Showing papers in "Contributions to Mineralogy and Petrology in 1995"

Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures

Abstract: A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe2+,Ca)-olivines, (Na,Mg,Fe2+,Ca)M2 (Mg,Fe2+, Ti, Fe3+, Al)M1 (Fe3+, Al,Si)2TETO6-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe2+) (Fe3+, Al, Cr)2O4-(Mg,Fe2+)2 TiO4 spinels and (Fe2+, Mg, Mn2+)TiO3-Fe2O3 rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the fo2 or the T-P-fo2 (or equivalently H-P-fo2, S-P-fo2, T-V-fo2) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.

Genesis of high Mg# andesites and the continental crust

Abstract: The continental crust has an andesitic composition with high Mg/(Mg+Fe) and Ni contents which may be too high to have formed by differentiation of basaltic magmas. Instead, mantle-derived, high Mg# andesites (HMA) may form a substantial component of the crust. HMA may be produced by partial melting of previously depleted, subsequently metasomatised mantle peridotite. However, they are more likely produced by reaction between ascending melts and mantle peridotite. HMA are less common than basalts among lavas in modern island arcs, but may have been more common in the past, may be produced in specific environments (such as “ridge subduction”), may be more common among plutonic rocks in the lower and middle crust than among lavas at the surface, and may be selectively preserved during later erosion and subduction processes.

Comparative study of yttrium and rare-earth element behaviours in fluorine-rich hydrothermal fluids

Abstract: The mineral ‘fluorite’ is utilized as a probe to investigate the behaviour of the pseudolanthanide yttrium with respect to the lanthanides (rare-earth elements, REE) in fluorine-rich hydrothermal solutions Hydrothermal vein fluorites are characterized by the close association of Y and REE, but in contrast to igneous and clastic rocks they show variable and nonchondritic Y/Ho ratios of up to 200 This suggests that Y and Ho, although similar in charge and size, may be fractionated in fluorine-rich medium-temperature aqueous fluids In such solutions Y acts as a pseudolanthanide heavier than Lu Y/Ho ratios of hydrothermal siderites are slightly below those of chondrites, suggesting that in (bi)carbonate-rich siderite-precipitating solutions Y may act as a Sm-like light pseudolanthanide This indicates that Y-Ho fractionation is not a sourcerelated phenomenon but depends on fluid composition Based on these results it is strongly recommended that discussions of normalized REE patterns in general should be extended to normalized Rare-Earth-and-Yttrium (REY) patterns (Y inserted between Dy and Ho), because the slightly variable behaviour of the pseudolanthanide yttrium with respect to the REE may provide additional geochemical information Available thermodynamic data suggest a negative correlation between Y/Ho and La/Ho during migration of a fluoriteprecipitating hydrothermal solution Cogenetic fluorites, therefore, should display either similar Y/Ho and similar La/Ho ratios, or a negative correlation between these ratios This criterion may help to choose samples suitable for Sm-Nd isotopic studies prior to isotope analysis However, in cogenetic hydrothermal vein fluorites the range of Y/Ho ratios is often almost negligible compared to the range of La/Ho ratios This may be explained by modification of REE distributions by post-precipitation processes involving (partial) loss of a separate LREE-enriched phase The presence of variable amounts of such an accessory phase in most fluorite samples is revealed by experiments employing stepwise incomplete fluorite decomposition Fluorites derived from and deposited near to igneous rocks apparently display chondritic Y/Ho ratios close to those of their igneous source-rocks However, a positive YSN anomaly is likely to develop as the distance between sites of REY mobilization and deposition increases

Oxygen isotope heterogeneity of the mantle deduced from global 18 O systematics of basalts from different geotectonic settings

Abstract: Based upon a compilation and analysis of O-isotope data for Neogene volcanic rocks worldwide, the δ18O variation for 743 basalts (historic lavas, submarine glasses, and lavas with <0.75 wt% H2O) is +2.9 to +11.4‰. Mid-ocean-ridge basalt (MORB) has a uniform O-isotope composition with δ180=+5.7±0.2‰. Basalts erupted in different tectonic settings have mean 18O/16O ratios that are both lower and higher than MORB, with continental basalts enriched in 18O by ca. 1‰ over oceanic basalts. The δ18O range for the subset of 88 basalts with Mg# [100·Mg(Mg+Fe2+)] 75–68, considered to be unmodified primary mantle partial melts, is +3.6 to +8.7‰. These features are a clear indication that: (1) the Earth's upper mantle is heterogeneous with respect to its O-isotope composition; (2) that both low-18O and high-18O reservoirs have contributed to basalt petrogenesis. Large-ion lithophile element-enriched basalts associated with subduction at convergent plate margins are slightly enriched in 18O, a characteristic that is considered to be an intrinsic feature of the subduction process. Intraplate oceanic and continental basalts have highly variable 18O/16O ratios, with individual localities displaying δ18O ranges in excess of 1.5 to 2‰. Systematic co-variations between O-, Sr-, Nd-, and Pb-isotope ratios reflect the same principal intramantle end-member isotopic components (DMM, HIMU, EM-I, EM-II) deduced from radiogenic isotope considerations and, therefore, imply that a common process is responsible for the origin of upper mantle stable and radiogenic isotope heterogeneity, namely the recycling of lithospheric material into the mantle.

