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.     

Timing of high-pressure metamorphic events in the Bulgarian Rhodopes from Lu–Hf garnet geochronology

Within the Mediterranean realm, the Rhodopes represent a nappe stack of oceanic and continental fragments assembled along the Eurasian continental margin during the Alpine orogeny. The timing of the high-pressure (HP) metamorphism has long been ambiguous, lacking detailed geochronological and geochemical control on subduction-exhumation and nappe stacking processes. Here we apply the Lu–Hf and Sm–Nd chronometers to a suite of representative eclogite samples covering two different key units of the Rhodopean nappe stack: (1) the Kimi Complex (Upper Allochthon) and (2) the Middle Allochthon. In addition to geochronology, we also determined whole rock Hf and Nd isotope compositions as well as major and trace element concentrations in order to constrain the nature of the eclogite protoliths. Two HP metamorphic events were revealed by Lu–Hf geochronology: (1) a Lower Cretaceous event in the Upper Allochthon (126.0 ± 1.7 Ma) and (2) an Eocene event in the Middle Allochthon (44.6 ± 0.7 Ma; 43.5 ± 0.4 Ma; 42.8 ± 0.5 Ma), at conditions of ca. 700°C/20–25 kbar. Our new data provide direct evidence for multiple subduction events in the Rhodopes. Exhumation and subsequent thrusting of the Middle Allochthon on the Lower Allochthon can be narrowed down to the time span between 42 and 34 Ma. In a broader tectonic context, the Eocene ages for the HP metamorphism support the view that the Rhodopes represent a large-scale tectonic window, exposing the deepest nappe units of the Hellenides.     

Reconstruction of the metamorphic <Emphasis Type="Italic">P–T</Emphasis> path from the garnet zoning in aluminous schists from the Tsogt Block,Mongolian Altai

The paper presents original authors’ data on aluminous schists in the Tsogt tectonic plate in the Southern Altai Metamorphic Belt. The nappe includes a medium-temperature/medium-pressure zonal metamorphic complex, whose metamorphic grade varies from the greenschist to epidote-amphibolite facies. The garnet and garnet–staurolite schists contain three garnet generations of different composition and morphology. The P–T metamorphic parameters estimated by mineralogical geothermometers and geobarometers and by numerical modeling with the PERPLEX 668 software provide evidence of two successive metamorphic episodes: high-gradient (of the andalusite–sillimanite type, geothermal gradient approximately 40–50°/km) and low-gradient (kyanite–sillimanite type, geothermal gradient approximately 27°/km). The P-T parameters of the older episode are T = 545–575°C and P = 3.1–3.7 kbar. Metamorphism during the younger episode was zonal, and its peak parameters were T = 560–565°C, P = 6.4–7.2 kbar for the garnet zone and T = 585–615°C, P = 7.1–7.8 kbar for the staurolite zone. The metamorphism evolved according to a clockwise P–T path: the pressure increased during the first episode at a practically constant temperature, and then during the second episode, the temperature increased at a nearly constant pressure. Such trends are typical of metamorphism related to collisional tectonic settings and may be explained by crustal thickening due to overthrusting. The regional crustal thickening reached at least 15–18 km.     

Ultrahigh-temperature metamorphism followed by two-stage decompression of garnet–orthopyroxene–sillimanite granulites from Ganguvarpatti,Madurai block,southern India

The Mg–Al granulites from Ganguvarpatti consist of orthopyroxene–sillimanite–garnet ± quartz as peak assemblage, with a few porphyroblasts of cordierite and sapphirine. These assemblages were strongly overprinted by late symplectites and coronas. Orthopyroxene inclusions in garnet and porphyroblast cores have the highest X _Mg (0.80) and Al₂O₃ content (10.7 wt%). The estimated near-peak metamorphic conditions (1,000±50°C and 11 kbar) using garnet–orthopyroxene geothermobarometry are consistent with those determined using a petrogenetic grid. The proposed multi-stage evolution process implies an initial decompression, deduced from multi-phase symplectites, followed by cooling during biotite formation. Further late decompression is explained from the orthopyroxene rims on biotite. This proposed P–T path thus suggests a unique and complex evolution history for the UHT granulites of southern India. Present results are comparable with similar adjacent terranes in the Gondwana supercontinent, but the lack of structural and geochronological data makes a link with any major metamorphic event uncertain.     

