extracted trachytic liquid will rise and continue to crystallize, generating a second mush zone from which rhyolite liquids may be extracted. Some of the compositional range observed in the Chefe Donsa deposits may result from the fresh intrusion of trachyte magma, which may also provide an eruption trigger. This model may have wider application in understanding the origin of the Daly Gap in Ethiopian magmas—intermediate liquids may not be extracted from crystal-liquid mushes due to insufficient crystallization to yield a rigid framework. The wide range of glass compositions characteristic of the proximal Chefe Donsa deposits is not recorded in temporally equivalent tephra deposits located in regional depocenters. Our results show that glass shards, which represent the material most likely transported to distal depocenters, occupy a limited compositional range at high SiO2 values and overlap some distal tephra deposits. These results suggest that distal tephra deposits may not faithfully record the potentially wide range in magma compositions present in a magmatic system just prior to eruption and that robust distal–proximal tephra correlations must include a careful analysis of the full range of materials in the proximal deposit.

Liquid immiscibility between silicate, carbonate and sulfide melts in melt inclusions hosted in co-precipitated minerals from Kerimasi volcano (Tanzania): evolution of carbonated nephelinitic magma

Abstract: The evolution of a carbonated nephelinitic magma can be followed by the study of a statistically significant number of melt inclusions, entrapped in co-precipitated perovskite, nepheline and magnetite in a clinopyroxene- and nepheline-rich rock (afrikandite) from Kerimasi volcano (Tanzania). Temperatures are estimated to be 1,100°C for the early stage of the melt evolution of the magma, which formed the rock. During evolution, the magma became enriched in CaO, depleted in SiO2 and Al2O3, resulting in immiscibility at ~1,050°C and crustal pressures (0.5–1 GPa) with the formation of three fluid-saturated melts: an alkali- and MgO-bearing, CaO- and FeO-rich silicate melt; an alkali- and F-bearing, CaO- and P2O5-rich carbonate melt; and a Cu–Fe sulfide melt. The sulfide and the carbonate melt could be physically separated from their silicate parent and form a Cu–Fe–S ore and a carbonatite rock. The separated carbonate melt could initially crystallize calciocarbonatite and ultimately become alkali rich in composition and similar to natrocarbonatite, demonstrating an evolution from nephelinite to natrocarbonatite through Ca-rich carbonatite magma. The distribution of major elements between perovskite-hosted coexisting immiscible silicate and carbonate melts shows strong partitioning of Ca, P and F relative to FeT, Si, Al, Mn, Ti and Mg in the carbonate melt, suggesting that immiscibility occurred at crustal pressures and plays a significant role in explaining the dominance of calciocarbonatites (sovites) relative to dolomitic or sideritic carbonatites. Our data suggest that Cu–Fe–S compositions are characteristic of immiscible sulfide melts originating from the parental silicate melts of alkaline silicate–carbonatite complexes.

Li isotopes and trace elements as a petrogenetic tracer in zircon: insights from Archean TTGs and sanukitoids

Abstract: We report δ7Li, Li abundance ([Li]), and other trace elements measured by ion probe in igneous zircons from TTG (tonalite, trondhjemite, and granodiorite) and sanukitoid plutons from the Superior Province (Canada) in order to characterize Li in zircons from typical Archean continental crust. These data are compared with detrital zircons from the Jack Hills (Western Australia) with U–Pb ages greater than 3.9 Ga for which parent rock type is not known. Most of the TTG and sanukitoid zircon domains preserve typical igneous REE patterns and CL zoning. [Li] ranges from 0.5 to 79 ppm, typical of [Li] in continental zircons. Atomic ratios of (Y + REE)/(Li + P) average 1.0 ± 0.7 (2SD) for zircons with magmatic composition preserved, supporting the hypothesis that Li is interstitial and charge compensates substitution of trivalent cations. This substitution results in a relatively slow rate of Li diffusion. The δ7Li and trace element data constrain the genesis of TTGs and sanukitoids. [Li] in zircons from granitoids is significantly higher than from zircons in primitive magmas in oceanic crust. TTG zircons have δ7Li (3 ± 8‰) and δ18O in the range of primitive mantle-derived magmas. Sanukitoid zircons have average δ7Li (7 ± 8‰) and δ18O higher than those of TTGs supporting genesis by melting of fluid-metasomatized mantle wedge. The Li systematics in sanukitoid and TTG zircons indicate that high [Li] in pre-3.9-Ga Jack Hills detrital zircons is a primary igneous composition and suggests the growth in proto-continental crust in magmas similar to Archean granitoids.