An experimental study of the effects of melt composition on plagioclase - melt equilibria at 5 and 10 kbar: implications for the origin of magmatic high-An plagioclase

Abstract: An experimental investigation of plagioclase crystallization in broadly basaltic/andesitic melts of variable Ca# (Ca/(Ca+Na)*100) and Al# (Al/(Al+Si)*100) values and H2O contents has been carried out at high pressures (5 and 10 kbar) in a solid media piston-cylinder apparatus. The H2O contents of glasses coexisting with liquidus or near-liquidus plagioclases in each experiment were determined via an FTIR spectroscopic technique. This study has shown that melt Ca# and Al#, H2O content and crystallization pressure all control the composition of liquidus plagioclase. Increasing melt Ca# and Al# increase An content of plagioclase, whereas the effect of increasing pressure is the opposite. However, the importance of the role played by each of these factors during crystallization of natural magmas varies. Melt Ca# has the strongest control on plagioclase An content, but melt Al# also exerts a significant control. H2O content can notably increase the An content of plagioclase, up to 10 mol% for H2O-undersaturated melts, and 20 mol% for H2O-saturated melts. Exceptionally calcic plagioclases (up to An100) in some primitive subduction-related boninitic and related rocks cannot be attributed to the presence of the demonstrated amounts of H2O (up to 3 wt%). Rather, they must be due to the involvement of extremely refractory (CaO/Na2O>18) magmas in the petrogenesis of these rocks. Despite the refractory nature of some primitive MORB glasses, none are in MORB. These plagioclases were likely produced from more refractory melts with CaO/Na2O=12–15, or from melts with exceptionally high Al2O3(>18%). Magmas of appropriate compositions to crystallize these most calcic plagioclases are sometimes found as melt inclusions in near liquidus phenocrysts from these rocks, but are not known among wholerock or glass compositions. The fact that such melts are not erupted as discrete magma batches indicates that they are effectively mixed and homogenized with volumetrically dominant, less refractory magmas. The high H2O contents (∼6 wt%) in some high-Al basaltic arc magmas may be responsible for the existence of plagioclases up to An95 in arc lavas. However, an alternative possibility is that petrogenesis involving melts with abnormally high CaO/Na2O values (>8) may account for the presence of highly anorthitic plagioclases in these rocks.

Partial melting and phase relations in high-grade metapelites: an experimental petrogenetic grid in the KFMASH system

Abstract: Petrogenetic grids are a powerful tool for understanding metamorphic terrains and many theoretical grids have been suggested for the process of granulite formation in metapelitic rocks, via fluid-absent biotite melting reactions. However, application of these grids has been difficult due to the lack of suitable experimental constraints. We present here an experimentally determined and tightly constrained petrogenetic grid for KFMASH system metapelites which extends from 840–1000°C and 5.0–12.5 kbar. Sixty four experiments on three KFMASH, mineral-mix, bulk compositions (XMg=0.62, 0.74, 0.86) provide phase composition and assemblage data from which a grid can be derived and constrained. Reversal experiments and consideration of the phase composition data show the experiments to be close to equilibrium. The KFMASH univariant fluid-absent biotite melting reactions occur between 850 and 870°C at 5 kbar and between 900 and 915°C at 10 kbar. These reactions are connected to equilibria beyond the stability of biotite to develop a fixed framework within which the phase assemblage evolution of metapelitic rocks can be interpreted. The effect of minor components on phase equilibria is evaluated using the experimentally determined grid as a simple-system reference. The temperature at which melting occurs in metapelites is strongly controlled by the concentrations of titanium and fluorine in biotite. Pressure-temperature pseudosections presented for each of the experimental compositions show both the univariant and divariant reactions available to a particular bulk composition, clearly illustrating the possible evolution of the phase assemblage. The pseudosections also constrain the stability limits of

A clinopyroxene geobarometer for basaltic systems based on crystal-structure modeling

Abstract: The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar) = 698.443 + 4.985-AlT - 26.826-Fe M1 2+ - 3.764-Fe3+ + 53.989-AlM1 + 3.948-Ti + 14.651.Cr - 700.431.Ca - 666.629.Na - 682. 848-MgM2 - 691.138-Fe M2 2+ - 688.384-Mn - 6.267-(MgM2)2 -4.144-(Fe M2 2+ ) where: (Fe M1 2+ -MgM2)/(Fe M2 2+ -MgM1) = e**(0.238-R3+ + 0.289.CNM - 2.315), CNM = Ca + Na + Mn, and R3+ = A1M1 + Fe3+ + Ti + Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within α 2 kbar (= 1 σ max. dev. ≤ 5 kbar; N = 29) in the range 0-24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al2O3 basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, αCaO and αSi02 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from high-er-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of A12O3 (< 18 wt%), variations of major elements in the melt do not reduce the accuracy of the geobarometer.

Textural evolution of synthetic fluid inclusions in quartz during reequilibration, with applications to tectonic reconstruction

Abstract: Experimental reequilibration of synthetic 10 wt% NaCl-H2O inclusions in natural quartz reveals that reequilibration textures show distinct differences depending upon the P-T path followed by the inclusion after formation. These differences combined with other geological information may be used to determine whether the sample (rock) followed a dominantly isothermal or isobaricP-T path following entrapment. The intensity and style of inclusion reequilibration features is related to the direction and magnitude of the departure of theP-T path from the original isochore for the inclusion. Thus, fluid inclusion reequilibration textures not only permit inclusionists to determine whether the rocks followed an isothermal or isobaric retrogradeP-T path, but also the magnitude of departure of this path from one that is isochoric.

Late Archaean crust-mantle interactions: geochemistry of LREE-enriched mantle derived magmas. Example of the Closepet batholith, southern India

Abstract: The Closepet batholith in South India is generally considered as a typical crustal granite emplaced 2.5 Ga ago and derived through partial melting of the surrounding Peninsular Gneisses (3.3 to 3.0 Ga). In the field, it appears as a composite batholith made up of at least two groups of intrusions. (a) An early SiO2-poor group (clinopyroxene quartz-monzonite and porphyritic phyritic monzogranite) is located in the central part of the batholith. These rocks display a narrow range in both initial 87Sr/86Sr (0.7017–0.7035) and ɛNd(−0.9to −4.1). (b) A later SiO2-rich group (equigranular grey and pink granites) is located along the interface between the SiO2-poor group and the Peninsular Gneisses. They progressively grade into migmatised Peninsular Gneisses, thus indicating their anatectic derivation. Their isotopic characteristics vary over a wide range (87Sr/86Sr ratios=0.7028–0.7336 and ɛNd values from-2.7 to-8.3, at 2.52 Ga). Field and geochronological evidence shows that the two groups are broadly contemporaneous (2.518–2.513 Ga) and mechanically mixed. This observation is supported by the chemical data that display well defined mixing trends in the ɛSr vs ɛNd and elemental variation diagrams. The continuous chemical variation of the two magmatic bodies is interpreted in terms of interaction and mixing of two unrelated end-members derived from different source regions (enriched peridotitic mantle and Peninsular Gneisses). It is proposed that the intrusion of mantle-derived magmas into mid-crustal levels occurred along a transcurrent shear zone; these magmas supplied additional heat and fluids that initiated anatexis of the surrounding crust. During this event, large-scale mixing occurred between mantle and crustal melts, thus generating the composite Closepet batholith. The mantle-derived magmatism is clearly associated with granulite facies metamorphism 2.51±0.01 Ga ago. Both are interpreted as resulting from a major crustal accretion event, possibly related to mantle plume activity.