The P–T–t paths of high-grade gneisses,Kaoko Belt,Namibia: Constraints from mineral data,U–Pb allanite and monazite and Sm–Nd/Lu–Hf garnet ages and garnet ion probe data

The Damara Orogeny is a late Neoproterozoic to Cambrian (ca. 570–480 Ma) intracratonic event that affected the Kaoko Belt, the inland branch of the Damara orogen and the Gariep Belt in Namibia and South Africa. This study focuses on the Pan-African evolution of part of the Kaoko Belt between the Puros shear zone and the Village mylonite zone which consists of Mesoproterozoic migmatitic para- and orthogneisses with minor granulite and amphibolite. Pseudosection modeling combined with thermobarometric calculations indicate that the para- and orthogneisses equilibrated at about 670–800 °C and ca. 0.6–0.8 GPa. Some garnets display a pronounced bell-shaped Ca, HREE, Y and Sr zoning, flat zoning profiles of Mn and Fe and concave upward concentration profiles of Sm and Nd. Pressure–temperature estimates obtained on these garnets reveal similar temperatures of 700–750 °C but slightly higher pressures of ca. 0.9 GPa. The preservation of distinct major and trace element zoning in garnet and the existence of broadly similar (near prograde) Sm–Nd and Lu–Hf garnet–whole rock ages of ca. 525 Ma obtained on the same sample indicate an extremely fast cooling path. Retrograde conditions persisted until ca. 490 Ma indicating a slow, late stage near isobaric cooling path. The resulting clockwise P–T–t path is consistent with crustal thickening through continent–continent collision followed by post-collisional extension and suggests that the upper amphibolite to granulite facies terrain of the central Kaoko Belt formed initially in a metamorphic field gradient of ca. 25–35 °C km^− 1 at moderately high 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.     

Osumilite and a spinel + quartz association in garnet–sillimanite gneiss from Rundvågshetta,Lützow-Holm Complex,East Antarctica

This is the first report of osumilite occurring as fine isolated inclusions within garnet porphyroblasts, as observed in garnet–sillimanite gneiss from Rundvågshetta, Lützow-Holm Complex, East Antarctica. The osumilite is characterized by high Si content (10.60 and 10.95 atoms based on 30 oxygens per formula unit), low Al content (2.99 and 3.82), a high content of M site-occupying cations (2.51 and 3.03), and high X_Mg values (about 0.81). We also report a spinel + quartz association found as inclusions within garnet porphyroblasts. Spinel grains, which are in direct contact with quartz and are spatially associated with sillimanite, show extremely high Zn contents (X_Zn^Spl = 0.33 ? 0.46) and high X_Mg values (0.45–0.54). The garnet is rimmed by sillimanite, K-feldspar, plagioclase, and quartz. Biotite and cordierite are found only as inclusions within garnet porphyroblasts, where biotite coexists with spinel–quartz or with rutile. Porphyroblastic garnet contains rutile needles and has low X_Mg values (about 0.36). The sillimanite contains a high Fe content (about 1.2 wt.% Fe₂O₃).The occurrence of osumilite and spinel + quartz indicates a clockwise pressure–temperature path of ultrahigh-temperature metamorphism, involving the following events: (1) the Rundvågshetta granulites suffered prograde metamorphism within the kyanite and sapphirine + quartz fields; (2) subsequent retrograde metamorphism, involving near-isothermal decompression, occurred in the orthopyroxene + sillimanite + quartz field; (3) the granulites passed through the garnet + cordierite + sillimanite + quartz field during decreasing temperature; (4) the granulites entered the osumilite stability field at around 8 kbar and 950 °C; and (5) the granulites retain a final record of retrograde metamorphism within the biotite + sillimanite + K-feldspar and quartz field at 6.1 kbar and about 830 °C.     

