Internally consistent geothermometers for garnet peridotites and pyroxenites

Mutual relationships among temperatures estimated with the most widely used geothermometers for garnet peridotites and pyroxenites demonstrate that the methods are not internally consistent and may diverge by over 200°C even in well-equilibrated mantle xenoliths. The Taylor (N Jb Min Abh 172:381–408, 1998) two-pyroxene (TA98) and the Nimis and Taylor (Contrib Mineral Petrol 139:541–554, 2000) single-clinopyroxene thermometers are shown to provide the most reliable estimates, as they reproduce the temperatures of experiments in a variety of simple and natural peridotitic systems. Discrepancies between these two thermometers are negligible in applications to a wide variety of natural samples (≤30°C). The Brey and Köhler (J Petrol 31:1353–1378, 1990) Ca-in-Opx thermometer shows good agreement with TA98 in the range 1,000–1,400°C and a positive bias at lower T (up to +90°C, on average, at T _TA98 = 700°C). The popular Brey and Köhler (J Petrol 31:1353–1378, 1990) two-pyroxene thermometer performs well on clinopyroxene with Na contents of ~0.05 atoms per 6-oxygen formula, but shows a systematic positive bias with increasing Na_Cpx (+150°C at Na_Cpx = 0.25). Among Fe–Mg exchange thermometers, the Harley (Contrib Mineral Petrol 86:359–373, 1984) orthopyroxene–garnet and the recent Wu and Zhao (J Metamorphic Geol 25:497–505, 2007) olivine–garnet formulations show the highest precision, but systematically diverge (up to ca. 150°C, on average) from TA98 estimates at T far from 1,100°C and at T < 1,200°C, respectively; these systematic errors are also evident by comparison with experimental data for natural peridotite systems. The older O’Neill and Wood (Contrib Mineral Petrol 70:59–70, 1979) version of the olivine–garnet Fe–Mg thermometer and all popular versions of the clinopyroxene–garnet Fe–Mg thermometer show unacceptably low precision, with discrepancies exceeding 200°C when compared to TA98 results for well-equilibrated xenoliths. Empirical correction to the Brey and Köhler (J Petrol 31:1353–1378, 1990) Ca-in-Opx thermometer and recalibration of the orthopyroxene–garnet thermometer, using well-equilibrated mantle xenoliths and TA98 temperatures as calibrants, are provided in this study to ensure consistency with TA98 estimates in the range 700–1,400°C. Observed discrepancies between the new orthopyroxene–garnet thermometer and TA98 for some localities can be interpreted in the light of orthopyroxene–garnet Fe³⁺ partitioning systematics and suggest localized and lateral variations in mantle redox conditions, in broad agreement with existing oxybarometric data. Kinetic decoupling of Ca–Mg and Fe–Mg exchange equilibria caused by transient heating appears to be common, but not ubiquitous, near the base of the lithosphere.     

Zr-in-rutile thermometry in HP/UHP eclogites from Western China

Four Zr-in-rutile thermometry calibrations are applied to eclogites from Western China. Here, we show that if rutile grows in equilibrium with Qtz and Zrn, and is isolated inside garnet, it preserves its Zr composition and does not undergo compositional change due to cation exchange with the host garnet. It thus preserves the composition for the P–T conditions of its formation and the growth zoning of the host garnet. For the HP/UHP metamorphic temperature, the Tomkins et al. (J Metamorph Geol 25:703–713, 2007) calibration yields temperatures that agree well with previous studies, whereas the other three calibrations (Zack et al. in Contrib Mineral Petrol 148:471–488, 2004; Watson et al. in Contrib Mineral Petrol 151:413–433, 2006; Ferry and Watson in Contrib Mineral Petrol in 154:429–437, 2007), which do not include a pressure correction, give systematically lower temperatures. Zr contents of rutile inclusions within garnet show systematic decrease from garnet core to rim. The rutile inclusions in garnet rims contain the lowest Zr content, similar to that in the matrix. Analyses confirm that the pressure plays a significant role in modifying the primary temperature dependence of the Zr content of rutile. Rutiles trapped in garnets are unable to re-equilibrate easily during retrogression, but those in the matrix can do so, providing retrograde P–T path information.     

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.     

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).     

