Showing papers in "Contributions to Mineralogy and Petrology in 1993"

Experimental investigations of the role of H2O in calc-alkaline differentiation and subduction zone magmatism

Abstract: Phase relations of natural aphyric high-alumina basalts and their intrusive equivalents were determined through rock-melting experiments at 2 kb, H2O-saturated with fO2 buffered at NNO. Experimental liquids are low-MgO high-alumina basalt or basaltic andesite, and most are saturated with olivine, calcic plagioclase, and either high-calcium pyroxene or hornblende (±magnetite). Cr-spinel or magnetite appear near the liquidus of wet high-alumina basalts because H2O lowers the appearance temperature of crystalline silicates but has a lesser effect on spinel. As a consequence, experimental liquids follow calcalkaline differentiation trends. Hornblende stability is sensitive to the Na2O content of the bulk composition as well as to H2O content, with the result that hornblende can form as a near liquidus mineral in wet sodic basalts, but does not appear until liquids reach andesitic compositions in moderate Na2O basalts. Therefore, the absence of hornblende in basalts with low-to-moderate Na2O contents is not evidence that those basalts are nearly dry. Very calcic plagioclase (>An90) forms from basaltic melts with high H2O contents but cannot form from dry melts with normal are Na2O and CaO abundances. The presence of anorthite-rich plagioclase in high-alumina basalts indicates high magmatic H2O contents. In sum, moderate pressure H2O-saturated phase relations show that magmatic H2O leads to the early crystallization of spinel, produces calcic plagioclase, and reduces the total proportion of plagioclase in the crystallizing assemblage, thereby promoting the development of the calc-alkaline differentiation trend.

Experimental cpx/melt partitioning of 24 trace elements

Abstract: Cpx/melt partition coefficients have been determined by ion probe for 24 trace elements at natural levels in an alkali basalt experimentally equilibrated at 1,380°C and 3 GPa. One goal was to intercompare Ds for both high-field-strength elements and rare earth elements (REE) in a single experiment. Relative to the REE spidergram, Hf and Ti show virtually no anomaly, whereas Zr exhibits a major negative anomaly. Other incompatible elements (Ba, K, Nb) fall in the range of published values, as do elements such as Sr, Y, Sc, Cr and V. Pb shows a value intermediate between La and Ce. Values for Be, Li and Ga are reported for the first time, and show that Be is as incompatible as the light REEs whereas Li and Ga are somewhat more compatible than the heavy REE.

Temperatures and H 2 O contents of low-MgO high-alumina basalts

Abstract: Experimental evidence is used to estimate H2O contents in low-MgO high-alumina basalts (HABs) ( 8wt.% MgO) could have H2O contents reaching no more than 1–2wt.%. The more common low-MgO HABs could have existed as liquids within the crust with H2O contents of 4 wt.% or higher at temperatures<1100°C. Magmas with these high H2O contents will saturate with and exsolve aqueous fluid upon approaching the surface. They cannot erupt as liquids and must grow crystals at shallow depths, thus accounting for the abundant phenocrysts in low-MgO HABs and BAs.

Remobilisation of the continental lithosphere by a mantle plume: major-, trace-element, and Sr-, Nd-, and Pb-isotope evidence from picritic and tholeiitic lavas of the Noril'sk District, Siberian Trap, Russia

Abstract: The Late Permian to Early Triassic Siberian Traps have been sampled by drill core (core SG-9) and from surface exposure (section 1F) in the Noril'sk region of the Siberian Platform, Russia. Combined major, trace element, and Nd-, Sr-, and Pb-isotope data on selected samples through the Siberia Trap, offer new chemostratigraphic criteria for the identification and characterisation of two fundamentally different magma types and 9 of the 11 formations of lava developed near Noril'sk. A Lower Sequence of sub-alkalic basalts, tholeiites, and picritic basalts (upwards these are the Ivakinsky, Syverminsky, and Gudchichinsky formations) are overlain by an Upper Sequence of picritic basalts and tholeiites interbedded with tuffs (upwards, these are the Khakanchansky, Tuklonsky, Nadezhdinsky, Morongovsky, Mokulaevsky and Kharayelakhsky formations).The Gudchichinsky and Tuklonsky formations contain both picritic and tholeiitic lavas. The Tuklonsky formation tholeiites and picrites have moderate Gd/Yb (1.6–1.8), low TiO2 (0.45–0.95 wt%), a significant negative Ta and Nb anomaly (Nb/La =0.42–0.57) and unradiogenic Nd (ɛ Nd CHUR = to -4.6). In contrast, both the Gudchichinsky formation tholeiites and picrites have high Gd/Yb (2.3–3.1), and TiO2 (1.2–2.3 wt%), no significant Nb or Ta anomaly (Nb/La =0.8–1.1), and radiogenic Nd (ɛ Nd CHUR = to 7.3). The low-Ti and Nb/La, high La/Sm, and unradiogenic Nd-isotope signatures of the picritic Tuklonsky formation lavas and the tholeiitic lavas of the Upper Sequence are characteristic of magmas strongly influenced by material from the continental lithosphere, whereas the high-Ti and Nb/La, low La/Sm and radiogenic Nd-isotope signatures of the Lower Sequence are more comparable to deeper asthenospheric mantle-plume generated lavas similar to oceanic island basalts. The lavas overlying the Tuklonsky formation have mg-numbers of 0.63 to 0.68, and are more evolved than the Tuklonsky (Mg-number < 0.62) and have more radiogenic ɛ Nd CHUR (Tuklonsky:-0.03 to-4.66; Mokulaevsky: + 0.60 to + 1.61), but have many of the incompatible trace element features of the Tuklonsky sky type magma. These lavas show a progressive upwards decline in SiO2 (55–49 wt%), La/Sm (4.6–2.0), and ɛ UR Sr ( + 67 to + 13) which has previously been attributed to a decrease in the proportion of crustal material contributed to the magma. This paper explores and alternative model where a component of the crustal contribution might be derived from within an ancient region of the mantle lithosphere as recycled sediment rather than from the overlying continental crust.

