Experimental studies on three potassium-rich ultramafic rocks from Damodar Valley, East India

Summary An experimental study on the phase relationships of three potassium-rich ultramafic rocks from the Damodar Valley, Gondawana basins, has been performed under upper mantle P–T conditions (1.0–2.5 GPa, 700–1200 °C). The Mohanpur lamproite and Satyanarayanpur minette, both from the Raniganj basins, have been investigated with the addition of 15 wt% H₂O. No water was added in the experiments done on an olivine minette from the Jarangdih coal mine, Bokaro Basin, which originally contains 15 wt% CO₂ and 2.86 wt% H₂O. In all cases, olivine is the liquidus phase followed by phlogopite. The subsolidus assemblage for the three rocks is a phlogopite-bearing harzburgite, associated with apatite, Mg-ilmenite and carbonates for the Jarangdih rock; apatite, chromian spinel and carbonates and priderite (only between 1.0 and 1.2 GPa) in the case of the Mohanpur lamproite, and finally apatite, chromian spinel, rutile, and carbonate in the Satyanarayanpur sample. Although orthopyroxene is absent in the natural potassium-rich ultramafic rocks, its presence in the run products of the Jarangdih rock is possibly related to a reaction between olivine and a CO₂-bearing fluid phase. The presence of orthopyroxene in the run products of Mohanpur and Satyanarayanpur rocks may be due to a reaction between K-feldspar, olivine and a vapour phase to produce phlogopite and orthopyroxene. On the basis of present experimental investigation and isotopic studies made by previous investigators, it has been suggested that these K-rich rocks have crystallized from melts derived by vein-plus-wall-rock melting of a phlogopite-bearing harzburgite source rock. Received December 15, 1999; revised version accepted June 17, 2001     

Stability of phlogopite in ultrapotassic kimberlite-like systems at 5.5–7.5 GPa

Hydrous K-rich kimberlite-like systems are studied experimentally at 5.5–7.5 GPa and 1200–1450?°C in terms of phase relations and conditions for formation and stability of phlogopite. The starting samples are phlogopite–carbonatite–phlogopite sandwiches and harzburgite–carbonatite mixtures consisting of Ol?+?Grt?+?Cpx?+?L (±Opx), according to the previous experimental results obtained at the same P–T parameters but in water-free systems. Carbonatite is represented by a K- and Ca-rich composition that may form at the top of a slab. In the presence of carbonatitic melt, phlogopite can partly melt in a peritectic reaction at 5.5 GPa and 1200–1350?°C, as well as at 6.3–7.0 GPa and 1200?°C: 2Phl?+?CaCO₃ (L)?Cpx?+?Ol?+?Grt?+?K₂CO₃ (L)?+?2H₂O (L). Synthesis of phlogopite at 5.5 GPa and 1200–1350?°C, with an initial mixture of H₂O-bearing harzburgite and carbonatite, demonstrates experimentally that equilibrium in this reaction can be shifted from right to left. Therefore, phlogopite can equilibrate with ultrapotassic carbonate–silicate melts in a?≥?150?°C region between 1200 and 1350?°C at 5.5 GPa. On the other hand, it can exist but cannot nucleate spontaneously and crystallize in the presence of such melts in quite a large pressure range in experiments at 6.3–7.0 GPa and 1200?°C. Thus, phlogopite can result from metasomatism of peridotite at the base of continental lithospheric mantle (CLM) by ultrapotassic carbonatite agents at depths shallower than 180–195 km, which creates a mechanism of water retaining in CLM. Kimberlite formation can begin at 5.5 GPa and 1350?°C in a phlogopite-bearing peridotite source generating a hydrous carbonate–silicate melt with 10–15 wt% SiO₂, Ca# from 45 to 60, and high K enrichment. Upon further heating to 1450?°C due to the effect of a mantle plume at the CLM base, phlogopite disappears and a kimberlite-like melt forms with SiO₂ to 20 wt% and Ca#?=?35–40.     

Primitive basalts and andesites from the Mt. Shasta region,N. California: products of varying melt fraction and water content

Quaternary volcanism in the Mt. Shasta region has produced primitive magmas [Mg/(Mg+Fe^*)>0.7, MgO>8 wt% and Ni>150 ppm] ranging in composition from high-alumina basalt to andesite and these record variable extents ofmelting in their mantle source. Trace and major element chemical variations, petrologic evidence and the results of phase equilibrium studies are consistent with variations in H₂O content in the mantle source as the primary control on the differences in extent of melting. High-SiO₂, high-MgO (SiO₂=52% and MgO=11 wt%) basaltic andesites resemble hydrous melts (H₂O=3 to 5 wt%) in equilibrium with a depleted harzburgite residue. These magmas represent depletion of the mantle source by 20 to 30 wt% melting. High-SiO₂, high-MgO (SiO₂=58% and MgO=9 wt%) andesites are produced by higher degrees of melting and contain evidence for higher H₂O contents (H₂O=6 wt%). High-alumina basalts (SiO₂=48.5% and Al₂O₃=17 wt%) represent nearly anhydrous low degree partial melts (from 6 to 10% depletion) of a mantle source that has been only slightly enriched by a fluid component derived from the subducted slab. The temperatures and pressures of last equilibration with upper mantle are 1200°C and 1300°C for the basaltic andesite and basaltic magmas, respectively. A model is developed that satisfies the petrologic temperature constraints and involves magma generation whereby a heterogeneous distribution of H₂O in the mantle results in the production of a spectrum of mantle melts ranging from wet (calc-alkaline) to dry (tholeiitic).     

