Zr diffusion in titanite

Chemical diffusion of Zr under anhydrous, pO₂-buffered conditions has been measured in natural titanite. The source of diffusant was either zircon powder or a ZrO₂–Al₂O₃–titanite mixture. Experiments were run in sealed silica glass capsules with solid buffers (to buffer at NNO or QFM). Rutherford Backscattering Spectrometry (RBS) was used to measure diffusion profiles. The following Arrhenius parameters were obtained for Zr diffusion parallel to c over the temperature range 753–1,100°C under NNO-buffered conditions: D _Zr = 5.33 × 10⁻⁷ exp(−325 ± 30 kJ mol⁻¹/RT) m² s⁻¹ Diffusivities are similar for experiments buffered at QFM. These data suggest that titanite should be moderately retentive of Zr chemical signatures, with diffusivities slower than those for O and Pb in titanite, but faster than those for Sr and the REE. When applied in evaluation of the relative robustness of the recently developed Zr-in-titanite geothermometer (Hayden and Watson, Abstract, 16th V.M. Goldschmidt Conference 2006), these findings suggest that Zr concentrations in titanite will be less likely to be affected by later thermal disturbance than the geothermometer based on Zr concentrations in rutile (Zack et al. in Contrib Mineral Petrol 148:471–488, 2004; Watson et al. in Contrib Mineral. Petrol, 2006), but much less resistant to diffusional alteration subsequent to crystallization than the Ti-in-Zircon geothermometer (Watson and Harrison in Science 308:841–844, 2005).     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

Reply to “Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.”

The comment by Day et al. (Contrib Mineral Petrol, 2012) (1) discusses the validity of the previously obtained oxygen isotope data for El Hierro and La Palma (Canary Island) olivines, (2) questions the approach by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) of using weakly correlated variations of δ¹⁸O_olivine values with X _px (proportion of pyroxenite-derived melt in the parental magma), and (3) provides reasons why oxygen isotope data by secondary ion mass spectrometry (SIMS) “offer sensitive means for detecting melt-crust interactions.” We respond these comments and report a new set of oxygen isotope measurements performed by SIMS and single-grain laser fluorination methods. These measurements confirm our previous data and conclusions and demonstrate the ability of the SIMS technique to analyze O isotopes in terrestrial samples with 2-sigma uncertainty better than ±0.25 ‰.     

Application of the Ti-in-quartz thermobarometer to rutile-free systems. Reply to: a comment on: ‘TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz’ by Thomas et al.

The premise of the Wilson et al. comment is that the Ti-in-quartz solubility calibration (Thomas et al. in Contrib Mineral Petrol 160:743–759, 2010) is fundamentally flawed. They reach this conclusion because P–T estimates using the Ti-in-quartz calibration differ from their previous interpretations for crystallization conditions of the Bishop and Oruanui rhyolites. If correct, this assertion has far-reaching implications, so a careful assessment of the Wilson et al. reasoning is warranted. Application of the Ti-in-quartz calibration as a thermobarometer in rutile-free rocks requires an estimation of TiO₂ activity in the liquid ( (liquid–rutile); referenced to rutile saturation) and an independent constraint on either P or T to obtain the crystallization temperature or pressure, respectively. The foundation of Wilson et al.’s argument is that temperature estimates obtained from Fe–Ti oxide thermometry accurately reflect crystallization conditions of quartz in the two rhyolites discussed. We maintain that our experimental approach is sound, the thermodynamic basis of the Ti-in-quartz calibration is fundamentally correct, and our experimental results are robust and reproducible. We suggest that the reason Wilson et al. obtain implausible pressure estimates is because estimates for T and they used as input values for the Ti-in-quartz calibration are demonstrably too high. Numerous studies show that Fe–Ti oxide temperature estimates of some rhyolites are substantially higher than those predicted by well-constrained phase equilibria. In this reply, we show that when reasonable input values for T and (liquid–rutile) are used, pressure estimates obtained from the Ti-in-quartz calibration are well aligned with phase equilibria and essentially identical to melt inclusion volatile saturation pressures.     