Redox states of lithospheric and asthenospheric upper mantle

Abstract: The oxidation state of lithospheric upper mantle is heterogeneous on a scale of at least four log units. Oxygen fugacities ( $$f_{O_2 } $$ ) relative to the FMQ buffer using the olivine-orthopyroxene-spinel equilibrium range from about FMQ-3 to FMQ+1. Isolated samples from cratonic Archaean lithosphere may plot as low as FMQ-5. In shallow Proterozoic and Phanerozoic lithosphere, the relative $$f_{O_2 } $$ is predominantly controlled by sliding Fe3+-Fe2+ equilibria. Spinel peridotite xenoliths in continental basalts follow a trend of increasing $$f_{O_2 } $$ with increasing refractoriness, to a relative $$f_{O_2 } $$ well above graphite stability. This suggests that any relative reduction in lithospheric upper mantle that may occur as a result of stripping lithosphere of its basaltic component is overprinted by later metasomatism and relative oxidation. With increasing pressure and depth in lithosphere, elemental carbon becomes progressively refractory and carbon-bearing equilibria more important for $$f_{O_2 } $$ control. The solubility of carbon in H2O-rich fluid (and presumably in H2O-rich small-degree melts) under the P,T conditions of Archaean lithosphere is about an order of magnitude lower than in shallow modern lithosphere, indicating that high-pressure metasomatism may take place under carbon-saturated conditions. The maximum $$f_{O_2 } $$ in deep Archaen lithosphere must be constrained by equilibria such as EMOG/D. If the marked chemical depletion and the orthopyroxene-rich nature of Archaean lithospheric xenoliths is caused by carbonatite (as opposed to komatiite) melt segregation, as suggested here, then a realistic lower $$f_{O_2 } $$ limit may be given by the H2O +C=CH4+O2 (C-H2O) equilibrium. Below C −H2O a fluid becomes CH4 rather than CO2-bearing and carbonatitic melt presumably unstable. The actual $$f_{O_2 } $$ in deep Archaean lithosphere is then a function of the activities of CO2 and MgCO3. Basaltic melts are more oxidized than samples from lithospheric upper mantle. Mid-ocean ridge (MORB) and ocean-island basalts (OIB) range between FMQ-1 (N-MORB) and about FMQ +2 (OIB). The most oxidized basaltic melts are primitive island-arc basalts (IAB) that may fall above FMQ+3. If basalts are accurate $$f_{O_2 } $$ probes of their mantle sources, then asthenospheric upper mantle is more oxidized than lithosphere. However, there is a wide range of processes that may alter melt $$f_{O_2 } $$ relative to that of the mantle source. These include partial melting, melt segregation, shifts in Fe3+/Fe2+ melt ratios upon decompression, oxygen exchange with ambient mantle during ascent, and low-pressure volatile degassing. Degassing is not very effective in causing large-scale and uniform $$f_{O_2 } $$ shifts, while the elimination of buffering equilibria during partial melting is. Upwelling graphite-bearing asthenosphere will decompress along $$f_{O_2 } $$ -pressure paths approximately parallel to the graphite saturation surface, involving reduction relative to FMQ. The relative $$f_{O_2 } $$ will be constrained to below the CCO equilibrium and will be a function of $$a_{CO_2 } $$ . Upwelling asthenosphere whose graphite content has been exhausted by partial melting, or melts that have segregated and chemically decoupled from a graphite-bearing residuum will decompress along $$f_{O_2 } $$ -decompression paths controlled by continuous Fe3+-Fe2+ solid-melt equilibria. These equilibria will involve increases in $$f_{O_2 } $$ relative to the graphite saturation surface and relative to FMQ. Melts that finally segregate from that source and erupt on the earth's surface may then be significantly more oxidized than their mantle sources at depth prior to partial melting. The extent of melt oxidation relative to the mantle source may be directly proportional to the depth of graphite exhaustion in the mantle source.

Influence of fluorine on the enrichment of high field strength trace elements in granitic rocks

Abstract: The solubilities of zircon, rutile, manganocolumbite (MnNb2O6), manganotantalite (MnTa2O6), and the rare earth phosphates LaPO4, GdPO4, and YbPO4 in water-saturated haplogranitic melts containing 0–6 wt.% F were measured at 800° C and 2 kbar. The melt compositions investigated differ only in their F content, the proportions of Na, K, Al, and Si are identical in all experiments. While the solubilities of the rare earth phosphates are independent of F, the solubilities of all other minerals studied strongly increase with F. The TiO2 content of haplogranitic melt in equilibrium with rutile increases linearly from 0.26 wt.% without F to 0.47 wt.% for melts containing 6 wt.% F. Over the same range of F concentrations, the ZrO2 content of the melt in equilibrium with zircon increases with the square of the F content from less than 0.01 wt.% to 0.25 wt.%. The linear increase for rutile and the quadratic relationship for zircon suggest a complexing mechanism. Probably nonbridging oxygen atoms (NBO) expelled from coordination with Al by reaction with F form complexes with Ti and Zr, the ratio of NBO: metal cation being 1:1 for Ti, and 2:1 for Zr. Direct complexing by F is also a possibility. As titanium oxide phases and zircon are major sinks for HFS elements such as Ti, Nb, Ta, Zr, Hf, Th and REE in granites, their increased solubility in the presence of F favors the enrichment of these elements in residual mels. The Nb and Ta content of rutile in granitic pegmatites is due to extended solid solution of rutile with columbite group minerals, such as manganocolumbite and manganotantalite. The solubility of these components also increases with F, MnTa2O6 being more soluble than MnNb2O6. Rutile fractionation could therefore account for the increase in Ta/Nb frequently observed in highly differentiated granites. The solubility of the rare earth phosphates increases strongly from LaPO4 to GdPO4 to YbPO4, which explains the enrichment of heavy rare earth elements in highly evolved granites. In the presence of F, many HFS elements will be highly incompatible in granitic systems. Therefore, in a suite of granitic rocks generated by differentiation from the same source magma, a strong correlation should exist between HFS elements and F. However, because of the influence of F on the solubility of refractory phases such as zircon, a similar correlation could also result from different batches of magma containing different amounts of F equilibrating with the same refractory phase.

Olivine-melt and orthopyroxene-melt equilibria

Abstract: The use of non-regular solution models for silicate melts allows saturation temperatures to be calculated with an accuracy of±10 K for Mg and Fe, olivine or orthopyroxene components; and±20 K for Mn, Co and Ni components. This accuracy is comparable to that of the temperature measurement in the experiments with which the models are calibrated. The errors in the temperature calculation are less than a third of those associated with a regular solution model of mineral-melt equilibria. The values of thermodynamic properties predicted by these empirical solution models are larger than those found calorimetrically, but provide a better fit to the existing experimental data. The calculation of thermochemical properties of olivine and orthopyroxene species in both the crystalline and melt phases allows the calculation of mineral-melt\(K_{D_M /{\text{Mg}}}^{\alpha /L} \)s; the values calculated are within one standard error of those reported in the literature. Eruption temperatures calculated from the composition of Hawaiian tholeiite glasses range from 1135 to 1185°C, and are comparable to measured lava temperatures. These temperatures are lower than those calculated for Atlantic MORB confirming that extensive fractional crystallisation has occurred.