Crystal scale anatomy of a dying supervolcano: an isotope and geochronology study of individual phenocrysts from voluminous rhyolites of the Yellowstone caldera

Abstract: A voluminous (>600 km3) and long-lived (~520–75 ka) phase of rhyolitic eruptions followed collapse of the Yellowstone caldera 640 ka. Whether these eruptions represent a dying cycle, or the growth of a new magma chamber, remains an important question. We use new U–Th zircon ages and δ18O values determined by ion microprobe, and sanidine Pb isotope ratios determined by laser ablation, to investigate the genesis of voluminous post-caldera rhyolites. The oldest post-caldera rhyolites, erupted between ~520 and 470 ka, exhibit extreme age and oxygen isotopic heterogeneity, requiring derivation from individual parcels of low-δ18O melts. We find a progressive increase in zircon homogeneity for rhyolite eruptions from ~260 to 75 ka, with homogeneous low-δ18O zircon values of 2.7–2.8‰ that are in equilibrium with low-δ18O host melts for the majority of the youngest eruptions. New sanidine Pb isotope data define separate arrays for post-caldera rhyolites and the caldera-forming tuffs that preceded them, indicating that they were not sourced from a mushy Lava Creek Tuff batholith that remained after caldera collapse. Rather, our new age and isotopic data indicate that the post-caldera rhyolites were generated by remelting of a variety of intracaldera source rocks, consisting of pre-Lava Creek Tuff volcanic and plutonic rocks and earlier erupted post-Lava Creek Tuff rhyolites. Batch assembly of low-δ18O melts starting at ~260 ka resulted in progressive homogenization, followed by differentiation and cooling up until the last rhyolite eruption ~75 ka, a trend that we interpret to be characteristic of a dying magma reservoir beneath the Yellowstone caldera.

A comparative study of melt-rock reactions in the mantle: laboratory dissolution experiments and geological field observations

Abstract: Systematic variations in mineralogy and chemical composition across dunite-harzburgite (DH) and dunite-harzburgite-lherzolite (DHL) sequences in the mantle sections of ophiolites have been widely observed. The compositional variations are due to melt-rock reactions as basaltic melts travel through mantle peridotite, and may be key attributes to understanding melting and melt transport processes in the mantle. In order to better understand melt-rock reactions in the mantle, we conducted laboratory dissolution experiments by juxtaposing a spinel lherzolite against an alkali basalt or a mid-ocean ridge basalt. The charges were run at 1 GPa and either 1,300°C or 1,320°C for 8–28 h. Afterward, the charges were slowly cooled to 1,200°C and 1 GPa, which was maintained for at least 24 h to promote in situ crystallization of interstitial melts. Cooling allowed for better characterization of the mineralogy and mineral compositional trends produced and observed from melt-rock reactions. Dissolution of lherzolite in basaltic melts with cooling results in a clinopyroxene-bearing DHL sequence, in contrast to sequences observed in previously reported isothermal-isobaric dissolution experiments, but similar to those observed in the mantle sections of ophiolites. Compositional variations in minerals in the experimental charges follow similar melt-rock trends suggested by the field observations, including traverses across DH and DHL sequences from mantle sections of ophiolites as well as clinopyroxene and olivine from clinopyroxenite, dunite, and wehrlite dikes and xenoliths. These chemical variations are controlled by the composition of reacting melt, mineralogy and composition of host peridotite, and grain-scale processes that occur at various stages of melt-peridotite reaction. We suggest that laboratory dissolution experiments are a robust model to natural melt-rock reaction processes and that clinopyroxene in replacive dunites in the mantle sections of ophiolites is genetically linked to clinopyroxene in cumulate dunite and pyroxenites through melt transport and melt-rock reaction processes in the mantle.

Petrogenesis of the Neogene volcanic units in the NE–SW-trending basins in western Anatolia, Turkey

Abstract: The western Anatolian volcanic province formed during Eocene to Recent times is one of the major volcanic belts in the Aegean–western Anatolian region. We present new chemical (whole-rock major and trace elements, and Sr, Nd, Pb and O isotopes) and new Ar/Ar age data from the Miocene volcanic rocks in the NE–SW-trending Neogene basins that formed on the northern part of the Menderes Massif during its exhumation as a core complex. The early-middle Miocene volcanic rocks are classified as high-K calc-alkaline (HKVR), shoshonitic (SHVR) and ultrapotassic (UKVR), with the Late Miocene basalts being transitional between the early-middle Miocene volcanics and the Na-alkaline Quaternary Kula volcanics (QKV). The early-middle Miocene volcanic rocks are strongly enriched in large ion lithophile elements (LILE), have high 87Sr/86Sr(i) (0.70631–0.71001), low 143Nd/144Nd(i) (0.512145–0.512488) and high Pb isotope ratios (206Pb/204Pb = 18.838–19.148; 207Pb/204Pb = 15.672–15.725; 208Pb/204Pb = 38.904–39.172). The high field strength element (HFSE) ratios of the most primitive early-middle Miocene volcanic rocks indicate that they were derived from a mantle source with a primitive mantle (PM)-like composition. The HFSE ratios of the late Miocene basalts and QKV, on the other hand, indicate an OIB-like mantle origin—a hypothesis that is supported by their trace element patterns and isotopic compositions. The HFSE ratios of the early-middle Miocene volcanic rocks also indicate that their mantle source was distinct from those of the Eocene volcanic rocks located further north, and of the other volcanic provinces in the region. The mantle source of the SHVR and UKVR was influenced by (1) trace element and isotopic enrichment by subduction-related metasomatic events and (2) trace element enrichment by “multi-stage melting and melt percolation” processes in the lithospheric mantle. The contemporaneous SHVR and UKVR show little effect of upper crustal contamination. Trace element ratios of the HKVR indicate that they were derived mainly from lower continental crustal melts which then mixed with mantle-derived lavas (~20–40%). The HKVR then underwent differentiation from andesites to rhyolites via nearly pure fractional crystallization processes in the upper crust, such that have undergone a two-stage petrogenetic evolution.