Basanite–nephelinite suite from early Kilauea: carbonated melts of phlogopite–garnet peridotite at Hawaii’s leading magmatic edge

A basanite–nephelinite glass suite from early submarine Kilauea defines a continuous compositional array marked by increasing concentrations of incompatible components with decreasing SiO₂, MgO, and Al₂O₃. Like peripheral and post-shield strongly alkalic Hawaiian localities (Clague et al. in J Volcanol Geotherm Res 151:279–307, 2006; Dixon et al. in J Pet 38:911–939, 1997), the early Kilauea basanite–nephelinite glasses are interpreted as olivine fractionation products from primary magnesian alkalic liquids. For early Kilauea, these were saturated with a garnet–phlogopite–sulfide peridotite assemblage, with elevated dissolved CO₂ contents responsible for the liquids’ distinctly low-SiO₂ concentrations. Reconstructed primitive liquids for early Kilauea and other Hawaiian strongly alkalic localities are similar to experimental 3 GPa low-degree melts of moderately carbonated garnet lherzolite, and estimated parent magma temperatures of 1,350–1,400°C (olivine–liquid geothermometry) match the ambient upper mantle geotherm shortly beneath the base of the lithosphere. The ~3 GPa source regions were too hot for stable crystalline carbonate and may have consisted of ambient upper mantle peridotite containing interstitial carbonate–silicate or carbonatitic liquid, possibly (Dixon et al. in Geochem Geophys Geosyst 9(9):Q09005, 2008), although not necessarily, from the Hawaiian mantle plume. Carbonate-enriched domains were particularly susceptible to further melting upon modest decompression during upward lithospheric flexure beneath the advancing Hawaiian Arch, or by conductive heating or upward drag by the Hawaiian mantle plume. The early Kilauea basanite–nephelinite suite has a HIMU-influenced isotopic character unlike other Hawaiian magmas (Shimizu et al. in EOS Tran Amer Geophys Union 82(47): abstr V12B-0962, 2001; Shimizu et al. in Geochim Cosmochim Acta 66(15A):710, 2002) but consistent with oceanic carbonatite involvement (Hoernle et al. in Contrib Mineral Petrol 142:520–542, 2002). It may represent the melting products of a fertile domain in the ambient upper mantle impinged upon and perturbed by the sustained plume source that feeds later shield-stage magmatism.     

Cordierite as an indicator of thermodynamic conditions of petrogenesis

A refined thermodynamic model of H₂O and CO₂ bearing cordierite based on recent data on volatile incorporation into cordierite (Thompson et al. in Contrib Mineral Petrol 142:107–118, 2001; Harley and Carrington in J Petrol 42:1595–1620, 2001) reflects non-ideality of channel H₂O and CO₂ mixing. The dependence of cordierite H₂O and CO₂ contents on P, T and equilibrium fluid composition has been calculated for the range 600–800°C and 200–800 MPa. It has been used for establishing thermodynamic conditions of cordierite formation and the following retrograde P–T paths of cordierite rocks from many localities. Estimates of the H₂O and CO₂ activities have shown that cordierites in granites, pegmatites and high-pressure granulites were formed in fluid-saturated conditions and wide range of H₂O/CO₂ relations. Very low cordierite H₂O contents in many migmatites may be caused not only by fluid-undersaturated conditions at rock formation and H₂O leakage on retrograde P–T paths but also by the presence of additional volatile components like CH₄ and N₂. The pressure dependence of cordierite-bearing mineral equilibria on fluid H₂O/CO₂ relations has been evaluated.     