Evidence for excess argon during high pressure metamorphism in the dora maira massif (Western Alps, Italy), using an ultra-violet laser ablation microprobe 40 Ar- 39 Ar technique

Abstract: Ultra-high pressure eclogite/amphibolite grade metamorphism of the Dora Maira Massif in the western Alps is a well established and intensively studied event. However, the age of peak metamorphism and early cooling remains controversial. The 40Ar-39 Ar step-heating and laser spot ages from high pressure phengites yield plateau ages as old as 110 Ma which have been interpreted as the time of early cooling after the high pressure event. Recent U/Pb and Sm/Nd results challenge this assertion, indicating a much younger age for the event, around 45 Ma, and hence a radically different timing for the tectonic evolution of the western Alps. In a new approach to the problem, samples from the undeformed Hercynian metagranite, Brossasco, were studied using an ultra-violet laser ablation microprobe technique for 40Ar-39 Ar dating. The new technique allowed selective in situ analysis, at a spatial resolution of 50 urn, of quartz, phengite, biotite and K-feldspar. The results demonstrate the frequent occurrence of excess argon with high 40Ar-39 Ar ratios (1000–10000) and a strong relationship between apparent ages and metamorphic textures. The highest excess argon ratios are always associated with high closure temperature minerals or large diffusion domains within single mineral phases. The best interpretation of this relationship seems to be that excess argon was incorporated in all phases during the high pressure event, then mixed with an atmospheric component during rapid cooling and retrogression, producing a wide range of argon concentrations and 40Ar/36Ar ratios. Step-heating analysis of minerals with this mixture would produce linear arrays on a40Ar/36Ar versus 40Ar/36 Ar correlation diagram, leading to geologically meaningless plateau ages, older than the true closure age. In the present case, some ages in the range 60–110 Ma could be explained by the presence of excess argon incorporated around 40–50 Ma ago. Similar results found in other high pressure terrains in the Alps may reconcile the argon geochronometer with other systems such as Rb/Sr, U/Pb or Sm/Nd. This study therefore calls for an increasing use of high resolution in situ sampling techniques to clarify the meaning of 40Ar/ 36 Ar ages in many high pressure terrains.

Reassessment of the garnet-clinopyroxene Fe-Mg exchange thermometer: II. Thermodynamic analysis

Abstract: The garnet (Grt)-clinopyroxene (Cpx) Fe-Mg exchange thermometer has been re-evaluated through analysis of phase equilibrium experiments defining the Fe-Mg exchange between Grt and Cpx, Grt and O1 (O1 = Olivine), and Cpx and O1, together with ther- mophysical and other phase equilibrium constraints on solid solution and individual end-member properties. Results show that all data are mutually compatible if the heterogeneity range of Grt and Cpx in run products previously obtained by Pattison and Newton (PN) are accounted for in assessing equilibrium Grt-Cpx com- positions. Derived mixing properties are in good agree- ment with results from numerous recent phase equilib- rium studies. Application of the newly calibrated ther- mometer to a number of amphibolite to granulite facies terrains indicatcs temperatures between 70 and 200 ~ C above PN's thermometer, and general compatibility with independent temperature estimates.

Multipath diffusion in geochronology

Abstract: Recent developments in microanalytical tools such as the ion and laser microprobe have revealed spatial distributions of radiogenic isotopes in minerals which cannot be explained by a simple volume diffusion mechanism. Although it is known that diffusion of a substance along extended defects (such as dislocations, exsolution lamellae, micropores, microfractures, fission tracks, etc.), which may serve as high-diffusivity pathways in a crystal, can significantly influence the bulk diffusivity of a mineral, this has largely been ignored in the field of geochronology. A general numerical model has been developed, which solves coupled multipath diffusion equations that describe the simultaneous diffusion of a solute species through both the crystal lattice (via volume diffusion) and high-diffusivity pathways (via short-circuit diffusion) under non-steady state conditions. Addition of a radioactive source term to the appropriate equations further allows for the modelling of integrated cooling ages and closure temperatures, and has direct pertinence to geochronological and thermochronologial studies. Three key criteria can be used to distinguish multipath diffusion mechanisms from volume diffusion mechanisms: (a) non-Fickian concentration profiles, (b) enhanced solute diffusivity with increasing mineral grain size, and (c) a lack of any correlation between closure temperatures (and cooling ages) and larger grain sizes. With multipath diffusion, the effective diffusion dimension a for certain minerals appears to remain on the order of the grain size, and the model can adequately explain observed increases in the bulk diffusion coefficient D b with a in the hydrothermal bomb data of previous Ar diffusion studies. Arrhenius diagrams of a multipath diffusion D b vs 1/T will consist of curves that have a kink in them, reflecting a continuous change in the relative importance of the different diffusion mechanisms with temperature. The most important consequence of multipath diffusion is that the overall bulk diffusion coefficient D b of a diffusing species can be enhanced significantly above its volume diffusion coefficient D v . As a result, integrated ages and effective closure temperatures (T c ) can be much lower than those predicted assuming only a volume diffusion mechanism, to the extent that minerals normally characterized by low volume-diffusion T c may potentially have older integrated ages that minerals normally associated with higher volume-diffusion T c .