Relationship between plagioclase crystallization and cooling rate in basaltic melts

Abstract: Rock textures commonly preserve a record of the near-surface crystallization history of volcanic rocks. Under conditions of simple cooling without convection or mixing, textures will reflect sample cooling rate, the temperature at which crystallization was initiated, and the distribution of mineral phase precipitation across the crystallization interval. Compilation of plagioclase size and number density data on natural (dike, sill and lava lake) and experimental samples suggests that (1) growth and nucleation rates of plagioclase in natural basaltic samples are a predictable function of cooling rate, and (2) the observed crystallization rate dependence on cooling rate is similar to that observed in experiments initiated at subliquidus temperatures. Comparison of natural and experimental samples thus suggests that most basalts crystallize under conditions of heterogeneous nucleation, with the number density of preexisting nucleii partially controlling textural responses to cooling rate changes. Time scales of crystallization and cooling in magmatic systems are intimately linked through a balance between heat removal from the system and heat evolved through crystallization. Evaluation of textural data in the context of recent numerical models of crystallization in simple (one- and two-component systems) provides new insight into regularities in the crystallization behavior of basaltic magmas. For example, the rate of change in crystal size (and number density, as dictated by mass balance) has been used as a measure of the relative importance of time scales of crystallization and cooling in numerical models of crystallizing systems. In natural samples, plagioclase size scales with the length scale of cooling such that a logarithmic plot of grain size as a function of normalized distance across the dike has a slope that appears approximately independent of dike width (solidification time). Comparison with available textural data for other phenocryst phases suggests that the same may be true for pyroxene and magnetite crystallization, with each phase having a characteristic slope probably controlled by the thermodynamic properties of the crystallizing phase. Measured crystal size distributions are unimodal and show maximum frequencies in the smaller size classes; distributions broaden and the grain size at peak frequency increases with increasing crystallization times (decreasing cooling rates). In contrast, partially crystallized Makaopuhi lava lake samples have crystal size distributions that decrease exponentially with increasing crystal size. Measured size distributions in dikes can be explained by late stage modification of Makaopuhi-type distributions through loss of small crystals, possibly the consequence of growth without nucleation. Finally, this compilation of the textural response of basaltic magmas to changes in cooling rate suggests that empirical calibrations of crystallization rate dependence on cooling rate from natural samples provide a reasonable model for plagioclase crystallization in near-surface basaltic systems. Predicted growth rates will be slow and relatively constant (10-10–10-11 cm/s) for crystallization times expected in most shallow volcanic systems (<1000 years).

Thermodynamic data from redox reactions at high temperatures. I. An experimental and theoretical assessment of the electrochemical method using stabilized zirconia electrolytes, with revised values for the Fe-“FeO”, Co-CoO, Ni-NiO and Cu-Cu2O oxygen buffers, and new data for the W-WO2 buffer

Abstract: The accuracy and reliability of high temperature thermodynamic data obtained from oxygen concentration cells with stabilized zirconia (SZ) electrolytes are assessed. The experimental apparatus and methods needed to obtain precise results are described. We then test the apparatus, firstly on symmetrical cells of the type: $$Pt, M + M_x O|CSZ|M + M_x O, Pt$$ where M=C, Ni, Co or Fe; and then by examining all the possible permutations of heterogenous cells with these four oxygen buffers. Simultaneous linear regression of all the data (624 readings from 14 different cells) shows that the overall precision of the results is ±100 J/mol (one standard deviation). The results are in good agreement with the available calorimetric data. Although the agreement with previous electrochemical work is also good, the high precision of the present results reveals small systematic differences, and accordingly we recommend small adjustments to the existing values for these buffers. The revised equations are (\(\mu _{O_2 } \) in J/mol, temperature in K, reference pressure 105 Pa): $$\begin{gathered} Cu - Cu_2 O( \pm 80): \hfill \\ - 347,705 + 246.096 T \hfill \\ - 12.9053 T In T (700< T< 1,338) \hfill \\ Ni - NiO( \pm 200): \hfill \\ - 478,967 + 248.514 T \hfill \\ - 9.7961 T In T (700< T< 1.700) \hfill \\ Co - CoO( \pm 200): \hfill \\ - 492,186 + 509.322 T - 53.284 T In T \hfill \\ + 0.02518 T^2 (700< T< 1,394) \hfill \\ - 484,276 + 235,092 T \hfill \\ - 11.3440 T In T(1,394< T< 1,760) \hfill \\ \end{gathered} $$

Accessory phase controls on the geochemistry of crustal melts and restites produced during water-undersaturated partial melting

Abstract: The profound geochemical conseqences of accessory phase behaviour during partial melting of highgrade metapelites are demonstrated with reference to two geochemically distinct crustal melts produced by biotite dehydration melting reactions under granulite facies (kbar, 860°CC) conditions. These two leucogneiss suites, from the Brattstrand Bluffs coastline, eastern Antarctica, have similar field relations, transport distances (10–100 s of metres) and major element chemistry. Type 1 leucogneisses have low Zr, Th and LREE, positive Eu anomalies and Zr/Zr* and LREEt/LREEt * values less than 1.0 (i.e. less than required to saturate the melt). Mass balance constraints suggest that these melts have been extracted before equilibration with host melanosomes. The dry, peraluminous nature of vapour-undersaturated melts inhibits monazite and zircon solubility and results in concentration of these phases in the residue. Melts are consequently depleted in LREE and HREE. Melanosomes show complementary enrichment in LREE, while HREE patterns are dominated by residual garnet. Type 2 leucogneisses, in contrast, have strongly enriched Zr, Th and LREE abundances, negative Eu anomalies and Zr/Zr* and LREEt/LREEt *>1 resulting from accessory phase entrainment. Vapour-absent partial melting under moderate (6–8 kbar) pressure granulite-facies conditions of a pelitic source containing monazite is likely to give disequilibrium melts depleted in LREE and HREE as monazite and garnet are concentrated in the residue. If temperatures are high enough (850–870° C) to permit relatively large degrees of partial melting then the feldspar component of the source will be removed almost completely, giving melts with large positive Eu anomalies. Melts formed under vapour-present conditions are unlikely to show such extreme LREE and HREE depletion or positive Eu anomalies, even at high degrees of partial melting. Disequilibrium melting coupled with source entrainment could fortuitously produce REE and trace element signatures similar to those typical of S-type granites and usually ascribed to equilibrium melting conditions.