K-feldspar–quartz and K-feldspar–plagioclase phase boundary interactions in garnet–orthopyroxene gneiss's from the Val Strona di Omegna, Ivrea–Verbano Zone, northern Italy

A detailed study based on textural observations combined with microanalysis [back scattered electron imaging (BSE) and electron microprobe analysis (EMPA)] and microstructural data transmission electron microscopy (TEM) has been made of K-feldspar micro-veins along quartz–plagioclase phase and plagioclase–plagioclase grain boundaries in granulite facies, orthopyroxene–garnet-bearing gneiss's (700–825 °C, 6–8 kbar) from the Val Strona di Omegna, Ivrea–Verbano Zone, northern Italy. The K-feldspar micro-veins are commonly associated with quartz and plagioclase and are not found in quartz absent regions of the thin section. This association appears to represent a localised reaction texture resulting from a common high grade dehydration reaction, namely: amphibole + quartz = orthopyroxene + clinopyroxene + plagioclase + K-feldspar + H₂O, which occurred during the granulite facies metamorphism of these rocks. There are a number of lines of evidence for this. These include abundant Ti-rich biotite, which was apparently stable during granulite facies metamorphism, and total lack of amphibole, which apparently was not. Disorder between Al and Si in the K-feldspar indicates crystallisation at temperatures >500 °C. Myrmekite and albitic rim intergrowths in the K-feldspar along the K-feldspar–plagioclase interface could only have formed at temperatures >500–600 °C. Symplectic intergrowths of albite and Ca-rich plagioclase between these albitic rim intergrowths and plagioclase suggest a high temperature grain boundary reaction, which most likely occurred at the start of decompression in conjunction with a fluid phase. Relatively high dislocation densities (>2 × 10⁹ to 3 × 10⁹/cm²) in the K-feldspar suggest plastic deformation at temperatures >500 °C. We propose that this plastic deformation is linked with the extensional tectonic environment present during the mafic underplating event responsible for the granulite facies metamorphism in these rocks. Lastly, apparently active garnet grain rims associated with side inclusions of K-feldspar and quartz and an exterior K-feldspar micro-vein indicate equilibrium temperatures within 20–30 °C of the peak metamorphic temperatures estimated for the sample (770 °C). Contact between these K-feldspar micro-veins and Fe-Mg silicate minerals, such as garnet, orthopyroxene, clinopyroxene or biotite along the interface, is observed to be very clean with no signs of melt textures or alteration to sheet silicates. This lends support to the idea that these micro-veins did not originate from a melt and, if fluid induced, that the water activity of these fluids must have been relatively low. All of these lines of evidence point to a high grade origin for the K-feldspar micro-veins and support the hypothesis that they formed during the granulite facies metamorphism of the metabasite layers in an extensional tectonic environment as the consequence of localised dehydration reactions involving the breakdown of amphibole in the presence of quartz to orthopyroxene, clinopyroxene, plagioclase, K-feldspar and H₂O. It is proposed that the dehydration of the metabasite layers to an orthopyroxene–garnet-bearing gneiss over a 4-km traverse in the upper Val Strona during granulite facies metamorphism was a metasomatic event initiated by the presence of a high-grade, low H₂O activity fluid (most likely a NaCl–KCl supercritical brine), related to the magmatic underplating event responsible for the Mafic Formation; and that this dehydration event did not involve partial melting. Received: 15 February 2000 / Accepted: 26 June 2000     

Trace element zoning in garnet from the Kwoiek Area,British Columbia: disequilibrium partitioning during garnet growth?