Pb-Sr-Nd isotopic compositions and trace element geochemistry of megacrysts and melilitites from the Tertiary Urach volcanic field: source composition of small volume melts under SW Germany

Abstract: The Urach volcanic field is unique within the Tertiary–Quaternary European volcanic province (EVP) due to more than 350 tuffaceous diatremes and only sixteen localities with extremely undersaturated olivine melilitite. We report representative Pb-Sr-Nd isotopic compositions and incompatible trace element data for twenty-two pristine augite, Cr-diopside, hornblende, and phlogopite megacryst samples from the diatremes, and seven melilitite whole rocks. The Pb isotopic compositions for melilitites and comagmatic megacrysts have very radiogenic 206Pb/204Pb ratios of 19.4 to 19.9 and plot on the northern hemisphere mantle reference line (NHRL). The data indicate absence of an old crustal component as reflected in the high 207Pb/204Pb ratios of many basalts from the EVP. This inference is supported by 206Pb/204Pb ratios of ∼17.6 to 18.3 and ɛNd of ∼−7.8 to +1.6 for five phlogopite xenocryst samples reflecting a distinct and variably rejuvenated lower Hercynian basement. The 87Sr/86Sr ratios of 0.7033 to 0.7035 in the comagmatic megacrysts are low relative to their moderately radiogenic Nd isotopic compositions (ɛNd +2.2 to +5.1) and consistent with a long-term source evolution with a low Rb/Sr ratio and depletion in light rare-earth elements (LREE). The melilitite whole-rock data show a similar range in Nd isotopic ratios as determined for the megacrysts but their Sr isotopic compositions are often much more radiogenic due to surface alteration. The REE patterns and incompatible trace element ratios of the melilitites (e.g. Nb/Th, Nb/U, Sr/Nd, P/Nd, Ba/Th, Zr/Hf) are similar to those in ocean island basalts (OIB); negative anomalies for normalized K and Rb concentrations support a concept of melt evolution in the lithospheric mantle. Highly variable Ce/Pb ratios of 29 to 66 are positively correlated with La/Lu, La/K2O, and Ba/Nd and interpreted to reflect melting in the presence of residual amphibole and phlogopite. The data suggest an origin of the melilitites from a chemical boundary layer very recently enriched by melts from old OIB sources. We suggest that the OIB-like mantle domains represent low-temperature melting heterogeneities in an upwelling asthenosphere under western Europe.

Experimental modal metasomatism of a spinel lherzolite and the production of amphibole-bearing peridotite

Abstract: Experiments have been done which simulate the modal metasomatism of spinel lherzolite by partial melts of the subducted slab. The experiments were designed so that the metasomatizing melts were generated during the experiments by partial melting of a slab analog (basaltic composition amphibolite). The melts are thought to be representative of hybridizing melts in that they are derived by high-pressure partial melting under conditions appropriate to a hot slab geotherm. During the experiments, the melts infiltrate into and metasomatize a model depleted peridotite. Chemical modifications to minerals in the peridotite are of the same nature and extent as those found in naturally metasomatized spinel lherzolites. Modal metasomatism produced pargasitic amphiboles in runs at 1.5 GPa and in all but the highest temperature run at 2.0 GPa. The amphiboles are indistinguishable from amphiboles found in amphibole-bearing peridotites from supra-subduction zone environments. Systematic variations in amphibole composition suggest that the melt infiltration process in the experiments involved continuous modification of the composition of the infiltrating melt as observed around inferred quenched melt (i.c., amphibolite or amphibolite/clinopyroxenite) veins in xenoliths and massif peridotites. The compositions of the initial and final mineral phases in the experiments and those of the metasomatizing melts are used to derive amphibole formation reactions at 1.5 and 2.0 GPa that are similar in form to those inferred in studies of natural amphibole-bearing peridotites. The metasomatism reactions show that the extent of amphibole formation in peridotite at 1.5 and 2.0 GPa will, in general, be limited by clinopyroxene and spinel abundance.

Melilitites: partial melts of the thermal boundary layer?

Abstract: Silica-poor, calcium-rich melilitites form a chemical and isotopic end-member of the spectrum of mafic magmas of the Tertiary-Quaternary volcanic province of western and central Europe. We propose that these unusual magmas are derived by partial melting of the thermal boundary layer (TBL) at the base of the European lithosphere. The processes involved in the evolution of the TBL have been constrained using major and trace element and Nd-Sr-Pb isotope data for Tertiary melilitites from the Urach, Hegau, and Rhine graben regions of Germany. The initiation of boundary layer evolution is limited in time by a major phase of Permo-Carboniferous rifting and associated magmatism postdating the Hercynian orogeny which would have destroyed the existing TBL by delamination. Model calculations indicate that the isotopic composition of the melilitite source cannot develop within the TBL over geologically reasonable periods of time (250–300 Million years) if the TBL evolves solely by incorporation of small degree (<0.1%) partial melts from an underlying, convecting, depleted (MORB-source) mantle reservoir. On the basis of this observation, the regional geodynamic setting and the melilitite data, we propose that an isotopically distinct mantle plume, impinging on the base of the European lithosphere during the Early Cenozoic, is involved in the petrogenesis of the melilitite magmas.

Paleoproterozoic (1.90–1.86 Ga) arc volcanism in the Flin Flon Belt, Trans-Hudson Orogen, Canada

Abstract: Geochemical and isotopic (Nd, Sr) data are reported on Paleoproterozoic (1904–1864 Ma), maficintermediate ( 1870 Ma) collision and subsequent intra-arc deformation.

Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif, Western Alps): implications for element recycling during subduction

Abstract: Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfiuorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyro-pe-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO2-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preser ved. In contrast, the kyanite inclusions in pyrope preserve primary H2O-CO2 low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO2 in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H2O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO2 and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a H 2 O rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous ( < 1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.