Garnet–orthopyroxene (GOPX) geothermometer: a comparative study

The garnet–orthopyroxene pairs are commonly found in the assemblages of basic granulites/charnockite and hence are suitable for estimating equilibrium temperature of these metamorphic rocks. At present, there are many calibrations of garnet–orthopyroxene thermometer that may confuse geologists in choosing a reliable thermometer. To test the accuracy of the garnet–orthopyroxene thermometers, we have applied 14 models formulated by a number of workers since 1980 to date. We have collated 51 samples from the literature all over the world, which has been processed through the “Gt-Opx.EXE” software. Based on the present study, we have identified a set of the best among all the 14 models which were considered under this comparative study. We have concluded that the five garnet–orthopyroxene (Gt-Opx) thermometers are the most valid and reliable of this kind of thermometer: Aranovich and Berman (Am Mineral 82:345–353, 1997), Raith et al. (Earth Sci 73:211–244, 1983), Harley (Contrib Mineral Petrol 86:359–373, 1984), Nimis and Grütter (Contrib Mineral Petrol 159:411–427, 2010), and Sen and Bhattacharya (Contrib Mineral Petrol 88:64–71, 1984).     

Thermodynamics of mixing in diopside–jadeite,CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–NaAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript>, solid solution from static lattice energy calculations

Static lattice energy calculations (SLEC), based on empirical interatomic potentials, have been performed for a set of 800 different structures in a 2 × 2 × 4 supercell of C2/c diopside with compositions between diopside and jadeite, and with different states of order of the exchangeable Na/Ca and Mg/Al cations. Excess static energies of these structures have been cluster expanded in a basis set of 37 pair-interaction parameters. These parameters have been used to constrain Monte Carlo simulations of temperature-dependent properties in the range of 273–2,023 K and to calculate a temperature–composition phase diagram. The simulations predict the order–disorder transition in omphacite at 1,150 ± 20°C in good agreement with the experimental data of Carpenter (Mineral Petrol 78:433–440, 1981). The stronger ordering of Mg/Al within the M1 site than of Ca/Na in the M2 site is attributed to the shorter M1–M1 nearest-neighbor distance, and, consequently, the stronger ordering force. The comparison of the simulated relationship between the order parameters corresponding to M1 and M2 sites with the X-ray refinement data on natural omphacites (Boffa Ballaran et al. in Am Mineral 83:419–433, 1998) suggests that the cation ordering becomes kinetically ineffective at about 600°C.     

Reply to ‘Comment on “The beginnings of hydrous mantle wedge melting” by Till et al.’ by Green, Rosenthal and Kovacs

The comment of Green et al. debates the interpretation of the temperature of the H₂O-saturated peridotite solidus and presence of silicate melt in the experiments of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) at <1,000?°C. The criticisms presented in their comment do not invalidate any of the most compelling observations of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) as discussed in the following response, including the changing minor element and Mg# composition of the solid phases with increasing temperature in our experiments with 14.5?wt% H₂O at 3.2?GPa, as well as the results of our chlorite peridotite melting experiments with 0.7?wt% H₂O. The point remains that Till et al. (Contrib Mineral Petrol 163:669–688, 2012) present data that call into question the H₂O-saturated peridotite solidus temperature preferred by Green (Tectonophysics 13(1–4):47–71, 1972; Earth Planet Sci Lett 19(1):37–53, 1973; Can Miner 14:255–268, 1976); Millhollen et al. (J Geol 82(5):575–587, 1974); Mengel and Green (Stability of amphibole and phlogopite in metasomatized peridotite under water-saturated and water-undersaturated conditions, Geological Society of Australia Special Publication, Blackwell, pp 571-581, 1989); Wallace and Green (Mineral Petrol 44:1–19, 1991) and Green et al. (Nature 467(7314):448–451, 2010).     

Coupling of oceanic and continental crust during Eocene eclogite-facies metamorphism: evidence from the Monte Rosa nappe,western Alps

