Contrib Mineral Petrol Research Articles

A fundamental dispute: A discussion of “On some fundamentals of igneous petrology” by Bruce D. Marsh, Contributions to Mineralogy and Petrology (2013) 166: 665–690

Marsh (Contrib Miner Petrol 166:665–690, 2013) again claims that crystal-free basalt magmas are unable to differentiate in crustal magma chambers and regards layered intrusions as primarily due to the repeated emplacement of crystal suspensions. He ignores an earlier critique of his unconventional inferences (Latypov, J Petrol 50:1047–1069, 2009) as well as a wealth of petrographic, geochemical and experimental evidence supporting the dominant role of fractional crystallization in the solidification of layered intrusions. Most tellingly, the cryptic variations preserved in the Skaergaard and many other basaltic layered intrusions would require an exceedingly implausible sequence of phenocrystic magmas but are wholly consistent with in situ fractional crystallization. A major flaw in Marsh’s hypothesis is that it dismisses progressive fractional crystallization within any magma chamber and hence prohibits the formation of crystal slurries with phenocrysts and melts that change systematically in composition in any feeder system. This inherent attribute of the hypothesis excludes the formation of layered intrusions anywhere.

Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 2: application to Taupo Volcanic Zone rhyolites

Constraining the pressure of crystallisation of large silicic magma bodies gives important insight into the depth and vertical extent of magmatic plumbing systems; however, it is notably difficult to constrain pressure at the level of detail necessary to understand shallow magmatic systems. In this study, we use the recently developed rhyolite-MELTS geobarometer to constrain the crystallisation pressures of rhyolites from the Taupo Volcanic Zone (TVZ). As sanidine is absent from the studied deposits, we calculate the pressures at which quartz and feldspar are found to be in equilibrium with melt now preserved as glass (the quartz +1 feldspar constraint of Gualda and Ghiorso, Contrib Mineral Petrol 168:1033. doi: 10.1007/s00410-014-1033-3 . 2014). We use glass compositions (matrix glass and melt inclusions) from seven eruptive deposits dated between ~320 and 0.7 ka from four distinct calderas in the central TVZ, and we discuss advantages and limitations of the rhyolite-MELTS geobarometer in comparison with other geobarometers applied to the same eruptive deposits. Overall, there is good agreement with other pressure estimates from the literature (amphibole geobarometry and H2O–CO2 solubility models). One of the main advantages of this new geobarometer is that it can be applied to both matrix glass and melt inclusions—regardless of volatile saturation. The examples presented also emphasise the utility of this method to filter out spurious glass compositions. Pressure estimates obtained with the new rhyolite-MELTS geobarometer range between ~250 to ~50 MPa, with a large majority at ~100 MPa. These results confirm that the TVZ hosts some of the shallowest rhyolitic magma bodies on the planet, resulting from the extensional tectonic regime and thinning of the crust. Distinct populations with different equilibration pressures are also recognised, which is consistent with the idea that multiple batches of eruptible magma can be present in the crust at the same time and can be tapped simultaneously by large eruptive events.

Rare earth element–SiO2 systematics of island arc crustal amphibolite migmatites from the Asago body of the Yakuno Ophiolite, Japan: a field evaluation of some model predictions

The two most commonly invoked processes for generating silicic magmas in intra-oceanic arc environments are extended fractional crystallization of hydrous island arc basalt magma or dehydration melting of lower crustal amphibolite. Brophy (Contrib Mineral Petrol 156:337-357, 2008) has proposed on theoretical grounds that, for liquids >~65 wt% SiO 2 , dehydration melting should yield, among other features, a negative correlation between rare earth ele- ment (REE) abundances and increasing SiO 2 , while frac- tional crystallization should yield a positive correlation. If correct, the REE-SiO 2 systematics of natural systems might be used to distinguish between the two processes. The Per- mian-age Asago body within the Yakuno Ophiolite, Japan, has amphibolite migmatites that contain felsic veins that are believed to have formed from dehydration melting, thus forming an appropriate location for field verification of the proposed REE-SiO 2 systematics for such a process. In addi- tion to a negative correlation between liquid SiO2 and REE abundance for liquids in excess of ~65 % SiO 2 , another important model feature is that, at very high SiO2 contents (75-76 %), all of the REE should have abundances less than

The importance of defining chemical potentials, substitution mechanisms and solubility in trace element diffusion studies: the case of Zr and Hf in olivine