Mesozoic thermal evolution of the southern African mantle lithosphere

The thermal structure of Archean and Proterozoic lithospheric terranes in southern Africa during the Mesozoic was evaluated by thermobarometry of mantle peridotite xenoliths erupted in alkaline magmas between 180 and 60 Ma. For cratonic xenoliths, the presence of a 150–200 °C isobaric temperature range at 5–6 GPa confirms original interpretations of a conductive geotherm, which is perturbed at depth, and therefore does not record steady state lithospheric mantle structure.

Xenoliths from both Archean and Proterozoic terranes record conductive limb temperatures characteristic of a “cratonic” geotherm (40 mW m⁻²), indicating cooling of Proterozoic mantle following the last major tectonothermal event in the region at 1 Ga and the probability of thick off-craton lithosphere capable of hosting diamond. This inference is supported by U–Pb thermochronology of lower crustal xenoliths [Schmitz and Bowring, 2003. Contrib. Mineral. Petrol. 144, 592–618].

The entire region then suffered a protracted regional heating event in the Mesozoic, affecting both mantle and lower crust. In the mantle, the event is recorded at 150 Ma to the southeast of the craton, propagating to the west by 108–74 Ma, the craton interior by 85–90 Ma and the far southwest and northwest by 65–70 Ma. The heating penetrated to shallower levels in the off-craton areas than on the craton, and is more apparent on the southern margin of the craton than in its western interior. The focus and spatial progression mimic inferred patterns of plume activity and supercontinent breakup 30–100 Ma earlier and are probably connected.

Contrasting thermal profiles from Archean and Proterozoic mantle result from penetration to shallower levels of the Proterozoic lithosphere by heat transporting magmas. Extent of penetration is related not to original lithospheric thickness, but to its more fertile character and the presence of structurally weak zones of old tectonism. The present day distribution of surface heat flow in southern Africa is related to this dynamic event and is not a direct reflection of the pre-existing lithospheric architecture.     

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).     

Megacrysts from the Grib kimberlite pipe (Arkhangelsk Province, Russia)

The megacryst suite of the Grib kimberlite pipe (Arkhangelsk province, Russia) comprises garnet, clinopyroxene, magnesian ilmenite, phlogopite and garnet-clinopyroxene intergrowths. Crystalline inclusions, mainly of clinopyroxene and picroilmenite, occur in garnet megacrysts. Ilmenite is characterized by a wide range in the contents of MgO (10.6–15.5 wt.%) and Cr₂O₃ (0.7–8.3 wt.%). Megacryst garnets show wide variations in Cr₂O₃ (1.3–9.6 wt.%) and CaO (3.6–11.0 wt.%) but relatively constant MgO (15.4–22.3 wt.%) and FeO (5.2–9.9 wt.%). The pyroxenes also show wide variations in such oxides as Cr₂O₃, Al₂O₃ and Na₂O (0.56–2.95; 0.86–3.25; 1.3–3.0 wt.%, respectively). The high magnesium and chromium content of all these minerals puts them together in one paragenetic group. This conclusion was confirmed by studies of the crystalline inclusions in megacrysts, which demonstrate similar variations in composition. Low concentration of hematite in ilmenite suggests reducing conditions during crystallization. P–T estimates based on the clinopyroxene geothermobarometer (Contrib. Mineral. Petrol. 139 (2000) 541) show wide variations (624–1208 °C and 28.8–68.0 kbars), corresponding to a 40–45 mW/m² conductive geotherm. The majority of Gar-Cpx intergrowths differ from the corresponding monomineralic megacrysts in having higher Mg contents and relatively low TiO₂. The minerals from the megacryst association, as a rule, differ from the minerals of mantle xenoliths, but garnets in ilmenite-bearing peridotite xenoliths are compositionally similar to garnet megacrysts. The common features of trace element composition of megacryst minerals and kimberlite (they are poor in Zr group elements) suggest a genetic relationship. The origin of the megacrysts is proposed to be genetically connected with kimberlite magma-chamber evolution on the one hand and with associated mantle metasomatism on the other. We suggest that, depending on the primary melt composition, different paragenetic associations of macro/megacrysts can be crystallized in kimberlites. They include: (1) Fe–Ti (Mir, Udachnaya pipes); (2) high-Mg, Cr (Zagadochna, Kusova pipes); (3) high-Mg, Cr, Ti (Grib pipe).     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.     