High precision U–Pb geochronology of rutile from quartz–carbonate–white mica–rutile veins that are hosted within eclogite and schist of the Monte Rosa nappe, western Alps, Italy, indicate that the Monte Rosa nappe was at eclogite-facies metamorphic conditions at 42.6 ± 0.6 Ma. The sample area [Indren glacier, Furgg zone; Dal Piaz (2001) Geology of the Monte Rosa massif: historical review and personal comments. SMPM] consists of eclogite boudins that are exposed inside a south-plunging overturned synform within micaceous schist. Associated with the eclogite and schist are quartz–carbonate–white mica–rutile veins that formed in tension cracks in the eclogite and along the contact between eclogite and surrounding schist. Intrusion of the veins at about 42.6 Ma occurred at eclogite-facies metamorphic conditions (480–570°C, >1.3–1.4 GPa) based on textural relations, oxygen isotope thermometry, and geothermobarometry. The timing of eclogite-facies metamorphism in the Monte Rosa nappe determined in this study is identical to that of the Gran Paradiso nappe [Meffan-Main et al. (2004) J Metamorphic Geol 22:261–281], confirming that these two units have shared the same Alpine metamorphic history. Furthermore, the Gran Paradiso and Monte Rosa nappes underwent eclogite-facies metamorphism within the same time interval as the structurally overlying Zermatt-Saas ophiolite [∼50–40 Ma; e.g., Amato et al. (1999) Earth Planet Sci Lett 171:425–438; Mayer et al. (1999) Eur Union Geosci 10:809 (abstract); Lapen et al. (2003) Earth Planet Sci Lett 215:57–72]. The nearly identical P–T–t histories of the Gran Paradiso, Monte Rosa, and Zermatt-Saas units suggest that these units shared a common Alpine tectonic and metamorphic history. The close spatial and temporal associations between high pressure (HP) ophiolite and continental crust during Alpine orogeny indicates that the HP internal basement nappes in the western Alps may have played a key role in exhumation and preservation of the ophiolitic rocks through buoyancy-driven uplift. Coupling of oceanic and continental crust may therefore be critical in preventing permanent loss of oceanic crust to the mantle.     

Heat capacity,entropy and phase equilibria of stishovite

The low-temperature heat capacity (C _P) of stishovite (SiO₂) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol⁻¹ K⁻¹, which is considerably smaller (by 2.86 J mol⁻¹ K⁻¹) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).     

Thermochemistry of sulfide liquids III: Ni-bearing liquids at 1 bar

Experiments were performed in the system O–S–Fe–Ni designed to extend our understanding of the chemistry of sulfide liquids. Results indicate that adding nickel to Fe-rich sulfide liquids in equilibrium with silicate liquids extends their stability field to much higher oxygen fugacities and lower sulfur fugacities. Increasing Ni/Fe at a given temperature and sulfur and oxygen fugacity is accompanied by a significant decrease in the oxygen content of the sulfide liquid. Results of these experiments are combined with data from the literature to calibrate an associated regular solution model for O–S–Fe–Ni liquids. This model represents a complete refit of the associated regular solution model of Kress (Contrib Mineral Petrol 139:316–325, 2000). The resulting model is combined with the olivine solution model of Hirschmann (Am Mineral 76:1232–1248, 1991) to explore the effect of variations in oxygen and sulfur fugacities on the distribution of Fe and Ni between olivine and sulfide liquid. Predicted olivine–sulfide distribution trends parallel those observed by Gaetani and Grove (Geochim Cosmochim Acta 61:1829–1846, 1997), Gaetani and Grove (Earth Planet Sci Lett 169:147–163, 1999), Brenan and Caciagli (Geochim Cosmochim Acta 64:307–320, 2000) and Brenan (Geochim Cosmochim Acta 67:2663–2681, 2003), but are systematically offset toward lower predicted Ni in the sulfide. Nevertheless our results are consistent with the assertion that low K _D ^os values in magmatic ore deposits such as the J-M Reef reflect high iron contents in the sulfides combined with relatively high oxygen fugacities.

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Quantifying garnet-melt trace element partitioning using lattice-strain theory: assessment of statistically significant controls and a new predictive model