Experimental tests of garnet peridotite oxygen barometry

Abstract: We have performed experiments aimed at testing the calibration of oxygen barometers for the garnet peridotite [garnet (Gt)-olivine (Ol)-orthopyroxene (Opx)] phase assemblage. These involved equilibrating a thin layer of garnet sandwiched between layers of olivine and orthopyroxene at 1300°C and 23–35 kbar for 1–7 days. Oxygen fugacity was controlled (but not buffered) by using inner capsules of Fe−Pt alloy or graphitc or molybdenum sealed in welded Pt outer capsules. Post-experiment measurement of fO2 was made by determining the compositions of Pt-Fe alloy sensors at the interface between garnet and olivine + orthopyroxene layers. The composition of alloy in equilibrium with olivine + orthopyroxene was approached from Fe-oversaturated and Fe-undersaturated conditions in the same experiment with, in general, excellent convergence. Product phase compositions were determined by electron microprobe and a piece of the garnet layer saved for 57Fe Mossbauer spectroscopy. The latter gave the Fe3+ content of the garnet at the measured P-T-fO2 conditions. Approach to equilibrium was checked by observed shifts in Fe3+ content and by the approach of garnet-olivine Fe−Mg partitioning to the expected value. The compositions of the phases were combined with mixing properties and thermodynamic data to calculate an apparent fO2 from two possible garnet oxybarometers:- (1) $$\begin{gathered} 2Ca_3 Fe_2 Si_3 O_{12} + 2Mg_3 Al_2 Si_3 O_{12} + 4FeSiO_3 = 2Ca_3 Al_2 Si_3 O_{12} \hfill \\ Gt Gt Opx Gt \hfill \\ + 8FeSi_{0.5} O_2 + 6MgSiO_3 + O \hfill \\ Ol Opx \hfill \\ \end{gathered} $$ and (2) $$\begin{gathered} 2Fe_3 Fe_2 Si_3 O_{12} = 8FeSi_{0.5} O_2 + 2FeSi_3 O_2 \hfill \\ Gt Ol Opx \hfill \\ \end{gathered} $$ Comparison of calculated fO2s with those measured by the Pt-Fe sensors demonstrated that either barometer gives the correct answer within the expected uncertainty. Data from the first (Luth et al. 1990) has an uncertainty of about 1.6 logfO2 units, however, while that from equilibrium (2) (Woodland and O'Neill 1993) has an error of +/- 0.6 log units, comparable to that of the spinel peridotite oxybarometer. We therefore conclude that equilibrium (2) may be used to calculate the fO2 recorded by garnet peridotites with an uncertainty of about +/- 0.6 log units, providing the potential to probe the oxidation environment of the deep continental lithosphere. Preliminary application based on data from Luth et al. (1990) indicates that garnet peridotite xenoliths from Southern Africa record oxygen fugacities about 3.0 log units below the FMQ (fayalite-magnetite-quartz) buffer. These are substantially more reducing conditions than those recorded by continental spinel lherzolites which typically give oxygen fugacities close to FMQ (Wood et al. 1990).

Melt inclusions in high-An plagioclase from the Gorda Ridge: an example of the local diversity of MORB parent magmas

Abstract: The use of ocean floor basalt chemistry as a tool to investigate mantle composition and processes requires that we work with basalts that have been modified little since leaving the mantle. One source of such basalts is melt inclusions trapped in primitive crystals. However, obtaining information from these melt inclusions is complicated by the fact that melt inclusions in natural basalts are essentially always altered by post-entrapment crystallization. This requires that we develop techniques for reconstructing the original trapped liquid compositions. We conducted a series of experiments to reverse the effects of post-entrapment crystallization by re-heating the host crystals to their crystallization temperature. For these experiments we used plagioclase crystals separated from a single Gorda Ridge lava. The crystallization temperature for these crystals was determined by a set of incremental re-heating experiments to be ∼1240–1260° C. The inclusions are primitive, high Ca-Al basaltic melts, saturated with plagioclase, olivine and Al-rich chromite at low pressure. The inclusion analyses can be linked to the host lava composition by low pressure fractionation. The major element composition of the re-homogenized melt inclusions within each crystal is relatively constant. However, the incompatible element analyses have extremely wide ranges. The range of La/Sm and Ti/Zr from inclusions analyzed from a single sample from the Gorda Ridge exceeds the range reported for lavas sampled from the entire ridge. The pyroxene compositions predicted to be in equilibrium with the melt inclusion trace element signature cover much of the range represented by pyroxenes from abyssal peridotites. The volumetric proportions of the magmas entering the base of the crust can be evaluated using frequency distribution of melt inclusion compositions. This distribution suggests that the array of magmas was skewed towards the more depleted compositions, with little evidence for an enriched component in this system. This pattern is more consistent with a dynamic flow model of the mantle or of a passive flow model where the melts produced in the peripheral areas of the melting regime were not focused to the ridge.

Metasomatism in mantle xenoliths from Gees, West Eifel, Germany: Evidence for the genesis of calc-alkaline glasses and metasomatic Ca-enrichment

Abstract: We have investigated new samples from the Gees mantle xenolith suite (West Eifel), for which metasomatism by carbonatite melt has been suggested. The major metasomatic change is transformation of harzburgites into phlogopite-rich wehrlites. Silicate glasses are associated with all stages of transformation, and can be resolved into two major groups: a strongly undersaturated alkaline basanite similar to the host magma which infiltrated the xenoliths during ascent, and Si-Al-enriched, variably alkaline glass present exclusively within the xenoliths. Si-Al-rich glasses (up to 72 wt% SiO2 when associated with orthopyroxene (Opx) are usually interpreted in mantle xenoliths as products of decompressional breakdown of hydrous phases like amphibole. In the Gees suite, however, amphibole is not present, nor can the glass be related to phlogopite breakdown. The Si-Al-rich glass is compositionally similar to glasses occurring in many other xenolith suites including those related to carbonatite metasomatism. Petrographically the silicate glass is intimately associated with the metasomatic reactions in Gees, mainly conversion of harzburgite orthopyroxene to olivine + clinopyroxene. Both phases crystallize as microlites from the glass. The chemical composition of the Si-Al-enriched glass shows that it cannot be derived from decompressional melting of the Gees xenoliths, but must have been present prior to their entrainment in the host magma. Simple mass-balance calculations, based on modal analyses, yield a possible composition of the melt prior to ascent of the xenoliths, during which glass + microlite patches were modified by dissolution of olivine, orthopyroxene and spinel. This parental melt is a calc-alkaline andesite (55–60 wt% SiO2), characterized by high Al2O3 (ca. 18 wt%). The obtained composition is very similar to high-alumina, calc-alkaline melts that should form by AFC-type reactions between basalt and harzburgite wall rock according to the model of Kelemen (1990). Thus, we suggest that the Si-Al-enriched glasses of Gees, and possibly of other suites as well, are remnants of upper mantle hybrid melts, and that the Gees suite was metasomatized by silicate and not carbonatite melts. High-Mg, high-Ca composition of metasomatic olivine and clinopyroxene in mantle xenoliths have been explained by carbonatite metasomatism. As these features are also present in the Gees suite, we have calculated the equilibrium Ca contents of olivine and clinopyroxene using the QUI1F thermodynamical model, to show that they are a simple function of silica activity. High-Ca compositions are attained at low a SiO2 and can thus be produced during metasomatism by any melt that is Opx-undersaturated, irrespective of whether it is a carbonatite or a silicate melt. Such low a SiO2 is recorded by the microlites in the Gees Si-Al-rich glasses. Our results imply that xenolith suites cannot confidently be related to carbonatite metasomatism if the significance of silicate glasses, when present, is not investigated.