H 2 O storage capacity of olivine and low-Ca pyroxene from 10 to 13 GPa: consequences for dehydration melting above the transition zone

Abstract: The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C, the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation $$ C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). $$ Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations of $$ D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} $$ from this study and estimates of $$ D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} $$ , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values of $$ D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} $$ at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence on viscosity and other transport properties.

Electrical conductivity of amphibole-bearing rocks: influence of dehydration

Abstract: We investigated the electrical conductivity of amphibole-bearing rocks under the conditions of the middle to lower crust. Alternating current measurements were performed in the frequency range of 10–106 Hz in a cubic-anvil high-pressure apparatus at 0.5–1.0 GPa and 373–873 K. The electrical conductivity of these rocks is weakly temperature dependent below ~800 K with modest anisotropy and relatively low conductivity (~5 × 10−3 S/m at ~750 K with the activation enthalpy of 64–67 kJ/mol). However, the electrical conductivity starts to increase with temperature more rapidly above ~800 K (activation enthalpy of 320–380 kJ/mol). The infrared spectroscopy observations indicate that dehydration occurs in this high temperature regime. The observed high activation enthalpy and the reproducibility suggest that the enhanced conductivity is not due to the direct effect caused by the generation of conductive fluids. Dehydration of amphibole is associated with the oxidation of iron (from ferrous to ferric), and we suggest that the increased conductivity associated with dehydration is caused by oxidation. This effect may explain high electrical conductivity observed in some regions of the continental crust.

Modification of fluid inclusions in quartz by deviatoric stress. III: Influence of principal stresses on inclusion density and orientation

Abstract: Extraction of useful geochemical, petrologic and structural information from deformed fluid inclusions is still a challenge in rocks displaying moderate plastic strain. In order to better understand the inclusion modifications induced by deviatoric stresses, six deformation experiments were performed with a Griggs piston-cylinder apparatus. Natural NaCl–H2O inclusions in an oriented quartz crystal were subjected to differential stresses of 250–470 MPa at 700–900 °C and at 700–1,000 MPa confining pressure. Independently of the strain rate and of the crystallographic orientation of the quartz, the inclusions became dismembered and flattened within a crystallographic cleavage plane subperpendicular to σ1. The neonate (newly formed) inclusions that result from dismemberment have densities that tend towards equilibrium with Pfluid = σ1 at Tshearing. These results permit ambiguities in earlier deformation experiments on CO2–H2O–NaCl to be resolved. The results of the two studies converge, indicating that density changes in neonate inclusions are promoted by high differential stresses, long periods at high P and high T, and fluid compositions that maximize quartz solubility. Neonates spawned from large precursor inclusions show greater changes in density that those spawned from small precursors. These findings support the proposal that deformed fluid inclusions can serve as monitors of both the orientation and magnitude of deviatoric stresses during low-strain, ductile deformation of quartz-bearing rocks.

Prediction of plagioclase-melt equilibria in anhydrous silicate melts at 1-atm

Abstract: Many models for plagioclase-melt equilibria have been proposed over the past 30 years, but the focus is increasingly on the effects of water content and pressure. However, many geological and petrological applications concern low pressure and low water systems, such as the differentiation of large terrestrial basaltic magma chambers, and lunar and asteroidal magmatism. There is, therefore, a justified need to quantify the influence of anhydrous liquid composition on the composition of equilibrium plagioclase at 1-atm. With this in mind, a database of over 500 experimentally determined plagioclase-liquid pairs has been created. The selected low pressure, anhydrous, experiments include both natural and synthetic liquids, whose compositions range from basalt to rhyolite. Four equations are proposed, derived from this data. The first is based on a thermodynamically inspired formalism, explicitly integrating the effect of temperature. This equation uses free energies and activities of crystalline anorthite available from the literature. For the activity of anorthite in the liquid phase, it is found that current models of the activity of individual oxides are insufficient to account for the experimental results. We have therefore derived an empirical expression for the variation of anorthite activity in the liquid as a function of melt composition, based upon inversion of the experimental data. Using this expression allows the calculation of plagioclase composition with a relative error less than 10%. However, in light of the fact that temperature is not necessarily known for many petrological applications, an alternative set of T-independent equations is also proposed. For this entirely empirical approach, the database has been divided into three compositional groups, treated independently for regression purposes: mafic–ultramafic, alkali-rich mafic–ultramafic, and intermediate-felsic. This separation into distinct subgroups was found to be necessary to maintain errors below acceptable limits, but results across group boundaries were found to be comparable. Overall, 50% of plagioclase compositions are predicted to within 2% of the experimentally derived value, and 90% to within 5%, representing a significant improvement over existing models.