Petrology of the Chilliwack batholith, North Cascades, Washington : Generation of calc-alkaline granitoids by melting of mafic lower crust with variable water fugacity

Abstract: Calc-alkaline granitoid rocks of the Oligocene-Pliocene Chilliwack batholith, North Cascades, range from quartz diorites to granites (57–78% SiO2), and are coeval with small gabbroic stocks. Modeling of major element, trace element, and isotopic data for granitoid and mafic rocks suggests that: (1) the granitoids were derived from amphibolitic lower crust having REE (rare-earth-element) and Sr-Nd isotopic characteristics of the exposed gabbros; (2) lithologic diversity among the granitoids is primarily the result of variable water fugacity during melting. The main effect of fH 2 O variation is to change the relative proportions of plagioclase and amphibole in the residuum. The REE data for intermediate granitoids (quartz diorite-granodiorite; Eu/Eu*=0.84–0.50) are modeled by melting with fH 2 O<1 kbar, leaving a plagioclase + pyroxene residuum. In contrast, data for leucocratic granitoids (leuco-granodiorites and granites; Eu/Eu* =1.0–0.54) require residual amphibole in the source and are modeled by melting with fH 2 O=2–3 kbar. Consistent with this model, isotopic data for the granitoids show no systematic variation with rock type (87Sr/86Sri =0.7033–0.7043; eNd(0)=+3.3 to +5.5) and overlap significantly with data for the gabbroic rocks (87Sr/86Sri =0.7034–0.7040; eNd(0)=+3.3 to +6.9). The fH 2 O variations during melting may reflect additions of H2O to the lower crust from crystallizing basaltic magmas having a range of H2O contents; Chillwack gabbros document the existence of such basalts. One-dimensional conductive heat transfer calculations indicate that underplating of basaltic magmas can provide the heat required for large-scale melting of amphibolitic lower crust, provided that ambient wallrock temperatures exceed 800°C. Based on lithologic and geochemical similarities, this model may be applicable to other Cordilleran batholiths.

Partitioning of platinum-group elements and Au in the Fe-Ni-Cu-S System: experiments on the fractional crystallization of sulfide melt reply

Abstract: Partitioning of platinum-group elements (PGE) between sulfide liquid and monosulfide solid solution (mss) has been investigated by crystallizingmss from Fe−Ni−Cu sulfide liquid at 1,000–1,040° C, using bulk compositions and PGE contents typical of magmatic sulfides associated with mafic and ultramafic systems. Products were analyzedin situ for PGE and Au using SIMS. Sulfide liquid compositions were more Ni- and Cu-rich than coexistingmss. Liquid/mss partition coefficients are: Os-0.23±0.04, Ir-0.28±0.11, Ru-0.24±0.05, Rh-0.33±0.06, Pt-4.8±0.7, Pd-4.8±1.9, Au-11.4. Partitioning of PGE is independent of PGE concentration and Ni content in the composition range investigated. Additionally, Henry's law appears to be obeyed up to minor-element contents in the sulfide liquid andmss. Osmium, Ir, Ru, and Rh are compatible elements in the anhydrous Fe−Ni−Cu−S system, whereas Pt, Pd and Au are incompatible elements. These affinities correspond to the partitions of PGE between massive and Cu-rich magmatic sulfides. However, the detailed precious-metal compositions of the Cu-rich sulfides of mafic rock systems, disseminated ores of komatiites and Cu-rich assemblage of droplet ore from the Noril'sk-Talnakh deposits are not consistent with those expected for pristine fractionated sulfide liquids.

Origin and differentiation of picritic arc magmas, Ambae (Aoba), Vanuatu

Abstract: Key aspects of magma generation and magma evolution in subduction zones are addressed in a study of Ambae (Aoba) volcano, Vanuatu. Two major lava suites (a low-Ti suite and high-Ti suite) are recognised on the basis of phenocryst mineralogy, geochemistry, and stratigraphy. Phenocryst assemblages in the more primitive low-Ti suite are dominated by magnesian olivine (mg ∼80 to 93.4) and clinopyroxene (mg ∼80 to 92), and include accessory Cr-rich spinel (cr ∼50 to 84). Calcic plagioclase and titanomagnetite are important additional phenocryst phases in the high-Ti suite lavas and the most evolved low-Ti suite lavas. The low-Ti suite lavas span a continuous compositional range, from picritic (up to ∼20 wt% MgO) to high-alumina basalts (<5 wt% MgO), and are consistent with differentiation involving observed phenocrysts. Melt compositions (aphyric lavas and groundmasses) in the low-Ti suite form a liquid-line of descent which corresponds with the petrographically-determined order of crystallisation: olivine + Cr-spinel, followed by clinopyroxene + olivine + titanomagnetite, and then plagioclase + clinopyroxene + olivine + titanomagnetite. A primary melt for the low-Ti suite has been estimated by correcting the most magnesian melt composition (an aphyric lava with ∼10.5 wt% MgO) for crystal fractionation, at the oxidising conditions determined from olivine-spinel pairs (fo2 ∼FMQ + 2.5 log units), until in equilibrium with the most magnesian olivine phenocrysts. The resultant composition has ∼15 wt% MgO and an mg Fe2 value of ∼81. It requires deep (∼3 GPa) melting of the peridotitic mantle wedge at a potential temperature consistent with current estimates for the convecting upper mantle (T p ∼1300°C). At least three geochemically-distinct source components are necessary to account for geochemical differences between, and geochemical heterogeneity within, the major lava suites. Two components, one LILE-rich and the other LILE- and LREE-rich, may both derive from the subducting ocean crust, possibly as an aqueous fluid and a silicate melt respeetively. A third component is attributed to either differnt degrees of melting, or extents of incompatible-element depletion, of the peridotitic mantle wedge.

Rutile solubility and mobility in supercritical aqueous fluids

Abstract: Experimental and thermodynamic data and the apparent immobility of Ti under metamorphic conditions suggest that rutile is very insoluble in aqueous fluids at upper crustal conditions. New solubility measurements at 1.0–2.93 GPa and 800–1200°C show, however, that under certain pressure and temperature conditions rutile is quite soluble in H2O. Solubilities were estimated from the measured weight loss of a single crystal equilibrated with a known mass of fluid in a piston cylinder apparatus. Measured solubilities in H2O range from 0.15 wt% (wt loss crystal/wt fluid) at 2.93 GPa and 1000°C to 1.9% at 1.0 GPa and 1100°C. Solubility increases with increasing temperature and with decreasing pressure in a manner given by the following fit to the experimental data: $$\log _{10} m_{Ti} = - 7049/T - (0.589* P)/T + 5.14$$ wherem Ti is the molality of Ti in the fluid,T is in degress Kelvin andP is in MPa. The effect of fluid composition on rutile solubility was also examined at 1.0 GPa and 1000°C for H2O-CO2, 1m NaCl, and 1m HF fluids. Kesults suggest that solubility depends on the mole fraction of H2O in the fluid but is independent of ionic strength and fluid pH. This behavior implies that Ti dissolves as the neutrally-charged hydrolysis product Ti(OH)4. The free energy of this species was calculated for each set of experimental conditions. TheP-T dependence of rutile solubility suggests that aqueous fluids derived from subducted oceanic lithosphere would dissolve rutile or other Ti-rich minerals from the deepest portion of the mantle wedge and precipitate them at higher levels. Subsequent melting of the base of the mantle wedge would form HFSE-depleted IAB.