Trace element zoning in garnets from two contact-metamorphosed rocks from the Kwoiek area, British Columbia (Hollister 1969a), was measured with an ion microprobe. Zoning profiles have three distinct parts with chemical breaks defined by co-variation of major and trace elements. Important features of the trace element zoning profiles are: (1) roughly bell-shaped zoning profiles for Y and the HREEs, (2) an abrupt increase in Ti at a point midway through each garnet with inflections in the zoning profiles of other elements (Li, Na, Cr, V, Y, Zr, and the HREE), and (3) irregular Cr and V profiles. Unlike Mn zoning, the zoning profiles of most other trace elements cannot be easily modeled using simple Rayleigh fractionation models. Ti activity in the two samples is buffered by phase relations with ilmenite. Garnets from a continuously heated contact metamorphic environment should display continuous Ti zoning profiles if equilibrium was maintained and provided the Ti buffering assemblage did not change during garnet growth. The irregular Ti profiles suggest disequilibrium behavior. Several elements (Cr, V) may indicate breakdown of a phase enriched in trace elements during metamorphism. The source for the mass excess of these elements is probably the refractory cores of ilmenite grains. Either differing matrix transport rates of trace lements or interface kinetic controlled segregation could explain the unusual trace element behavior at the element inflection point. The preferred explanation involves segregation of elements at the interface of the garnet that were trapped during episodes of rapid garnet growth.     

Eclogite-facies fluid infiltration: constraints from δ18O zoning in garnet

In situ analysis reveals that eclogite-facies garnets are zoned in δ¹⁸O with lower values in the core and rims that are ~1.5 to 2.5 ‰ higher. This pattern is present in 9 out of 12 garnets analyzed by SIMS from four orogenic eclogite terranes, and correlates with an increase in the mole fraction of pyrope and Mg/Fe ratio from core to rim, indicating prograde garnet growth. At the maximum temperatures and the time-scales experienced by these garnets, calculated intragranular diffusion distances for oxygen are small (<5 μm), indicating that δ¹⁸O records primary growth zoning and not diffusive exchange. The oxygen isotope gradients are larger than could form due to temperature changes during closed-system mineral growth. Thus, gradients reflect the compositions of fluids infiltrating during prograde metamorphism. Values of δ¹⁸O in garnet cores range from ?1 to 15 ‰, likely preserving the composition of the eclogite protoliths. Two garnet cores from the Almenningen eclogite in the Western Gneiss Region, Norway, have δ¹⁸O ~?1 ‰ and are the first negative δ¹⁸O eclogites identified in the region. In contrast with orogenic eclogites, seven high δ¹⁸O garnets (>5 ‰) from two kimberlites are homogeneous in δ¹⁸O, possibly due to diffusive exchange, which is possible for prolonged periods at higher mantle temperatures. Homogeneity of δ¹⁸O in garnets outside the normal mantle range (5–6 ‰) may be common in kimberlitic samples.     

Experimental evaluation of garnet–clinopyroxene geothermometry as applied to eclogites

This study performed equilibrium experiments in order to evaluate previously proposed formulations of the garnet (Grt)–clinopyroxene (Cpx) thermometer as applied to eclogites. The starting material is fine-grained powder of natural eclogite (<10 μm), whose main constituents are Grt (Fe:Mg:Ca∼44:28:28), Cpx (Na pfu∼0.55–0.60), phengite, quartz and rutile. Experimental conditions are 1,100–1,250°C at 2.5 GPa, and the run duration is 193–334 h. The experimental run products mainly consist of Grt, Cpx, and glass. In a preliminary experiment at 1,000°C for 144 h, Cpx grains are clearly zoned and most Grt grains maintain primary compositions. In the higher T (≥1,100°C) and longer run (≥193 h) experiments, Cpx in the run products becomes poorer in Na and higher in Fe/Mg compared with the starting material, and each grain does not show clear chemical zoning. Garnet compositions become poorer in Ca [Ca/(Fe+Mn+Mg+Ca)∼0.2–0.25] and lower in Fe/Mg compared with the starting material. The average composition of Cpx and the average of Ca-poor Grt compositions in each run product were used to evaluate previously proposed formulations of the Grt–Cpx thermometer. Temperatures calculated with formulations by Pattison and Newton (1989) and Berman et al. (1995) are much lower than the experimental temperatures, even though these formulations are based on the compositional bracketing-type experiment. One of the reasons for this discrepancy might be uncertainty of solid-solution properties of Al in Cpx, because the value of the excess interaction parameter for Al in the generally low-Al Cpx modeled by Berman et al. (1995) is much higher than those proposed by independent experiments, resulting in the estimated temperatures being significantly lower than the experimental temperatures.     