Assessment of the garnet–clinopyroxene Fe–Mg exchange thermometer using new experimental data

A detailed high-pressure experimental study of two mafic xenoliths, in which coexisting garnet and clinopyroxene (± plagioclase, spinel and olivine) were crystallized over a P–T range of 10–30 kbar and 950–1200°C, has revealed significant differences in temperatures from those estimated for coexisting garnets and clinopyroxenes using the Ellis & Green Fe–Mg exchange thermometer. The results show perfect matching at 30 kbar, 1150–1200°C, but increasing deviation at lower pressure and lower temperature, with the Ellis & Green calibration reaching a Δ T (overestimate) of c. 145°C at 10–12 kbar and 950°C. The grossular content of the garnet increases from c. 21 mol.% at 10 kbar to 26–31 mol.% at 30 kbar. These results confirm other recent experimental studies that show that the pressure correction, and possibly to a lesser extent the correction for grossular content, applied by Ellis & Green, are not appropriate for lower pressure conditions, and give estimated temperatures that are significantly high when applied to granulitic terranes formed at c. 10 kbar. The new reconnaissance results allow a graphical interpolation of a garnet–clinopyroxene geothermometer based on the Fe–Mg exchange reaction which should be applicable to assemblages formed under lower crustal conditions.     

Diamonds and their mineral inclusions from the A154 South pipe, Diavik Diamond Mine, Northwest territories, Canada

Mineral inclusions recovered from 100 diamonds from the A154 South kimberlite (Diavik Diamond Mines, Central Slave Craton, Canada) indicate largely peridotitic diamond sources (83%), with a minor (12%) eclogitic component. Inclusions of ferropericlase (4%) and diamond in diamond (1%) represent “undetermined” parageneses.

Compared to inclusions in diamonds from the Kaapvaal Craton, overall higher CaO contents (2.6 to 6.0 wt.%) of harzburgitic garnets and lower Mg-numbers (90.6 to 93.6) of olivines indicate diamond formation in a chemically less depleted environment. Peridotitic diamonds at A154 South formed in an exceptionally Zn-rich environment, with olivine inclusions containing more than twice the value (of  52 ppm) established for normal mantle olivine. Harzburgitic garnet inclusions generally have sinusoidal rare earth element (REE_N) patterns, enriched in LREE and depleted in HREE. A single analyzed lherzolitic garnet is re-enriched in middle to heavy REE resulting in a “normal” REE_N pattern. Two of the harzburgitic garnets have “transitional” REE_N patterns, broadly similar to that of the lherzolitic garnet. Eclogitic garnet inclusions have normal REE_N patterns similar to eclogitic garnets worldwide but at lower REE concentrations.

Carbon isotopic values (δ¹³C) range from − 10.5‰ to + 0.7‰, with 94% of diamonds falling between − 6.3‰ and − 4.0‰. Nitrogen concentrations range from below detection (< 10 ppm) to 3800 ppm and aggregation states cover the entire spectrum from poorly aggregated (Type IaA) to fully aggregated (Type IaB). Diamonds without evidence of previous plastic deformation (which may have accelerated nitrogen aggregation) typically have < 25% of their nitrogen in the fully aggregated B-centres. Assuming diamond formation beneath the Central Slave to have occurred in the Archean [Westerlund, K.J., Shirey, S.B., Richardson, S.H., Gurney, J.J., Harris, J.W., 2003b. Re–Os systematics of diamond inclusion sulfides from the Panda kimberlite, Slave craton. VIIIth International Kimberlite Conference, Victoria, Canada, Extended Abstracts, 5p.], such low aggregation states indicate mantle residence at fairly low temperatures (< 1100 °C). Geothermometry based on non-touching inclusion pairs, however, indicates diamond formation at temperatures around 1200 °C. To reconcile inclusion and nitrogen based temperature estimates, cooling by about 100–200 °C shortly after diamond formation is required.     

The influence of Fe<Superscript>3+</Superscript> on garnet–orthopyroxene and garnet–olivine geothermometers

Applying Fe²⁺–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe³⁺ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO₂ buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe³⁺/Fe²⁺ ratios were generated. The Fe³⁺ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fe_total = Fe²⁺, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe²⁺–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe³⁺ in garnet (i.e. using only measured Fe²⁺) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe³⁺ whilst direct accounting of Fe³⁺ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers.     