The diffusion, substitution mechanism and solubility limits of Zr and Hf in synthetic forsterite (Mg2SiO4) and San Carlos olivine (Mg0.9Fe0.1)2SiO4 have been investigated between 1,200 and 1,500 °C as a function of the chemical potentials of the components in the system MgO(FeO)–SiO2–ZrO2(HfO2). The effect of oxygen fugacity and crystallographic orientation were also investigated. The solubilities of Zr in forsterite are highest and diffusion fastest when the coexisting three-phase source assemblage includes ZrSiO4 (zircon) or HfSiO4 (hafnon), and lower and slower, respectively, when the source assemblage includes MgO (periclase). This indicates that Zr and Hf substitute on the octahedral sites in olivine, charge balanced by magnesium vacancies. Diffusion is anisotropic, with rates along the crystal axes increasing in the order a < b < c. The generalized diffusion relationship as a function of chemical activity (as \(a_{{{\text{SiO}}_{2} }}\)), orientation and temperature is: \(logD_{\text{Zr}} = \frac{1}{4}loga_{{{\text{SiO}}_{2} }} + logD_{0} - \left( {\frac{{368 \pm 17\;{\text{kJ}}\;{\text{mol}}^{ - 1} }}{{2.303\;{\text{RT}}}}} \right)\) where the values of log D 0 are −3.8(±0.5), −3.4(±0.5) and −3.1(±0.5) along the a, b and c axes, respectively. Most experiments were conducted in air (fO2 = 10−0.68 bars), but one at fO2 = 10−11.2 bars at 1,400 °C shows no resolvable effect of oxygen fugacity on Zr diffusion. Hf is slightly more soluble in olivine than Zr, but diffuses slightly slower. Diffusivities of Zr in experiments in San Carlos olivine at 1,400 °C, fO2 = 10−6.6 bars are similar to those in forsterite at the same conditions, showing that the controls on diffusivities are adequately captured by the simple system (nominally iron-free) experiments. Diffusivities are in good agreement with those measured by Spandler and O’Neill (Contrib Miner Petrol 159:791–818, 2010) in San Carlos olivine using silicate melt as the source at 1,300 °C, and fall within the range of most measurements of Fe–Mg inter-diffusion in olivine at this temperature. Forsterite–melt partitioning experiments in the CaO–MgO–Al2O3–SiO2–ZrO2/HfO2 show that the interface concentrations from the diffusion experiments represent true equilibrium solubilities. Another test of internal consistency is that the ratios of the interface concentrations between experiments buffered by Mg2SiO4 + Mg2Si2O6 + ZrSiO4 or Mg2SiO4 + ZrSiO4 + ZrO2 (high silica activity) to those buffered by Mg2SiO4 + MgO + ZrO2 (low silica activity) agree well with the ratios calculated from thermodynamic data. This study highlights the importance of buffering chemical potentials in diffusion experiments to provide constraints on the interface diffusant concentrations and hence validate the assumption of interface equilibrium.

Amphibole as an archivist of magmatic crystallization conditions: problems, potential, and implications for inferring magma storage prior to the paroxysmal 2010 eruption of Mount Merapi, Indonesia

Amphibole is widely employed to calculate crystallization temperature and pressure, although its potential as a geobarometer has always been debated. Recently, Ridolfi et al. (Contrib Mineral Petrol 160:45–66, 2010) and Ridolfi and Renzulli (Contrib Mineral Petrol 163:877–895, 2012) have presented calibrations for calculating temperature, pressure, fO2, melt H2O, and melt major and minor oxide composition from amphibole with a large compositional range. Using their calibrations, we have (i) calculated crystallization conditions for amphibole from eleven published experimental studies to examine the problems and the potential of the new calibrations; and (ii) calculated crystallization conditions for amphibole from basaltic–andesitic pyroclasts erupted during the paroxysmal 2010 eruption of Mount Merapi in Java, Indonesia, to infer pre-eruptive conditions. Our comparison of experimental and calculated values shows that calculated crystallization temperatures are reasonable estimates. Calculated fO2 and melt SiO2 content yields potentially useful estimates at moderately reduced to moderately oxidized conditions and intermediate to felsic melt compositions. However, calculated crystallization pressure and melt H2O content are untenable estimates that largely reflect compositional variation in the crystallizing magmas and crystallization temperature and not the calculated parameters. Amphibole from Merapi’s pyroclasts yields calculated conditions of ~200–800 MPa, ~900–1,050 °C, ~NNO + 0.3–NNO + 1.1, ~3.7–7.2 wt% melt H2O, and ~58–71 wt% melt SiO2. We interpret the variations in calculated temperature, fO2, and melt SiO2 content as reasonable estimates, but conclude that the large calculated pressure variation for amphibole from Merapi and many other arc volcanoes is evidence for thorough mixing of mafic to felsic magmas and not necessarily evidence for crystallization over a large depth range. In contrast, bimodal pressure estimates obtained for other arc magmas reflect amphibole crystallization from mafic and more evolved magmas, respectively, and should not necessarily be taken as evidence for crystallization in two reservoirs at variable depth.