Deformation behavior of migmatites: insights from microstructural analysis of a garnet–sillimanite–mullite–quartz–feldspar-bearing anatectic migmatite at Rampura–Agucha,Aravalli–Delhi Fold Belt,NW India

International Journal of Earth Sciences - In the present study we investigate the microstructural development in mullite, quartz and garnet in an anatectic migmatite hosted within a Grenvillian-age...     

Dating high-grade metamorphism—constraints from rare-earth elements in zircon and garnet

We integrate petrography and SIMS REE analyses of garnet and polyphase zircon from a pelitic granulite adjacent to the Ronda peridotite, Betic Cordillera, southern Spain to constrain the significance of zircon U-Pb geochronology. Sillimanite inclusions in garnet rims suggest that they grew during decompression, and Ca enrichment in their rims records initiation of partial melting. Chondrite-normalised REE profiles of zircon cores are typically magmatic (positive La to Lu slope and Ce anomaly), whereas overgrowths have flat or negatively sloping heavy-REE profiles (Gd-Lu). The presence of rimmed zircon grains only in the garnet rims and the matrix suggests that this zircon phase grew after garnet had already sequestered heavy REEs, a process documented here by progressive depletion of heavy REE in the garnets from centre to rim. Combined with the textural evidence, we suggest that the U-Pb age of 21.3ǂ.3 Ma obtained from the zircon rims dates a point on this decompression path rather than the peak metamorphic pressure.     

Dating magmatic and hydrothermal processes using andradite-rich garnet U–Pb geochronometry

Andradite-rich garnet is a common U-bearing mineral in a variety of alkalic igneous rocks and skarn deposits, but has been largely neglected as a U–Pb chronometer. In situ laser ablation-inductively coupled plasma mass spectrometry U–Pb dates of andradite-rich garnet from a syenite pluton and two iron skarn deposits in the North China craton demonstrate the suitability and reliability of the mineral in accurately dating magmatic and hydrothermal processes. Two hydrothermal garnets from the iron skarn deposits have homogenous cores and zoned rims (Ad₈₆Gr₁₁ to Ad₉₈Gr₁) with 22–118 ppm U, whereas one magmatic garnet from the syenite is texturally and compositionally homogenous (Ad₇₀Gr₂₂ to Ad₇₇Gr₁₄) and has 0.1–20 ppm U. All three garnets have flat time-resolved signals obtained from depth profile analyses for U, indicating structurally bound U. Uranium is correlated with REE in both magmatic and hydrothermal garnets, indicating that the incorporation of U into the garnet is largely controlled by substitution mechanisms. Two hydrothermal garnets yielded U–Pb dates of 129 ± 2 (2σ; MSWD = 0.7) and 130 ± 1 Ma (2σ; MSWD = 0.5), indistinguishable from zircon U–Pb dates of 131 ± 1 and 129 ± 1 Ma for their respective ore-related intrusions. The magmatic garnet has a U–Pb age of 389 ± 3 Ma (2σ; MSWD = 0.6), consistent with a U–Pb zircon date of 388 ± 2 Ma for the syenite. The consistency between the garnet and zircon U–Pb dates confirms the reliability and accuracy of garnet U–Pb dating. Given the occurrence of andradite-rich garnet in alkaline and ultramafic magmatic rocks and hydrothermal ore deposits, our results highlight the potential utilization of garnet as a powerful U–Pb geochronometer for dating magmatism and skarn-related mineralization.     