Garnet lherzolites from Somerset Island,Canada and aspects of the nature of perturbed geotherms

Garnet lherzolite xenoliths of similar petrography and mineralogy are found in the Elwin Bay, Nanorluk, and Amayersuk kimberlites. The xenoliths are either coarse equant to coarse tabular or porphyroclastic in texture. Compositions of coexisting pyroxenes indicates equilibration at 1000–1270° C at 34–41 kb (Wood-Banno/Wood method) or 865–1200° C at 29–36 kb (Wells/Wood method). No simple correlation exists between textural types and equilibration temperature. A primary spinel-bearing garnet lherzolite has equilibrated at 840° C at 21 kb (Wells/Wood) and provides the only known example of a xenolith with relatively high Cr/Cr+Al which has equilibrated at the spinel to garnet lherzolite transition along the continental geotherm. The pressure and temperature estimates for the xenoliths lie above those of the steady state geotherm and indicate that a perturbed geotherm existed in this region at the time of kimberlite intrusion. The formation of perturbed geotherms is discussed and it is considered that the upper high temperature limbs of inflected geotherms are transient pseudogeotherms generated in response to a thermal aureole about a rising mantle diapir and that the lherzolites which define such a geotherm represent a telescoped section of the mantle and include xenoliths derived from above and below the point of kimberlite liquid segregation. The lower temperature limbs of inflected geotherms are considered to be representative of the steady state geotherm and are sampled by the kimberlite which after segregation from the diapir rises at a much faster rate than the parent diapir and passes through material which is unaffected by the diapir thermal aureole.     

Exsolution textures in orthopyroxene in aluminous granulites as indicators of UHT metamorphism: New evidence from the Eastern Ghats Belt, India

Highly aluminous orthopyroxene, coexisting with sapphirine, cordierite, sillimanite, quartz and garnet in various combinations, constitute granoblastic mosaic peak metamorphic assemblages in aluminous granulites from three localities in the Eastern Ghats Belt, India. Orthopyroxene contains four types of intergrowths: (a) involving sapphirine with or without cordierite, (b) involving spinel, but without sapphirine, (c) involving cordierite, but without sapphirine and spinel, and (d) involving garnet, without sapphirine, spinel or cordierite. On the basis of textural and compositional data, origin of the intergrowths is ascribed to breakdown of Mg-Tschermak component, locally also involving Fe- and Ti-Tschermak. An attempt is made to compute the “pre-breakdown” compositions of orthopyroxene by image analysis, which shows maximum Al₂O₃ content of 13.4 wt.% in the pristine orthopyroxene. Geothermometry, phase equilibria consideration and application of existing experimental data on alumina solubility in orthopyroxene coexisting with sapphirine and quartz, collectively indicate extreme thermal conditions of metamorphism (> 1000 °C) for the studied assemblages. This re-affirms the notion that Al₂O₃ solubility in orthopyroxene is the most powerful indicator of UHT metamorphism (Harley, S.L., 2004. Extending our understanding of ultrahigh temperature crustal metamorphism. J. Mineral. Petrol. Sci. 99, 140–158). The intergrowths are considered to have formed due to cooling from the thermal peak spanning a temperature range of approximately 150 °C. Appearance of diverse types of intergrowths is probably related to subtle differences in bulk composition, particularly Fe:Mg ratios.     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

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.     

Analysis of experimental data on divalent cation diffusion kinetics in aluminosilicate garnets with application to timescales of peak Barrovian metamorphism,Scotland