Primary Ca-rich carbonatite magma and carbonate-silicate-sulphide liquid immiscibility in the upper mantle

Abstract: A primary carbonate phase with Ca/(Ca+Mg) in the range 0.85–0.95 has been identified in a metasomatized, depleted harzburgite nodule from Montana Clara Island, Canary Islands; textural relations show that this carbonate represents a quenched liquid. Although magnesian carbonate melts have been described from upper mantle peridotites, this is the first reported occurrence of a primary magma within peridotite nodules which has the composition of calciocarbonatite, by far the most common carbonatite type occurring in crustal complexes. The carbonate in the Montana Clara harzburgite host is restricted to wehrlitic alteration zones and is intimately associated with a second generation of minerals, mainly olivine, clinopyroxene and spinel, with glass of syenitic composition, and with Fe−Cu-rich sulphides. The metasomatic assemblage was formed by reaction of a sodiumbearing dolomitic melt, derived from a somewhat deeper level in the upper mantle, with the harzburgite mineral assemblage at a pressure of 15 kbars, or lower. As a result of the reaction the residual carbonatite melt became more enriched in calcium. The calciocarbonatite and sulphide phases almost invariably form globules in the silicate glass, indicating the existence of three immiscible liquids under upper mantle conditions. Several alkaline complexes contain carbonatites occurring with syenitic rock types and its seems feasible that the formation of such close associations might have been influenced by processes of liquid immiscibility which took place under upper mantle conditions.

Magmatic metasomatism and formation of the Merensky reef, Bushveld Complex

Abstract: The rare earth element (REE) contents of pyroxenes and other minerals from the Merensky reef and stratigraphically adjacent rocks of the Atok section, Bushveld Complex, have been determined with the ion microprobe. Merensky reef clinopyroxene and orthopyroxene contain much higher and more variable concentrations of the REE than their cumulus counterparts in rocks several meters below the reef. Chondrite-normalized Merensky clinopyroxene Ce contents vary from ≈10 to 90 for Ce and from ≈4 to 17 for Yb. They also possess deep, negative Eu anomalies, the Eu anomalics being deeper for crystals having high REE contents and relatively shallow for pyroxenes with low REE contents. Similar compositional characteristics are displayed by Cl-rich apatite, which is an accessory phase in the rocks. Interstitial pyroxene in cumulates above and below the reef also tends to have elevated REE contents and in general is not in equilibrium with coexisting cumulus minerals. The melt from which the cumulus minerals crystallized falls within the compositional range of continental basalts; that from which Merensky and postcumulus pyroxenes crystallized is inferred to be much more highly enriched in REE than any normal tholeiitic or alkalic basalt. Despite their highly evolved nature in terms of the REE, the Merensky reef pyroxenes are not evolved in terms of major elements. The decoupling of incompatible trace and major elements is best explained by a metasomatic process. It is speculated that metasomatism involved upward percolation of hydrated silicate melt through and its reaction with the crystalline cumulate pile. The fact that the rocks enriched in the platinum group elements are also those that show evidence for metasomatism suggests that these elements were also metasomatically redistributed.

Geochemical characteristics of lava-field basalts from eastern Australia and inferred sources: Connections with the subcontinental lithospheric mantle?

Abstract: A large new database of major, trace elements and Sr-Nd isotopic ratios from 11 lava-field provinces in New South Wales and Queensland, eastern Australia allows detailed interpretation of the origin of these basaltic magmas. Isotopic signatures and trace element patterns identify an OIB-type (oceanic island basalt) source as a dominant component for most of these and some provinces appear to have additional significant components derived from the subcontinental lithospheric mantle (SCLM). The SCLM components have geochemical characteristics that overlap those observed in spinel lherzolite xenoliths (samples of shallow lithospheric mantle) from eastern Australia. These SCLM components show geochemical provinciality that indicates the occurrence of distinct geochemical lithospheric domains reflecting the timing and style of tectonic evolution of different regions. One component reflects modification by subduction-related processes during the late Paleozoic and Mesozoic, one records enrichment by fluids during old metasomatic events and another suggests a metasomatic event involving a distinctive amphibole and apatite-style enrichment. The composition and age distribution of volcanic lava-field provinces older than 10 Ma are consistent with a model involving a regional upwelling (elongated N-S along eastern Australia) of deep hot mantle related to marginal rifting and with OIB-type source geochemical characteristics. Thermal inhomogeneities within this plume swath resulted in small diapirs which may have undergone melt segregation at about 100 km and incorporated varying amounts of SCLM components there or from higher levels of the SCLM during ascent. Subsequent hot-spot generated central volcanoes overprinted this lava-field volcanism, tapped a similar OIB-type source component and truncated the thermal events.