Oxygen fugacity control in piston-cylinder experiments: a re-evaluation

Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) investigated a double capsule assembly for use in piston-cylinder experiments that would allow hydrous, high-temperature, and high-pressure experiments to be conducted under controlled oxygen fugacity conditions. Using a platinum outer capsule containing a metal oxide oxygen buffer (Ni–NiO or Co–CoO) and H2O, with an inner gold–palladium capsule containing hydrous melt, this study was able to compare the oxygen fugacity imposed by the outer capsule oxygen buffer with an oxygen fugacity estimated by the AuPdFe ternary system calibrated by Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010). H2O loss or gain, as well as iron loss to the capsule walls and carbon contamination, is often observed in piston-cylinder experiments and often go unexplained. Only a few have attempted to actually quantify various aspects of these changes (Brooker et al. in Am Miner 83(9–10):985–994, 1998; Truckenbrodt and Johannes in Am Miner 84:1333–1335, 1999). It was one of the goals of Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) to address these issues by using and testing the AuPdFe solution model of Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010), as well as to constrain the oxygen fugacity of the inner capsule. The oxygen fugacities of the analyzed melts were assumed to be equal to those of the solid Ni–NiO and Co–CoO buffers, which is incorrect since the melts are all undersaturated in H2O and the oxygen fugacities should therefore be lower than that of the buffer by 2 log \(a_{{{\text{H}}_{ 2} {\text{O}}}}\).

High-temperature cooling histories of migmatites from the High Himalayan Crystallines in Sikkim, India: rapid cooling unrelated to exhumation?

The High Himalayan Crystallines (HHCs) provide an excellent natural laboratory to study processes related to crustal melting, crustal differentiation, and the tectonic evolution of mountain belts because partial melting in these rocks occurred under well-defined tectonic boundary conditions (N–S collision of the Indian and the Eurasian plates) and the rocks have not been modified by subsequent metamorphic overprinting. We have used petrogenetic grids, kinetically constrained individual thermobarometry, pseudosection calculations, and reaction histories constrained by textural evidence to determine that the migmatites in the HHC of Sikkim attained peak P–T conditions of 750–800 °C, 9–12 kbar, followed by steep isothermal decompression to 3–5 kbar, and then isobaric cooling to ~600 °C. There may be a trend where rocks to the north [closer to the South Tibetan detachment system (STDS)] attained somewhat higher maximum pressures. The decompression may have been triggered by a reduction in density due to the production of melt (~20 vol%); minor amounts of additional melt may have been produced in individual packages of rock during decompression itself, depending on the exact geometry of the P–T path and the bulk composition of the rock. The stalling of rapid, isothermal exhumation at depths of 10–18 km (3–5 kbar) is related to metamorphic reactions that occur in these rocks. Geospeedometry indicates that at least a two-stage cooling history is required to describe the compositional zoning in all garnets. Both of these stages are rapid (several 100’s °C/my between 800 and 600 °C, followed by several 10’s °C/my between 600 and 500 °C), but there appears to be a spatial discontinuity in cooling history: Rocks to the south (closer to main central thrust) cooled more slowly than rocks to the north (closer to STDS). The boundary between these domains coincides with the discontinuity in age found in the same area by Rubatto et al. (Contrib Mineral Petrol 165:349–372, 2013). Combined with the information on petrologic phase relations, the data reveal the remarkable aspect that the rapid cooling and change of cooling rates all occurred after, rather than during, the rapid exhumation. This result underscores that high-temperature (e.g., >550 °C) cooling is a result of several processes in addition to exhumation and a one-to-one correlation of cooling and exhumation may sometimes be misplaced. Moreover, average cooling rates inferred from the closure temperatures of two isotopic systems should be interpreted judiciously in such nonlinearly cooling systems. While many aspects (e.g., isothermal decompression, isobaric cooling, duration of metamorphism, and cooling rates) of the pressure–temperature history inferred by us are consistent with the predictions of thermomechanical models that produce midcrustal channel flow, the occurrence of blocks with two different cooling histories within the HHC is not explained by currently available models. It is found that while exhumation may be initiated by surface processes such as erosion, the course of exhumation and its rate, at least below depths of ~15 km, is mostly controlled by a coupling between mechanical (density gain/loss) and chemical (metamorphic reactions) processes at depth.