Hornblende–garnet–plagioclase thermobarometry: a natural assemblage calibration of the thermodynamics of hornblende

Calibrations are presented for an independent set of four equilibria between end-members of garnet, hornblende, plagioclase and quartz. Thermodynamic data from a large internally-consistent thermodynamic dataset are used to determine the ΔG° of the equilibria. Then, with the known mixing properties of garnet and plagioclase, the non-ideal mixing in amphibole is derived from a set of 74 natural garnet–amphibole–plagioclase–quartz assemblages crystallised in the range 4–13 kbar and 500–800 °C. The advantage of using known thermodynamic data to calculate ΔG° is that correlated variations of composition with temperature and pressure are not manifested in fictive derived entropies and volumes, but are accounted for with non-ideal mixing terms. The amphibole is modelled using a set of ten independent end-members whose mixing parameters are in good agreement with the small amount of data available in the literature. The equilibria used to calibrate the amphibole non-ideal mixing reproduce pressures and temperatures with average absolute deviations of 1.1 kbar and 35 °C using an average pressure–temperature approach, and 0.8 kbar with an average pressure approach. The mixing data provide not only a basis for thermobarometry involving additional phases, but also for calculation of phase diagrams in complex amphibole-bearing systems. Received: 8 November 1999 / Accepted: 7 July 2000     

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.     

Deliquescence of NaCl–NaNO<Subscript>3</Subscript>, KNO<Subscript>3</Subscript>–NaNO<Subscript>3</Subscript>, and NaCl–KNO<Subscript>3</Subscript>salt mixtures from 90 to 120°C

We conducted reversed deliquescence experiments in saturated NaCl–NaNO₃–H₂O, KNO₃–NaNO₃–H₂O, and NaCl–KNO₃–H₂O systems from 90 to 120°C as a function of relative humidity and solution composition. NaCl, NaNO₃, and KNO₃ represent members of dust salt assemblages that are likely to deliquesce and form concentrated brines on high-level radioactive waste package surfaces in a repository environment at Yucca Mountain, NV. Discrepancy between model prediction and experiment can be as high as 8% for relative humidity and 50% for dissolved ion concentration. The discrepancy is attributed primarily to the use of 25°C models for Cl–NO₃ and K–NO₃ ion interactions in the current Yucca Mountain Project high-temperature Pitzer model to describe the nonideal behavior of these highly concentrated solutions.     

Compositional zoning of garnet porphyroblasts from the polymetamorphic Wölz Complex, Eastern Alps

We employ garnet isopleth thermobarometry to derive the P–T conditions of Permian and Cretaceous metamorphism in the Wölz crystalline Complex of the Eastern Alps. The successive growth increments of two distinct growth zones of the garnet porphyroblasts from the Wölz Complex indicate garnet growth in the temperature interval of 540°C to 560°C at pressures of 400 to 500 MPa during the Permian and temperatures ranging from 550°C to 570°C at pressures in the range of 700 to 800 MPa during the Cretaceous Eo-Alpine event. Based on diffusion modelling of secondary compositional zoning within the outermost portion of the first garnet growth zone constraints on the timing of the Permian and the Eo-Alpine metamorphic events are derived. We infer that the rocks remained in a temperature interval between 570°C and 610°C over about 10 to 20 Ma during the Permian, whereas the high temperature stage of the Eo-Alpine event only lasted for about 0.2 Ma. Although peak metamorphic temperatures never exceeded 620°C, the prolonged thermal annealing during the Permian produced several 100 µm wide alteration halos in the garnet porphyroblasts and partially erased their thermobarometric memory. Short diffusion profiles which evolved around late stage cracks within the first garnet growth zone constrain the crack formation to have occurred during cooling below about 450°C after the Eo-Alpine event.