The partitioning of copper between silicate melts and two-phase aqueous fluids: An experimental investigation at 1 kbar, 800¡ C and 0.5 kbar, 850¡ C

Abstract: Experiments were performed in the three phase system high-silica rhyolite melt+low-salinity aqueous vapor+hydrosaline brine, to investigate the partitioning equilibria for copper in magmatic-hydrothermal systems at 800° C and 1 kbar, and 850° C and 0.5 kbar. Daqm/mlt Cu and apparent equilibrium constants, Kaqm/mlt Cu,Na, between the aqueous mixture (aqm=quenched vapor+brine) and the silicate melt (mlt) are calculated. Daqm/mlt Cu increases with increasing aqueous chloride concentration and is a function of pressure. Kaqm/mlt Cu,Na=215(±73) at 1 kbar and 800° C and Kaqm/mlt Cu,Na=11(±6) at 0.5 kbar and 850°C. Decreasing pressure from 1 to 0.5 kbar lowers Kaqm/mlt Cu,Na by a factor of approximately 20. Data revealed no difference in Kaqm/mlt Cu,Na or Daqm/mlt Cu as a function of the melt aluminium saturation index. Within the 2-phase field the Kaqm/mlt Cu,Na show no variation with total aqueous chloride, indicating that copper-sodium exchange between the vapor, brine and silicate melt is independent of the mass proportion of vapor and brine. Model copper-sodium apparent equilibrium constants for the hydrosaline brine and the silicate melt revealed a negative dependence on pressure. Model apparent equilibrium constants for copper-sodium exchange between the brine and vapor were close to unity at 1 kbar and 800° C.

Phase diagram methods for graphitic rocks and application to the system C−O−H−FeO−TiO2−SiO2

Abstract: Carbon-saturated C−O−H (GCOH) fluids have only one compositional degree of freedom. This degree of freedom is specified by the variable X o that expresses the atomic fraction of oxygen relative to oxygen+hydrogen. The only valid constraint on the maximum in the activity of GCOH fluid species is related to the bulk composition of the fluid, as can be expressed by X o. In fluid-saturated graphitic rocks, mineral devolatilization reactions are the dominant factor is determining the redox state of the metamorphic environment. X o is directly proportional to the fo2 of GCOH fluid, and because its value can only be affected by fluid-rock interaction, it is an ideal measure of the redox character and composition of GCOH fluid. Phase diagrams as a function of X o are analogous to the P-T-Xco2 diagrams used for binary H2O−CO2 fluids; this analogy can be made rigorously if the C−O−H fluid composition is projected through carbon into the O−H subcomposition. After projection, the fluid is described as a binary fluid with the components O and H, and the compositional variable X o. Description of GCOH fluids in this manner facilitates construction of phase diagram projections that define the P-T stability of mineral assemblages for all possible fluid compositions as well as fluid-absent conditions. In comparison to phase diagrams with variables based on the properties of fluid species, P-T-X o diagrams more clearly constraint accessible fluid compositions and fluid evolution paths. Calculated P-T-X o projections are presented for the C−O−H−FeO−TiO2−SiO2 system, a limiting model for the stability of Fe−Ti oxides in graphitic metapelites and phase relations in metamorphosed iron-formations. With regard to the latter, the stability of the assemblage qtz+mag+gph has been a source of controversy. Both the calculated C−O−H−FeO−TiO2−SiO2 system petrogenetic grid and natural examples, suggest that this assemblage has a large P-T stability field. Discrepancies between earlier C−O−H−FeO−SiO2 system phase diagram topologies are reconciled by the qtz+mag+gph=sid+fa phase field, a barometric indicator for metamorphosed-iron formations. A more general implication of calculated P-T-X o phase relation is that few inorganic mineral-fluid equilibria appear to be capable of generating hydrogen-rich, fO2, GCOH fluids at crustal metamorphic conditions. The utility of P-T-X o diagrams derives from the use of a true compositional variable to describe fluid composition, this approach can be extended to the treatment of carbon-undersaturated systems, and provides a simple means of understanding metasomatic processes of graphite precipitation.

The effect of dissolved water on the oxidation state of iron in natural silicate liquids

Abstract: Ferric-ferrous ratios have been measured in 22 experiments on three natural compositions equilibrated at known temperature (950°–1100° C) and oxygen fugacity, and at water-saturated conditions over a pressure range from 0.05 to 0.2 GPa. There does not appear to be any reaction between the melt and the capsule material that affects the redox state of the iron in the melt. An empirical expression for the anhydrous behavior of the redox state of iron in each of these compositions has also been determined at 1 bar as a function of temperature and oxygen fugacity. A direct comparison of the hydrous ferric-ferrous values with the calculated anhydrous values shows that the dissolution of water in a per-alkaline rhyolite, andesite, and an augite minette has no effect on the redox state of the iron in these melts. This result parallels the effect of water on sulfide speciation in basaltic melts, and confirms published results on experimental hydrous basalts.

Melting of metasomatized subcontinental lithosphere: undersaturated mafic lavas from Rungwe, Tanzania