U-Pb geochronology of the Grenville Orogen of Ontario and New York: constraints on ancient crustal tectonics

Abstract: Based on lithological, structural and geophysi- cal characteristics, the Proterozoic Grenville Orogen of southern Ontario and New York has been divided into domains that are separated from each other by ductile shear zones In order to constrain the timing of meta- morphism, U-Pb ages were determined on metamorphic and igneous sphenes from marbles, calc-silicate gneisses, amphibolites, granitoids, skarns and pegmatites In addi- tion, U-Pb ages were obtained for monazites from meta- pelites and for a rutile from an amphibolite These mineral ages constrain the timing of mineral growth, the duration of metamorphism and the cooling history of the different domains that make up the southern part of the exposed Grenville Orogen Based on the ages from metamorphic minerals, regional and contact metamorphism occurred in the following intervals: Central Granulite Terrane:

Experimental study of liquid evolution in an Fe-rich, layered mafic intrusion: constraints of Fe-Ti oxide precipitation on the T-f O 2 and T-ϱ paths of tholeiitic magmas

Abstract: The Newark Island layered intrusion, a composite intrusion displaying a similar fractionation sequence to the Skaergaard, has both dikes which preserved liquids fed into the intrusion and chilled pillows of liquids resident in the chamber. This study reports experimentally determined one atmosphere liquid lines of descent of these compositions as a function of oxygen fugacity which varies from QFM (quartz-fayalite-magnetite) to 0.5 log10 units above IW (iron-wustite). These experiments reveal a strong oxygen fugacity dependence on the order of appearance and relative abundances of the Fe−Ti oxide minerals. Titanomagnetite saturates prior to ilmenite at QFM, but the order is reversed at lower oxygen fugacities. In the layered series of the Newark Island intrusion, ilmenite arrives shortly before titanomagnetite and the titanomagnetite/ilmenite ratio decreases monotonically after the cumulus appearance of titanomagnetite. Comparison of the crystallization sequence in the intrusion with that of the experiments requires that the oxygen fugacity in the intrusion increased relative to QFM before titanomagnetite saturation and decreased afterward, but always remained between the QFM and IW buffers. Similar trends in the modes of the Fe−Ti oxides (ilmenite and titanomagnetite) in the Skaergaard, Kiglapait, and Somerset Dam intrusions along with Fe2O3/FeO ratios in MORBs suggest that such a temperature-oxygen fugacity path may be typical of tholeiitic magma differentiation. Calculations of the temperature-density paths of the experimental liquids indicate that, at all possible oxygen fugacities, the density must have decreased abruptly after Fe−Ti oxide saturation. Accordingly, liquids replenishing the intrusion after Fe−Ti oxide saturation should pond at the bottom of the chamber, quenching against older cumulates. Field observation at the Newark Island intrusion confirm this prediction. The similarities in the fractionation paths of several other layered intrusions to that of the Newark Island intrusion suggest that the density of the liquids in these intrusions also decreased after Fe−Ti oxide saturation. Experiments on a suggested initial Skaergaard liquid are consistent with this model.

Geochemical and isotopic variations in the calc-alkaline rocks of Aeolian arc, southern Tyrrhenian Sea, Italy: constraints on magma genesis

Abstract: New geochemical and isotopic data are reported for calc-alkaline (CA) volcanics of the Aeolian arc. Three main groups are recognized: the Alicudi and Filicudi volcanics in the western part of the arc; the Panarea, Salina and Lipari (henceforth termed PSL) volcanics in the central part of the arc and the Stromboli suite which makes up the eastern part of the arc. Each group is characterized by distinctive isotopic ratios and incompatible element contents and ratios. 87Sr/86Sr values (0.70352–0.70538) increase from west to northeast, and are well correlated with 143Nd/144Nd (ɛNd from +4.8 to -1.5). Pb isotope ratios are fairly high (6/4=19.15–19.54; 7/4=15.61–15.71; 8/4=38.97–39.36), with a general increase of 7/4 and 8/4 values from Alicudi to PSL islands and Stromboli. LILE contents and some incompatible element ratios (e.g. Ba/La, La/Nb, Zr/Nb, Rb/Sr) increase from the western to the central part of the arc, whereas HFSE and REE abundances decrease. Opposite variations are often observed in the volcanics toward the north-east from PSL islands. To account for these features and the decoupling observed between isotopic compositions and incompatible element abundances and ratios, it is suggested that a mantle source with affinities to the MORB source is “metasomatized” by slab-derived, crustal components. The proportion of crustal material entrained in the mantle source increases from Alicudi to Stromboli, according to the Sr and Nd isotope variations. It is also proposed that slab derived hydrous fluids play an important role, but which is variable in different sectors of the arc. This is attributed to the metasomatizing agent having variable fluid/melt ratios, reflecting different types of mass transfer from the subducted contaminant (probably pelagic sediments) to the mantle wedge. Thus, it is suggested that the slab derived end-member has a high hydrous fluid/melt ratio in the PSL mantle source and a correspondingly lower ratio in the Alicudi and Stromboli sources.

A proposed mechanism for the growth of chalcedony

Abstract: The structural disparities that distinguish chalcedony from macrocrystalline quartz suggest that different crystallization mechanisms are operative during the growth of these two forms of silica. Although the paragenesis of chalcedony has provoked marked disagreement among researchers, a review of previous studies supports the idea that chalcedony can precipitate from slightly saturated aqueous solutions at relatively low temperatures (<100° C). These conditions for deposition suggest a model for chalcedony crystallization that involves the assembly of short-chain linear polymers via bridging silica monomers. This assembly occurs through a spiral growth mechanism activated by a screw dislocation withb=n/2 [110], wheren is an integer. The proposed model can account for a number of peculiarities that have been observed in chalcedony at the microstructural scale, such as: (1) the direction of fiber elongation along [110] rather than [001]; (2) the periodic twisting of chalcedony fibers about [110]; (3) the high density of Brazil twin composition planes; (4) the common intergrowth of moganite within chalcedony.

Effects of F, B2O3 and P2O5 on the solubility of water in haplogranite melts compared to natural silicate melts

Abstract: The effects of F, B2O3 and P2O5 on the H2O solubility in a haplogranite liquid (36 wt. % SiO2, 39 wt. % NaAlSi3O8, 25 wt. % KAlSi3O8) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H2O solubility increases with increasing F and B content of the melt. The H2O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H2O solubility increases from 5.94 to 8.22 wt. % H2O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H2O solubility increase of 0.53 mol H2O/mol F. With addition of 4.35 wt. % B2O3, the H2O solubility increases up to 6.86 wt. % H2O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H2O/mol B2O3. The results allow to define the individual effects of fluorine and boron on H2O solubility in haplogranitic melts with compositions close to that of H2O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H2O solubility was found to be negligible in natural melt compositions. The concominant increase in H2O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.