Extended planar defects and the rapid incorporation of Ti4+ into olivine

The formation of extended planar defects in minerals such as olivine is related to high point defect concentration and can be driven by large gradients in chemical potential, where the energy of the system is lowered by the ordering of defects along specific planes in the crystal. The presence of extended defects has the potential to create the (apparently) anomalous ionic diffusion in olivine as reported recently (Spandler and O’Neill in Contrib Mineral Petrol 159(6):791–818, 2010). High-resolution transmission electron microscopy and energy-filtered imaging were done using experimental samples designed to examine the impact of a TiO2 and f O2 on the potential to form such defects in ferromagnesian olivine. Doped basalt (5 wt% TiO2)–olivine reaction couple experiments were run at 1 atm and 1,310 and 1,410 °C for 50 h at various f O2, ranging from 102 below to 102 above the quartz–fayalite–magnetite buffer. Our results show that extended planar defects in olivine, parallel to {101}ol and occurring in ordered “clusters” with a prolate spheroid geometry ~5–25 nm across and extending up to 150 nm into the olivine, are present near the olivine–glass interfaces in all of our experimental high-TiO2 basalt–olivine samples. Increased Ti content in the olivine is associated with the defects; ordering of Ti4+ and octahedral site vacancies leads to a two- or three-layer superstructure in the olivine. Defect nucleation and growth is driven by the large TiO2 chemical potential gradient across the phase boundary at the start of the experiments, which provides access to microstructures not otherwise present.

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.

An experimental study of the Fe oxidation states in garnet and clinopyroxene as a function of temperature in the system CaO–FeO–Fe2O3–MgO–Al2O3–SiO2: implications for garnet–clinopyroxene geothermometry

Samples with eclogitic composition in the system CaO–FeO–Fe2O3–MgO–Al2O3–SiO2 were produced from various kinds of starting materials held in graphite-lined Pt capsules at a pressure of 2.5–3.0 GPa and temperatures of 800–1,300 °C using a piston-cylinder or Belt apparatus. Garnets and clinopyroxenes were characterized by analytical transmission electron microscopy and electron probe micro-analysis (EPMA). Fe3+/ΣFe ratios determined by electron energy-loss spectroscopy (EELS) decrease in clinopyroxene from 22.2 ± 3.4 % at 800 °C to 13.3 ± 5.4 % at 1,300 °C, while in garnet, they vary between 10.8 ± 1.5 and 15.4 ± 4.7 %, respectively. Temperature estimates according to Krogh (Contrib Mineral Petrol 99:44–48, 1988) reproduce the experimental temperature to ±60 °C without systematic deviations if total iron is used in the calculation. If only the Fe2+ content is used, which was obtained by combining EPMA and EELS results, the experimental temperature is underestimated by 33 °C on average at 800–1,200 °C and overestimated by 77 °C on average at 1,300 °C. These systematic deviations can be explained by the temperature-dependent ratio of Fe2+/ΣFe in garnet divided by that in clinopyroxene. Since the difference between the calculated and experimental temperature is relatively small, a Fe2+-based recalibration of the thermometer appears not to be necessary for the investigated system in the range of pressure, temperature and composition covered by the experiments of this study.

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).

A method for estimating the activity of titania in magmatic liquids from the compositions of coexisting rhombohedral and cubic iron–titanium oxides

A method is described for estimating the activity of titania (TiO2) in a magmatic liquid from the compositions of coexisting cubic oxide (spinel) and rhombohedral oxide (ilmenite). These estimates are derived from the thermodynamic models of Ghiorso and Evans (Am J Sci 308:957–1039, 2008; see also Sack and Ghiorso in Contrib Mineral Petrol 106:474–505, 1991a; Am Mineral 76:827-847, 1991b) and may be computed self consistently along with temperature and oxygen fugacity for an assumed pressure. The method is applied to a collection of 729 naturally occurring oxide pairs from rhyolites and dacites. For this suite of oxides, values of titania activity relative to rutile saturation range from 0.3 to 0.9. Genetically related groups of oxide pairs display activity–temperature trends with negative slopes at higher activities (0.6–0.9) or positive slopes at lower activities (0.3–0.7). Thermodynamic analysis supports the assumption of two-oxide, liquid equilibrium for the former group, but suggests that such an interpretation for oxide sequences with positive activity–temperature trends may be problematic. Application of the estimation method to oxide pairs from the Shiveluch Volcano and the Bishop Tuff reveals that the former are consistent with having equilibrated with known matrix glass compositions, whereas the latter pairs are inconsistent with equilibration with pre-eruptive liquids trapped in quartz inclusions.