As a complement to our efforts to update and revise the thermodynamic basis for predicting garnet-melt trace element partitioning using lattice-strain theory (van Westrenen and Draper in Contrib Mineral Petrol, this issue), we have performed detailed statistical evaluations of possible correlations between intensive and extensive variables and experimentally determined garnet-melt partitioning values for trivalent cations (rare earth elements, Y, and Sc) entering the dodecahedral garnet X-site. We applied these evaluations to a database containing over 300 partition coefficient determinations, compiled both from literature values and from our own work designed in part to expand that database. Available data include partitioning measurements in ultramafic to basaltic to intermediate bulk compositions, and recent studies in Fe-rich systems relevant to extraterrestrial petrogenesis, at pressures sufficiently high such that a significant component of majorite, the high-pressure form of garnet, is present. Through the application of lattice-strain theory, we obtained best-fit values for the ideal ionic radius of the dodecahedral garnet X-site, r ₀(3+), its apparent Young’s modulus E(3+), and the strain-free partition coefficient D ₀(3+) for a fictive REE element J of ionic radius r ₀(3+). Resulting values of E, D ₀, and r ₀ were used in multiple linear regressions involving sixteen variables that reflect the possible influence of garnet composition and stoichiometry, melt composition and structure, major-element partitioning, pressure, and temperature. We find no statistically significant correlations between fitted r ₀ and E values and any combination of variables. However, a highly robust correlation between fitted D ₀ and garnet-melt Fe–Mg exchange and D _Mg is identified. The identification of more explicit melt-compositional influence is a first for this type of predictive modeling. We combine this statistically-derived expression for predicting D ₀ with the new expressions for predicting E and r ₀ outlined in the first of our pair of companion papers into an updated set of formulae that use easy-to-measure quantities (e.g. garnet composition, pressure, temperature) to predict variations in E, r ₀, and D ₀. These values are used in turn to calculate D values for those garnets. The updated model substantially improves upon a previous model (van Westrenen et al. in Contrib Mineral Petrol 142:219–234, 2001), and accounts well for trivalent cation partitioning in nominally anhydrous systems up to at least 15 GPa, including for eclogitic bulk compositions and for Fe-rich systems appropriate to magmagenesis on the Moon and Mars. The new model is slightly less successful in predicting partitioning with strongly majoritic garnets, although the mismatch is much less than with the original 2001 model. Although it also improves upon the 2001 model in predicting partitioning in hydrous systems, the mismatch between model and observation is still unacceptably large. The same statistical tools were applied in an attempt to predict tetravalent partitioning as well, because lattice-strain based techniques are not applicable to such partitioning. However, no statistically significant predictive relationships emerged from that effort. Our analyses show that future efforts should focus on filling the gap in partitioning data between ∼10 and 25 GPa to evaluate more closely the gradual transition of garnet to majorite, and on systematically expanding the hydrous partitioning database to allow extension of our model to water-bearing systems.     

Effects of melt viscosity and silica activity on the rate and mechanism of quartz dissolution in melts of the CMAS and CAS systems

The dissolution rate of quartz in melts of the CMAS and CAS systems at 1,600°C and 1.5 GPa is a function of both the silica activity of the melt and its viscosity. In melts with low silica activity quartz dissolves more quickly than in higher aSiO₂ melts regardless of viscosity. For melts with equal aSiO₂, dissolution is faster in the low viscosity melt. Quartz dissolution is controlled by interface kinetics in three of the four melts used in this study for times much greater than predicted by the model of Zhang et al. (in Contrib Mineral Petrol 102:492–513 1989). One melt which was previously shown to adhere to the predicted behaviour at lower temperature shows a significant activation time at higher temperature. All the dissolution data indicate that there are likely to be three distinct domains of dissolution behaviour, although the details of why a particular melt falls in any one domain require further study. Although the current database is small, the relationship between quartz solubility and the dissolution constant indicate that solubility may be a useful parameter for predicting dissolution rates, particularly if silica activity and melt viscosity are also known.     

Crossover of cation partitioning in olivines: a combination of ab initio and Monte Carlo study

We report studies based on a combination of ab initio electronic structure and Monte Carlo (MC) technique on the problem of cation partitioning among inequivalent octahedral sites, M1 and M2 in mixed olivines containing Mg²⁺ and Fe²⁺ ions. Our MC scheme uses interactions derived out of ab initio, density functional calculations carried out on measured crystal structure data. Our results show that there is no reversal of the preference of Fe for M1 over M2 as a function of temperature. Our findings do not agree with the experimental findings of Redfern et al. (Phys Chem Miner 27:630–637, 2000), but are in agreement with those of Heinemann et al. (Eur J Mineral 18:673–689, 2006) and Morozov et al. (Eur J Mineral 17:495–500, 2005).     