Factors controlling the development of prism faces in granite zircons: a microprobe study

Abstract: Based on microprobe work, we present arguments that the size relations of the two common prisms {100} and {110} of accessory granite zircons are strongly influenced by chemical factors. Magmatic growth zoning patterns, which we have studied by means of backscattered electron imaging in special zircon sections orientated perpendicular to the c-axis, do not support previous models which assumed temperature or the degree of ZrSiO4 supersaturation to be the primary prism-form-directing factors. The element U, which usually occupies the Zr-sites of granite zircoms to some degree, is strongly suspected of producing an (adsorptive) growth-blocking effect for {110}-type faces thus creating crystals with {110}-dominated prism morphology. A second independent mechanism that is likely to form zircons with large {110} prisms is the common substitution Zr4++Si4+ versus Y(REE) and P contents (relative to Zr) are, according to our model, predestinated to produce zircons with large {100} prisms and vice versa.

A detailed isotopic and petrological study of a single garnet from the Gassetts Schist, Vermont

Abstract: Garnets, up to 1.2 cm across, from a metapelite in the Acadian metamorphic terrain of eastern Vermont have been analysed for major elements and segregated into different fractions for isotopic analysis. The garnets preserve abundant inclusions of minerals present during garnet growth which allow a nearly complete reaction history to be established. The Sm-Nd and U-Pb isotopic analyses yield concordant ages of ∼380 Ma for the rim of one garnet and this is interpreted as the formation age. The changing mineral assemblages through garnet growth, their evolving compositions and the thermodynamic dataset of Holland and Powell (1990) are used to put constraints on the P-T evolution during growth. These imply growth during heating from 540 to 635° C and decompression from 9.7 to 7.2 kbar, representing a temperature increase of 95° C and an uplift of 7 km during growth of the garnet. While growth during heating and decompression is consistent with both field evidence and analysis of garnet microstructures and is predicted by theoretical models of regional metamorphism, the extent of the temperature increase requires either very slow uplift (≤0.15 mm a-1) or an additional magmatic heat input. Slow uplift is precluded by existing constraints on both the duration of the uplift event and that of garnet growth and it is concluded that an external magmatic heat input is required. Comparison with published data on the timing of metamorphism in other parts of the terrain suggests that the peak occurred earlier in lower grade regions, a conclusion that is again supported by theoretical studies. Following the peak, cooling and uplift occurred at a modest rate consistent with simple isostatic recovery.

The effect of fluid and deformation on zoning and inclusion patterns in poly-metamorphic garnets

Abstract: Within the Bergen Arcs of W Norway, Caledonian eclogite facies assemblages (T≥650°C, P≥15 kbar) have formed from Grenvillian granulites (T= 800–900°C, P≥10 kbar) along shear zones and fluid pathways. Garnets in the granulites (grtI: Pyr56–40 Alm45–25Gro19–14) are unzoned or display a weak (ca. 1 wt% FeO over 1000μm) zoning. The eclogite facies rocks contain garnets inherited from their granulite facies protoliths. These relict garnets have certain areas with compositions identical to the garnets in their nearby granulite, but can be crosscut by bands of a more Almrich composition (grtII: Pyr31–41Alm40–47Gro17–21) formed during the eclogite facies event. These bands, orientated preferentially parallel or perpendicular to the eclogite foliation, may contain mineral filled veins or trails of eclogite-facies minerals (omphacite, amphibole, white mica, kyanite, quartz and dolomite). Steep compositional gradients (up to 9 wt% FeO over 40 μm) separate the two generations of garnets, indicating limited volume diffusion. The bands are interpreted as fluid rich channels where element mobility must have been infinitely greater than it was for the temperature controlled volume diffusion at mineral interfaces in the granulites. The re-equilibration of granulite facies garnets during the eclogite facies event must, therefore, be a function of fracture density (deformation) and fluid availability. The results cast doubts on modern petrological and geochronological methods that assume pure temperature controlled chemical re-equilibration of garnets.

Time scales of large volume silicic magma systems: Sr isotopic systematics of phenocrysts and glass from the Bishop Tuff, Long Valley, California

Abstract: The initial Sr isotopic compositions of glass and mineral separates from the 0.74 Ma Bishop Tuff ashflow in eastern California were determined to investigate the time scales of magmatic processes in a large silicic system. It was found that there is substantial isotopic heterogeneity, both between eruptive units and between glass and phenocryst phases of individual units. The frist-erupted, lower temperature units generally have higher initial 87Sr/86Sr than later crupted, higher temperature units. Within each unit, feldspar phenocrysts have the lowest 87Sr/86Sr, associated glass has higher 87Sr/86Sr, and biotite phenocrysts have the highest 87Sr/86Sr. These isotopic differences were produced by processes in the magma chamber and not by post-eruptive alteration. Two samples were similar Fe−Ti oxide temperatures but from widely separated localities have nearly identifical Sr isotopic characteristics, indicating the existence of compositionally uniform layers of substantial volume within the chamber. Trace element data indicate that the feldspars crystallized from a liquid represented by the associated glass, and that the feldspar-glass pairs are not accidental. The rhyolitic liquids of the Bishoptuff magma chamber apparently experienced increasing 87Sr/86Sr at a rate too fast for feldspar phenocrysts to remain in isotopic equilibrium. The increasing 87Sr/86Sr is caused primarily by radioactive decay of 87Rb in the high-Rb/Sr liquids and not primarily by assimilation of radiogenic wall-rock material. A self-consistent model can be constructed to account for all of the isotopic data except for those on biotite phenocrysts. The time scale for evolution of the system is bounded on the high side at about 500 ky by observations made on precaldera lavas, and on the low side at approximately 300 ky by the time necessary to establish homogeneous layers in an actively differentiating chamber. The deduced time scale is consistent with model Rb−Sr ages, which date the differentiation of low temperature liquids from higher temperature liquids, and is compatible with the observed isotopic disequilibrium between feldspars and glass because of the low diffusivity of Sr in fieldspars ( 3x105 years. The silicic-magma production rate within the Bishop Tuff magma chamber is estimated to be 10-3km3/y. The growth rate of alkali feldspar is estimated to be about 10-14 cm/s based on the Sr isotopic difference between sanidine and glass of the lower Bishop Tuff. The biotite population is inferred to be partially (>50 ppm) xenocrystic, the xenocrysts being introduced to the chamber less than one year prior to eruption.