We present a new statistical framework to analyze the diffusion data for divalent cations (Fe, Mg, Mn, and Ca) in aluminosilicate garnet using published experimental data and an Arrhenius relationship that accounts for dependence on temperature, pressure, garnet unit-cell dimension, and oxygen fugacity. The regression is based on Bayesian statistics and is implemented by the Markov chain Monte Carlo approach. All reported experimental uncertainties are incorporated, and the data are weighted by the precision of the experimental conditions. We also include a new term, the inter-experiment bias, to compensate for possible inconsistencies among experiments and to represent any experimental variability not explicitly presented in the Arrhenius relationship (e.g., water content, defect density). At high temperatures where most experiments were conducted, the diffusion coefficients calculated with the new parameters agree well with previous diffusion models (e.g., Chakraborty and Ganguly in Contrib Mineral Petrol, 111:74–86, 1992; Carlson in Am Mineral, 91:1–11, 2006). However, the down-temperature extrapolation leads to notable differences at lower temperatures for common petrological applications. For example, at 600 °C, the diffusion coefficients of Fe and Mn are one half-to-one order of magnitude faster and the diffusion coefficient of Ca is about one order of magnitude slower than calculated with parameters in Carlson (2006). Our statistical analysis also provides well-defined uncertainty bounds for timescale estimates based on garnet diffusion profiles. Application of the newly derived coefficients indicates that the timescale of the thermal peak of Barrovian metamorphism (Dalradian belt of Scotland) is about four to seven times longer than that estimated using previously published diffusion coefficients. The peak is still geologically brief, however—of the order of 10⁶ years (0.75 Myr +0.70/?0.36 Myr; ±1σ). This brevity requires pulsed advective heat input, as provided by syn-orogenic mafic magmatism in these rocks.     

Crustal contamination and crystal entrapment during polybaric magma evolution at Mt. Somma–Vesuvius volcano, Italy: Geochemical and Sr isotope evidence

New major and trace element analyses and Sr-isotope determinations of rocks from Mt. Somma–Vesuvius volcano produced from 25 ky BP to 1944 AD are part of an extensive database documenting the geochemical evolution of this classic region. Volcanic rocks include silica undersaturated, potassic and ultrapotassic lavas and tephras characterized by variable mineralogy and different crystal abundance, as well as by wide ranges of trace element contents and a wide span of initial Sr-isotopic compositions. Both the degree of undersaturation in silica and the crystal content increase through time, being higher in rocks produced after the eruption at 472 AD (Pollena eruption). Compositional variations have been generally thought to reflect contributions from diverse types of mantle and crust. Magma mixing is commonly invoked as a fundamental process affecting the magmas, in addition to crystal fractionation. Our assessment of geochemical and Sr-isotopic data indicates that compositional variability also reflects the influence of crustal contamination during magma evolution during upward migration to shallow crustal levels and/or by entrapment of crystal mush generated during previous magma storage in the crust. Using a variant of the assimilation fractional crystallization model (Energy Conservation–Assimilation Fractional Crystallization; [Spera and Bohrson, 2001. Energy-constrained open-system magmatic processes I: General model and energy-constrained assimilation and fractional crystallization (EC–AFC) formulation. J. Petrol. 999–1018]; [Bohrson, W.A. and Spera, F.J., 2001. Energy-constrained open-system magmatic process II: application of energy-constrained assimilation–fractional crystallization (EC–AFC) model to magmatic systems. J. Petrol. 1019–1041]) we estimated the contributions from the crust and suggest that contamination by carbonate rocks that underlie the volcano (2 km down to 9–10 km) is a fundamental process controlling magma compositions at Mt. Somma–Vesuvius in the last 8 ky BP. Contamination in the mid- to upper crust occurred repeatedly, after the magma chamber waxed with influx of new mantle- and crustal-derived magmas and fluids, and waned as a result of magma withdrawal and production of large and energetic plinian and subplinian eruptions.     

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 ‰.     

The garnet-clinopyroxene Fe-Mg geothermometer — a reinterpretation of existing experimental data

Experimental data on the partitioning of Fe²⁺ and Mg between garnet and clinopyroxene (Råheim and Green 1974; Mori and Green 1978; Ellis and Green 1979) have been used to construct a new expression for the garnet-clinopyroxene geothermometer, including a curvilinear relationship between In Kd and X _Ca(ga): T(°C)=((-6173(X_Ca)²+6731 X _Ca+1879 +10 P(kb))/(lnKd+1.393))–273Application of this geothermometer to a suite of samples of eclogites and associated omphacite-garnet-bearing gneisses from the uppermost allochthon within the North Norwegian Caledonides shows that the calculated temperatures do not vary with rather great variations in the mg number of the garnet (0.17–0.54) and Na content of the clinopyroxene (0.11–0.44). Temperatures below 900° C calculated using the present equation are somewhat lower than those obtained by the method of Powell (1985), the difference being larger for lower temperatures and lower values of X _Ca.