Abstract: This paper uses the geochemistry of primitive mafic lavas from the Rungwe volcanic province (southwestern Tanzania) to infer the source mineralogy and melting history. Post-Miocene mafic lavas from Rungwe include alkali basalts, basanites, nephelinites and picrites with up to 18.9 wt% MgO; nephelinites (>13.5% normative nepheline) are restricted to Kiejo volcano in the southern portion of the province. Rungwe lavas differ from most Western Rift volcanics in that they are not unusually potassic (K2O/Na2O ca. 0.40). Sparsely phyric mafic lavas contain phenocrysts and xenocrysts of plagioclase (An82–90), clinopyroxene (4.5–9.5 wt% Al2O3), and olivine (Fo79–88); one basanite contains a 1 mm xenocryst of apatite included in magnesian clinopyroxene. All samples have high abundances of incompatible elements (e.g., 0.7–2.2 wt% P2O5) and are enriched in REE relative to HFSE (Hf, Zr, Ti, Y), Cs, Ba, and K. Some incompatible element ratios are constant throughout the Rungwe suite (e.g., Zr/Nb, Sr/Ce, K/Rb), but other ratios are extremely variable and exceed the range measured in global Ocean Island Basalts (OIB) (e.g., Ba/Nb, Sm/Zr, La/Nb, Pb/Ce, Nb/U). The range in degree of silica saturation, and its excellent correlation with P2O5/Al2O3, indicate that the Rungwe suite records variable degrees of melting. Variations of individual incompatible trace element abundances in nephelinite and basanite samples suggest that the source contains metasomatic amphibole, ilmenite, apatite, and zircon. The Rungwe suite is interpreted as a series of low-percentage melts of CO2-rich peridotite at pressures that span the garnet-spinel transition. A geochemical comparison of Rungwe samples to lavas from other Western Rift volcanic centers requires that the source mineralogy varies along the rift axis, although each province is underlain by metasomatized peridotite. The incompatible trace element signatures of Western Rift lavas indicate that the source area is typically homogeneous on the scale of individual volcanoes, although lavas from each volcano reflect a range in degree of melting. Significantly, volcanoes with distinct geochemistry are always separated by major rift faults, suggesting that volcanic and tectonic surface features may correspond to metasomatic provinces within the subcontinental lithospheric mantle.

Diffusion of lead in plagioclase and K-feldspar: an investigation using Rutherford Backscattering and Resonant Nuclear Reaction Analysis

Abstract: Chemical diffusion of Pb has been measured in K-feldspar (Or93) and plagioclase of 4 compositions ranging from An23 to An93 under anhydrous, 0.101 MPa conditions. The source of diffusant for the experiments was a mixture of PbS powder and ground feldspar of the same composition as the sample. Rutherford Backscattering (RBS) was used to measure Pb diffusion profiles. Over the temperature range 700–1050°C, the following Arrhenius relations were obtained (diffusivities in m2s-1):

Petrogenesis of basalt-comendite and basalt-pantellerite suites, Terceira, Azores, and some implications for the origin of ocean-island rhyolites

Abstract: Petrogenetic modeling of the Recent lava succession of Santa Barbara and Pico Alto volcanoes and associated basaltic lavas indicates that there are two discrete lava series present, one erupted from the axial rift linking the two central volcanoes and one associated with monogenetic cones scattered around the flanks of Santa Barbara. The felsic lavas of both volcanoes are peralkaline and appear to be derived from associated basalts by fractional crystallization of an assemblage including essential amphibole. Trace element abundances in the felsic lavas, particularly those of Sr and REE, cannot be reconciled with an origin through partial melting of basaltic material at the base of the volcanic pile. The difference between the comenditic and pantelleritic differentiation trends of Santa Barbara and Pico Alto is attributed primarily to FO2 control of the crystallizing assemblage, probably related to thermal dissociation of magmatic water in the Santa Barbara magma chamber. This effect may be augmented by minor differences in parent basaltic compositions, the Pico Alto pantellerites being derived from the rift basalts whereas the Santa Barbara comendites are derived from the off-rift basalts. A compositional gap between 54 and 64% silica content in the lavas is not present if the suite is extended to include co-magmatic hypabyssal xenoliths, leading to the inference that the gap in this and other bimodal suites results solely from a relative inability of magma of intermediate composition to erupt.

Sr and Nd isotope data of apatite, calcite and dolomite as indicators of source, and the relationships of phoscorites and carbonatites from the Kovdor massif, Kola peninsula, Russia

Abstract: A detailed Sr−Nd isotopic study of primary apatite, calcite and dolomite from phoscorites and carbonatites of the Kovdor massif (380 Ma), Kola peninsula, Russia, reveals a complicated evolutionary history. At least six types of phoscorites and five types of carbonatite have been identified from Kovdor by previous investigators based on relative ages and their major and accessory minerals. Isotopic data from apatite define at least two distinct groups of phoscorite and carbonatite. Apatite from the earlier phoscorites and carbonatites (group 1) are characterized by relatively low87Sr/86Sr (0.70330–0.70349) and143Nd/144Nd initial ratios (0.51230–0.51240) with F=2.01–2.23 wt%, Sr=2185–2975 ppm, Nd=275–660 ppm and Sm=31.7–96.2 ppm. Apatite from the second group has higher87Sr/86Sr (0.70350–0.70363) and143Nd/144Nd initial ratios (0.51240–0.51247) and higher F (2.63–3.16 wt%), Sr (4790–7500 ppm), Nd (457–1074 ppm) and Sm (68.7–147.6 ppm) contents. This group corresponds to the later phoscorites and carbonatites. One apatite sample from a carbonatite from the earlier group fits into neither of the two groups and is characterized by the highest initial87Sr/86Sr (0.70385) and lowest143Nd/144Nd (0.51229) of any of the apatites. Within both groups initial87Sr/86Sr and143Nd/144Nd ratios show negative correlations. Strontium isotope data from coexisting calcite and dolomite support the findings from the apatite study. The Sr and Nd isotopic similarities between carbonatites and phoscorites indicate a genetic relationship between the two rock types. Wide variations in Sr and Nd isotopic composition within some of the earlier carbonatites indicate several distinct intrusive phases. Oxygen isotopic data from calcite and dolomite (δ18O=+7.2 to +7.7‰ SMOW) indicate the absence of any low-temerature secondary processes in phoscorites and carbonatites, and are consistent with a mantle origin for their parental melts. Apatite data from both groups of phoscorite plot in the depleted quadrant of an eNd versus eSr diagram. Data for the earlier group lie along the Kola Carbonatite Line (KCL) as defined by Kramm (1993) and data from the later group plot above the KCL. The evolution of the phoscorites and carbonatites cannot be explained by simple magmatic differentiation assuming closed system conditions. The Sr−Nd data can best be explained by the mixing of three components. Two of these are similar to the end-members that define the Kola Carbonatite Line and these were involved in the genesis of the early phoscorites and carbonatites. An additional component is needed to explain the isotopic characteristics of the later group. Our study shows that apatite from rocks of different mineralogy and age is ideal for placing constraints on mantle sources and for monitoring the Sr−Nd evolution of carbonatites.