Stable isotope geochemistry and phase equilibria of coesite-bearing whiteschists, Dora Maira Massif, western Alps

Abstract: Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The δ18O(smow) values of the quartz (after coesite) (δ18O=8.1 to 8.6‰, n=6), phengite (6.2 to 6.4‰, n=3), kyanite (6.1‰, n=2), garnet (5.5 to 5.8‰, n=9), ellenbergerite (6.3‰, n=1) and rutile (3.3 to 3.6‰, n=3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700–750 °C. Minimum pressures are 31–32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc+kyanite=pyrope+coesite+H2O, the a(H2O) must be reduced to 0.4–0.75 at 700–750 °C. The reduced a(H2O) cannot be due to dilution by CO2, as pyrope is not stable at X(CO2)>0.02 (T=750 °C; P=30 kb). In the absence of a more exotic fluid diluent (e.g. CH4 or N2), a melt phase is required. Granite solidus temperatures are ∼680 °C/30 kb at a(H2O)=1.0 and are calculated to be ∼70°C higher at a(H2O)=0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H2O) estimates for the whiteschist are 34±2 kb, 700–750 °C and 0.4–0.75. The oxygen isotope fractionation between quartz (δ18O=11.6‰) and garnet (δ18O=8.7‰) in the surrounding orthognesiss is identical to that in the coesitebearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (δD(SMOW)=-27 to-32‰), on secondary talc and chlorite rite after pyrope (δD=-39 to -44‰) and on the surrounding biotite (δD=-64‰) and phengite (δD=-44‰) gneiss. All phases appear to be in nearequilibrium. The very high δD values for the primary hydrous phases is consistent with an initial oceanicderived/connate fluid source. The fluid source for the retrograde talc+chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar δD, but dissimilar δ18O values of the coesite bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.

Fluid absent melting of a layered crustal protolith: implications for the generation of anatectic granites

Abstract: We report the result of H2O-undersaturated melting experiments on charges consisting of a layer of powdered sillimanite-bearing metapelite (HQ36) and a layer of powdered tonalitic gneiss (AGC150). Experiments were conducted at 10 kbar at 900°, 925° and 950°C. When run alone, the pelite yielded ∼40 vol% strongly peraluminous granitic melt at 900°C while the tonalite produced only ∼5 vol% weakly peraluminous granitic melt. At 950°C, the pelite and the tonalite yielded ∼50 vol% and ∼7 vol% granitic melt, respectively. When run side by side, the abundance of melt in the tonalite was ∼10 times higher at all temperatures than when it was run alone. In the pelite, the melt abundance increased by ∼25 vol%. When run alone, biotite dehydration-melting in the tonalite yielded orthopyroxene and garnet in addition to granitic melt. When run side by side only garnet was produced in addition to granitic melt. Experiments of relatively short duration, however, also contained Al-rich orthopyroxene. We suggest that the large increase in melt fraction in the tonalite is mainly a result of increased activity of Al2O3 in the melt, which lowers the temperature of the biotite dehydration-melting reaction. In the pelite, the increase in the abundance of melt is caused by transport of plagioclase component in the melt from the tonalite-layer to the pelite-layer. This has the effect of changing the bulk composition of this layer in the direction of “minimum-temperature” granitic liquids. Our results show that rocks which are poor melt-producers on their own can become very fertile if they occur in contact with rocks that contain components that destabilize the hydrous phase(s) and facilitate dehydration-melting. Because of this effect, the continental crust may have an even greater potential for granitoid melt production than previously thought. Our results also suggest that many anatectic granites most likely contain contributions from two or more different source rocks, which will be reflected in their isotopic and geochemical compositions.

Isotope and trace element evidence for three component mixing in the genesis of the North Luzon arc lavas (Philippines)

Abstract: Post-3Ma volcanics from the N Luzon arc exhibit systematic variations in 87Sr/86Sr (0.70327–0.70610), 143Nd/144Nd (0.51302–0.51229) and 208Pb*/206Pb* (0.981–1.035) along the arc over a distance of about 500 km. Sediments from the South China Sea west of the Manila Trench also exhibit striking latitudinal variations in radiogenic isotope ratios, and much of the isotopic range in the volcanics is attributed to variations in the sediment added to the mantle wedge during subduction. However, Pb-Pb isotope plots reveal that prior to subduction, the mantle end-member had high Δ8/4, and to a lesser extent high Δ7/4, similar to that in MORB from the Indian Ocean and the Philippine Sea Plate. Th isotope data on selected Holocene lavas indicate a source with unusually high Th/U ratios (4.5–5.5). Combined trace element and isotope data require that three end-members were implicated in the genesis of the N Luzon lavas: (1) a mantle wedge end-member with a Dupal-type Pb isotope signature, (2) a high LIL/HFS ‘subduction component’ interpreted to be a slab-derived hydrous fluid, and (3) an isotopically enriched end-member which reflects bulk addition (<5%) of subducted S China Sea terrigenous sediment. The 87Sr/86Sr ratios in the volcanics show a restricted range compared with that in the sediments, and this contrasts with 143Nd/144Nd and 208Pb*/206Pb*, both of which have similar ranges in the volcanics and sediments. Such differences imply that whereas the isotope ratios of Nd, Pb and Th are dominated by the component from subducted sediment, those of Sr reflect a larger relative contribution from the slab-derived fluid.

An experimental study of Fe-Mg partitioning between olivine and orthopyroxene at 1173, 1273 and 1423 K and 1.6 GPa

Abstract: The partitioning of Mg and Fe2+ between coexisting olivines and orthopyroxenes in the system MgO-FeO-SiO2 has been investigated experimentally at 1173, 1273, 1423 K and 1.6 GPa over the whole range of Mg/Fe ratios. The use of barium borosilicate as a flux to promote grain growth, and the identification by back-scattered electron imaging of resulting growth rims suitable for analysis by electron microprobe, results in coexisting olivine and orthopyroxenene compositions determined to a precision of±0.003 to 0.004 in molar Fe/(Mg+Fe). Quasi-reversal experiments were performed starting with Mg-rich olivine and Fe-rich orthopyroxene (low KD) and vice versa (high KD), which produced indistinguishable results. The distribution coefficient, KD, depends on composition and on temperature, but near Fe/(Mg+Fe)=0.1 (i.e. mantle compositions) these effects cancel out, and KD is insensitive to temperature. The results agree well with previous experimental investigations, and constrain the thermodynamic mixing properties of Mg-Fe olivine solid solutions to show small near-symmetric deviations from ideality, with \(W_{G_{Mg - Fe}^{ol} }\) between 2000 and 8000 J/mol. Multiple non-linear least squares regression of all data gave a best fit with \(W_{G_{Mg - Fe}^{ol} } = 5625 \pm 574 J/mol\) (implying 5450 J/mol at 1 bar) and \(W_{G_{Mg - Fe}^{opx} } = 2145 \pm 614 J/mol\), but the two WG parameters are so highly correlated with each other that our data are almost equally well fit with \(W_{G_{Mg - Fe}^{ol} } = 3700 \pm 800 J/mol\), as obtained by Wiser and Wood. This value implies \(W_{G_{Mg - Fe}^{opx} } = 280 \pm 900 J/mol\), apparently independent of temperature. Our experimental results are not compatible with the assessment of olivine-orthopyroxene equilibria of Sack and Ghiorso.