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 δ18Ool (~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 δ18Ool 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 δ18Ool 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 δ18Ool is weakly correlated (R2 = 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 δ18Ool 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 δ18Oolivine 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 ‰.

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.

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 (\( a_{{{\text{TiO}}_{ 2} }} \) (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 \( a_{{{\text{TiO}}_{ 2} }} \) 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 \( a_{{{\text{TiO}}_{ 2} }} \) (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.

Amphibole stability in primitive arc magmas: effects of temperature, H2O content, and oxygen fugacity

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).

Rare earth element–SiO2 systematics of mid-ocean ridge plagiogranites and host gabbros from the Fournier oceanic fragment, New Brunswick, Canada: a field evaluation of some model predictions

The two most commonly invoked processes for generating plagiogranites in mid-ocean ridge environments are extended fractional crystallization of mid-ocean ridge basalt (MORB) magma and “hydration melting” of hot, dry MOR gabbro initiated by the influx of seawater-derived hydrothermal fluids within localized zones of shear. Brophy (Contrib Mineral Petrol 158:99–111, 2009) has proposed on theoretical grounds that, for liquids greater than ~62 wt. % SiO2, hydration melting should yield, among other features, a negative correlation between rare earth element (REE) abundances and increasing SiO2, while fractional crystallization should yield a positive correlation. If correct, the REE–SiO2 systematics of natural systems might be used to distinguish between the two processes. The Ordovician Fournier oceanic fragment, New Brunswick, Canada, contains MOR gabbro-hosted plagiogranite veins and dikes that are believed to have formed from hydration melting, thus forming an appropriate location for field verification of the proposed REE–SiO2 systematics for such a process. In addition to a negative correlation between liquid SiO2 and REE abundance for liquids in excess of ~62% SiO2, other important model features include the following: (1) relative to a gabbro source rock, the degree of enrichment at liquids of 62 and 75% SiO2 decreases from the LREE to the HREE; (2) the degree of enrichment at 75% SiO2 approaches 1 for the HREE; (3) the rate of change of the degree of enrichment with increasing liquid SiO2 (i.e., the slope) diminishes from the LREE to the HREE. All of these predicted features are observed in the Fournier plagiogranites. Assuming an initial source rock equivalent to the host gabbro, an additional strongly LREE-enriched component must be added prior to melting in order to make the absolute REE abundances agree with the model values. The most likely candidates are the very seawater-derived hydrothermal fluids that triggered hydration melting in the first place.

Growth of multilayered polycrystalline reaction rims in the MgO–SiO2 system, part II: modelling

Part I of this contribution (Gardes et al. in Contrib Mineral Petrol, 2010) reported time- and temperature-dependent experimental growth of polycrystalline forsterite-enstatite double layers between single crystals of periclase and quartz, and enstatite single layers between forsterite and quartz. Both double and single layers displayed growth rates decreasing with time and pronounced grain coarsening. Here, a model is presented for the growth of the layers that couples grain boundary diffusion and grain coarsening to interpret the drop of the growth rates. It results that the growth of the layers is such that (Δx)2 ∝ t1−1/n, where Δx is the layer thickness and n the grain coarsening exponent, as experimentally observed. It is shown that component transport occurs mainly by grain boundary diffusion and that the contribution of volume diffusion is negligible. Assuming a value of 1 nm for the effective grain boundary width, the following Arrhenius laws for MgO grain boundary diffusion are derived: log Dgb,0Fo (m2/s) = −2.71 ± 1.03 and EgbFo = 329 ± 30 kJ/mol in forsterite and log Dgb,0En (m2/s) = 0.13 ± 1.31 and EgbEn = 417 ± 38 kJ/mol in enstatite. The different activation energies are responsible for the changes in the enstatite/forsterite thickness ratio with varying temperature. We show that significant biases are introduced if grain boundary diffusion-controlled rim growth is modelled assuming constant bulk diffusivities so that differences in activation energies of more than 100 kJ/mol may arise. It is thus important to consider grain coarsening when modelling layered reaction zones because they are usually polycrystalline and controlled by grain boundary transport.

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.