Melting phase relations of a mica–clinopyroxenite from the Milk River area, southern Alberta, Canada

Melting experiments were conducted on a mica–clinopyroxenite xenolith brought up in a minette dyke in southern Alberta, Canada, near Milk River. Both the minettes and mica–clinopyroxenite xenoliths were studied by Buhlmann et al. (Can J Earth Sci 37:1629–1650, 2000), who hypothesized that the minettes formed by partial melting of a mantle source containing clinopyroxene + phlogopite ± olivine, at pressures ≥1.7 GPa. In liquidus experiments performed on the most primitive minette in our previous study (Funk and Luth in Contrib Mineral Petrol 164:999–1009, 2012), we found a multiple saturation point where olivine and orthopyroxene coexisted with liquid at 1.77 GPa and 1,350 °C. We argued that the minette originally formed by partial melting of clinopyroxene + phlogopite, but had re-equilibrated with a harzburgite during ascent. In the current study, we wanted to test both the source region hypothesis of Buhlmann et al. and our re-equilibration hypothesis by studying the near-solidus phase equilibria of a mica + clinopyroxene assemblage. We found the solidus for our xenolith has a steep slope in P–T space and lies at temperatures above those of a normal cratonic geotherm, implying that this mica–clinopyroxenite is stable in the cratonic mantle. Melting could occur at greater depths, where the solidus is extrapolated to cross the geotherm or must be induced either by raising the temperatures of the surrounding rocks or by introducing hydrous fluids into the source. Our melts are in equilibrium with clinopyroxene and olivine. The compositions of the liquids derived from melting this xenolith are similar to madupitic lamproites from the Leucite Hills, Wyoming, studied by Carmichael (Contrib Mineral Petrol 15:24–66, 1967) and Barton and Hamilton (Contrib Mineral Petrol 66:41–49, 1978; Contrib Mineral Petrol 69:133–142, 1979). Barton and Hamilton (Contrib Mineral Petrol 69:133–142, 1979) proposed that the madupitic lamproites may have come from a source containing mica and pyroxene. This study supports their hypothesis. The composition of the most primitive minette from southern Alberta lies between our experimental melt and a population of representative mantle orthopyroxenes. We conclude from our study that the Milk River minettes were likely derived from a source containing phlogopite, clinopyroxene and trace amounts of apatite, which formed olivine upon melting. During ascent, the melts changed composition by reacting with orthopyroxene.     

Reply to the comments on “Xenoliths in ultrapotassic volcanic rocks in the Lhasa block: direct evidence for crust–mantle mixing and metamorphism in the deep crust”

Stepanov et al. (Contrib Mineral Petrol, 2017) question our conclusion that the UPVs in southern Tibet were derived by partial melting of an old, metasomatized subcontinental lithospheric mantle (SCLM) of the subducted Indian plate. Instead, they propose that these ultrapotassic volcanic rocks (UPVs) are shoshonitic and were generated in two steps: direct melting of crustal rocks first, and then the melts interacted with mantle peridotite. However, the trace element, isotopic, thermal, structural, and seismic evidence is consistent with the xenolith evidence (Wang et al in Contrib Mineral Petrol 172:62, 2016) for hybridisation of ascending Indian subcontinental lithospheric mantle-derived UPV magmas with the deep, isotopically unevolved, Tibetan crust. This necessitates a model whereby partial melting of subducting Indian SCLM generates the UPV suite of southern Tibet.     