Low-calcium garnet harzburgites from southern Africa: their relations to craton structure and diamond crystallization

Abstract: Low-Ca garnet harzburgite xenoliths contain garnets that are deficient in Ca relative to those that have equilibrated with diopside in the iherzolite assemblage. Minor proportions of these harzburgites are of wide-spread occurrence in xenolith suites from the Kaapvaal craton and are of particular interest because of their relation to diamond host rocks. The harzburgite xenoliths are predominantly coarse but one specimen from Jagersfontein and another from Premier have deformed textures similar to those of high-temperature peridotites. Analyses for many elements in the harzburgites and associated iherzolites form concordant overlapping trends. On the average, however, the harzburgites are deficient in Si, Ca, Al and Fe but enriched in Mg and Ni relative to the lherzolites. Both the harzburgites and lherzolites are enstatite-rich with mg numbers [100.Mg/(Mg+Fetotal)] greater than 92 and in these respects differ markedly from residues generated by extraction of MORB. Equilibration temperatures and depths calculated for the harzburgites have the ranges 600–1,400°C and 50–200 km. Those of deepest origin overlap the interval between low-and high-temperature lherzolites that commonly is observed in temperature-depth plots for the Kaapvaal craton, suggesting that some harzburgites may be concentrated relative to lherzolites at the base of the lithosphere. The low-Ca harzburgites and lherzolite xenoliths have overlapping depths of origin, gradational bulk chemical characteristics and similar textures, and therefore both are believed to have formed as residues of Archaen melting events. The harzburgites differ from the lherzolites only in that they are more depleted. Garnets and associated minerals in harzburgite xenoliths differ from minerals of the same assemblage that are included in diamonds in that the latter are more Cr-rich, Mg-rich and Ca-poor. Coarse crystals of low-Ca garnet with the compositional characteristics of diamond inclusions commonly occur as disaggregated grains in diamondiferous kimberlites. Their host rocks are presumed to have been harzburgites and dunites. The differences in composition between the disaggregated grains that are similar to diamond inclusions and those comprising xenoliths imply some differences in origin. Possibly the disaggregated harzburgites with diamond-inclusion mineralogy have undergone repeated partial melting and depletion near the base of the lithosphere subsequent to their primary depletion and aggregation in the craton. Equilibration with magnesite may have reduced the Ca contents of their garnets and decomposition of the magnesite during eruption may have caused their disaggregation.

Subsolidus reactions monitored by trace element partitioning: the spinel- to plagioclase-facies transition in mantle peridotites

Abstract: Mantle peridotites of the External Liguride (EL) Units (Northern Apennines) mainly consist of fertile spinel-lherzolites partially recrystallized to plagioclase-facies assemblages, and are consequently appropriate to investigate the interphase element partitioning related to the transition from spinel- to plagioclase-facies stability field. Evidence for the development of the plagioclase-facies assemblage is mainly given by: (1) large exsolution lamellae of orthopyroxene and plagioclase within spinel-facies clinopyroxene; (2) plagioclase rims around spinel; (3) granoblastic domains made up of olivine+plagioclase±clino-and orthopyroxene. In situ major and trace [REE (rare-earth elements), Ti, Sc, V, Cr, Sr, Y, Zr and Ba] element mineral analyses have been performed, by electron and ion probe, on selected samples which show the progressive development of the plagioclase-bearing assemblage. The main compositional variations observed during the change from spinel- to plagioclase-facies minerals are as follows: (1) clinopyroxenes decrease in Al, Na, Sr, Eu/Eu* and increase in Y, V, Sc, Cr, Zr and Ti; (2) amphiboles decrease in Eu/Eu*, Sr, Ba and increase in Zr and V; (3) spinels decrease in Al and increase in Cr and Ti. The most striking feature is the decoupling in the behaviour of similarly incompatible elements (D about 0.1) in clinopyroxene, e.g. Sr decrease is mirrored by Zr increase. Massbalance calculations indicate that the trace element interphase redistribution documented in the EL peridotites occurred in a closed system and in response to the metamorphic reaction governing the transition from the spinel- to the plagioclase-facies stability field. The observed element partitioning reveals, moreover, that subsolidus re-equilibration processes in the upper mantle produce HFSE (high-field-strength element)/REE fractionation in minerals, which must be evaluated for a reliable determination of mineral-melt distribution coefficients. The results of this study furnish evidence for subsolidus metamorphic evolution during decompression, without concomitant partial melting processes. This is consistent with the interpretation that the EL peridotites represent subcontinental lithospheric mantle emplaced at the surface in response to lithospheric thinning and tectonic denudation mechanisms related to the Triassic-Jurassic rifting of the Ligure-Piedmontese basin.

Two-feldspar geothermometry: a review and revision for slowly cooled rocks

Abstract: Recent improvements in the experimental and thermodynamic basis of two-feldspar geothermometry allow one to recover temperatures of coexistence more reliably. Some problems, however, persist: (1) the experimental solvi by Seck (1971a) and Elkins and Grove (1990) differ from each other; (2) it is not known to what extent Na−K−Ca exchange equilibrium is approached; (3) both solvi are probably metastable with regard to Al, Si order; (4) it is difficult to judge how closely high-temperature natural feldspars compare to this situation; (5) the thermodynamic treatment neglects phase transformations; (6) the temperature dependence of the Margules parameters used to model non-ideal mixing behaviour may not be linear; (7) it is not clear which expressions should be used to describe ideal activities. With these caveats in mind we treat the problem of retrograde resetting in high-grade metamorphic rocks that were slowly cooled under essentially dry conditions. Coexisting feldspars from such rocks commonly do not plot on a common isotherm. Thus temperatures derived from such pairs using any of the proposed two-feldspar geothermometers will necessarily be in error. We suggest that the non-equilibrium compositions result from retrograde intercrystalline K−Na exchange. This exchange continues after the plagioclase and alkali feldspar have already become essentially closed systems with respect to Al−Si exchange, which is a prerequisite for (Na,K)−Ca exchange. We use a modified version of the Fuhrman and Lindsley (1988) programme to reverse the K−Na exchange and derive concordant temperatures.