The geotherm of the lithosphere beneath Qilin, SE China: a re-appraisal and implications for P–T estimation of Fe-rich pyroxenites

The Qilin geotherm established by Xu et al. [Xu, X.S., O'Reilly, S.Y., Zhou, X.M. and Griffin, W.L., 1996. A xenolith-derived geotherm and the crust-mantle boundary at Qilin, southeastern China. Lithos, 38: 41–62.] using the Ellis and Green [Ellis D.J. and Green D.H., 1979. An experimental study of the effect of Ca upon garnet-clinopyroxene Fe-Mg exchange equilibria. Contrib. Mineral. Petrol., 71: 13–22]/Wood [Wood B.J., 1974. Solubility of alumina in orthopyroxene coexisting with garnet. Contrib. Mineral. Petrol. 46: 1-15] combination is in need of revision on the basis of re-evaluation of geothermobarometers, comparison of calculated pressures and temperatures with experimentally determined phase relationships and geological/geophysical data. The invalid assumption that all iron is present as Fe²⁺ in minerals, and the thermal destruction of equilibrium Fe–Mg exchange between clinopyroxene and garnet that may have resulted from heating of the Qilin xenoliths by the host magma resulted in unrealistically high temperatures estimated by the Ellis and Green's thermometer. An important implication arising from this study is that care must be taken when applying thermobarometers to Fe-rich pyroxenites for the purpose of geotherm construction and a comprehensive analysis is often required.     

A comment on: ‘TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz’, by Jay B. Thomas,E. Bruce Watson,Frank S. Spear,Philip T. Shemella,Saroj K. Nayak and Antonio Lanzirotti

Trace concentrations of Ti in quartz are used to indicate the pressure and temperature conditions of crystallization in the ‘TitaniQ’ geothermobarometer of Thomas et al. (Contrib Miner Petrol 160:743–759, 2010). It utilises the partitioning of Ti into quartz as an indicator of the pressures and/or temperatures of crystal growth. For a given value of TiO₂ activity in the system, if temperatures are inferred to ±20 °C, pressure is constrained to ±1 kbar and vice versa. There are significant contrasts, however, between the conclusions from TitaniQ and those for natural quartz (as well as other mineral phases) in volcanic rocks. Application of the TitaniQ model to quartz from the 27 ka Oruanui and 760 ka Bishop high-silica rhyolites, where the values of T, P and TiO₂ activity are constrained by other means (Fe–Ti oxide equilibria, melt inclusion entrapment pressures in gas-saturated melts, melt and amphibole compositions), yields inconsistent results. If realistic values are given to any two of these three parameters, then the value of the third is wholly unrealistic. The model yields growth temperatures at or below the granite solidus, pressures in the lower crust or upper mantle, or TiO₂ activities inconsistent with the mineralogical and chemical compositions of the magmas. CL imagery and measurements of Ti (and other elements) in quartz are of great value in showing the growth histories and changes in conditions experienced by crystals, but direct linkages to P, T conditions during crystal growth cannot be achieved.     

The<Emphasis Type="Italic"> ‘Profile’</Emphasis> method of calculating the composition of solid in magma fractionation,and its application to an alkaline volcano

A new profile mass balance procedure is presented to calculate the chemical composition of solid precipitated during cooling and crystallization of many tholeiitic and alkaline magmas. It is a variant of the earlier interval method (MacLean 2000, Contrib Mineral Petrol 139:85–100), and is also based on chemical variation diagrams of lava sequences (liquid profiles) constructed with a quantitative monitor of fractionation derived from the residual enrichment of an incompatible trace high field-strength element (HFSE). In this new profile method, the concentration of a component in solid is shown by mass transfer considerations to be a function of its mass on a liquid fractionation path (profile) and on a path (profile) of perfect incompatible enrichment. The latter hypothetically contains all of the component, hence subtraction of the amount contained in liquid will yield its mass in the solid. The calculations are straightforward and adaptable to both equilibrium and fractional crystallization processes. Corrections to the fractionation monitor for measured (solid/liquid distribution coefficient), estimates of "trapped liquid" in solid, and other variables, can be applied. The method is illustrated with chemical data for a suite of alkaline volcanic rocks from Mt. Erebus, Antarctica (Kyle et al. 1992, J Petrol 33:849–875). The lavas are silica-undersaturated, and range from nepheline-bearing basanite to phonolite. The solids correspond to those of ultrabasic rocks through most of fractionation, and are more SiO₂-undersaturated than the lavas.Editorial responsibility: I. Parsons