Origin of carbonatite magma during the evolution of ultrapotassic basite magma

Clinopyroxene phenocrysts in fergusite from a diatreme in the Dunkel’dyk potassic alkaline complex in the southeastern Pamirs, Tajikistan, and from carbonate veinlets cutting across this rock contain syngenetic carbonate, silicate, and complex melt inclusions. The homogenization of the silicate and carbonate material of the inclusions with the complete dissolution of daughter crystalline phases and fluid in each of them occur simultaneously at 1150?1180°C. The pressures estimated using fluid inclusions and mineral geobarometers were 0.5–0.7 GPa. The behavior of the inclusions during their heating and their geochemistry are in good agreement with the origin of carbonate melts via liquid immiscibility. Carbonatite magma was segregated at the preservation of volatile components (H₂O, CO₂, F, Cl, and S) in the melt, and this resulted in the crystallization of H₂O-rich minerals and carbonates and testifies that the magma was not intensely degassed during its ascent to the surface. The silicate melts are rich in alkalis (up to 4 wt % Na₂O and 12 wt % K₂O), H₂O, F, Cl, and REE (up to 1000 ppm), LREE, Ba, Th, U, Li, B, and Be. The diagrams of the concentrations of incompatible elements of these rocks typically show deep Nb, Ta, and Ti minima, a fact making them similar to the unusual type of ultrapotassic magmas: lamproites of the Mediterranean type. These magmas are thought to be generated in relation to subduction processes, first of all, the fluid transport of various components from a down-going continental crustal slab into overlying levels of the mantle wedge, from which ultrapotassic magmas are presumably derived.     

The effect of fluorine on phase relationships in the system KAlSiO4-Mg2SiO4-SiO2 at 28 kbar and the solution mechanism of fluorine in silicate melts

Phase relationships in the system kalsilite-forsterite-quartz with fluorine added by direct substitution for oxygen were examined at 28 kb. A large liquidus field for fluorphlogopite exists with approx. 4 wt% F added to the system and the thermal stability of phlogopite is increased by 300° C relative to the water saturated system. Fluorine expands the phase volume of enstatite relative to forsterite so that the peritectic point PHL+EN+FO+L, a model for melting of a phlogopite harzburgite, lies in the silica-undersaturated field. Experimental phlogopites have excess Si which correlates with F content and are Al-deficient. The high Si contents indicate solid solution with an end member intermediate between tri- and di-octahedral micas. Glasses with compositions analogous to partial melts from phlogopite harzburgite were examined by infrared spectroscopy in the mid- and far-IR regions. Results show that fluorine polymerises the melt by bonding with all the network modifying cations K, Mg and Al. At higher F contents, but still less than 1 wt%, tetrahedral KAlO₂-groups are complexed by fluorine and removed from the aluminosilicate network simultaneously polymerising and increasing the Si/(Si+Al) ratio of the network. However, when HF rather than F is present, the overall effect will be to depolymerise melts due to the effect of OH released by dissolution of HF. The presence of abundant Si-F bonds is considered unlikely even in silica-rich magmas: the viscosity decrease characteristic of fluorine-bearing melts can be attributed to the formation of fluoride complexes.     

Anatexis and fluid regime of the deep continental crust: New clues from melt and fluid inclusions in metapelitic migmatites from Ivrea Zone (NW Italy)

We investigate the inclusions hosted in peritectic garnet from metapelitic migmatites of the Kinzigite Formation (Ivrea Zone, NW Italy) to evaluate the starting composition of the anatectic melt and fluid regime during anatexis throughout the upper amphibolite facies, transition, and granulite facies zones. Inclusions have negative crystal shapes, sizes from 2 to 10 μm and are regularly distributed in the core of the garnet. Microstructural and micro‐Raman investigations indicate the presence of two types of inclusions: crystallized silicate melt inclusions (i.e., nanogranitoids, NI), and fluid inclusions (FI). Microstructural evidence suggests that FI and NI coexist in the same cluster and are primary (i.e., were trapped simultaneously during garnet growth). FI have similar compositions in the three zones and comprise variable proportions of CO₂, CH₄, and N₂, commonly with siderite, pyrophyllite, and kaolinite, suggesting a COHN composition of the trapped fluid. The mineral assemblage in the NI contains K‐feldspar, plagioclase, quartz, biotite, muscovite, chlorite, graphite and, rarely, calcite. Polymorphs such as kumdykolite, cristobalite, tridymite, and less commonly kokchetavite, were also found. Rehomogenized NI from the different zones show that all the melts are leucogranitic but have slightly different compositions. In samples from the upper amphibolite facies, melts are less mafic (FeO + MgO = 2.0–3.4 wt%), contain 860–1700 ppm CO₂ and reach the highest H₂O contents (6.5–10 wt%). In the transition zone melts have intermediate H₂O (4.8–8.5 wt%), CO₂ (457–1534 ppm) and maficity (FeO + MgO = 2.3–3.9 wt%). In contrast, melts at granulite facies reach highest CaO, FeO + MgO (3.2–4.7 wt%), and CO₂ (up to 2,400 ppm), with H₂O contents comparable (5.4–8.3 wt%) to the other two zones. Our results represent the first clear evidence for carbonic fluid‐present melting in the Ivrea Zone. Anatexis of metapelites occurred through muscovite and biotite breakdown melting in the presence of a COH fluid, in a situation of fluid–melt immiscibility. The fluid is assumed to have been internally derived, produced initially by devolatilization of hydrous silicates in the graphitic protolith, then as a result of oxidation of carbon by consumption of Fe³⁺‐bearing biotite during melting. Variations in the compositions of the melts are interpreted to result from higher T of melting. The H₂O contents of the melts throughout the three zones are higher than usually assumed for initial H₂O contents of anatectic melts. The CO₂ contents are highest at granulite facies, and show that carbon‐contents of crustal magmas are not negligible at high T. The activity of H₂O of the fluid dissolved in granitic melts decreases with increasing metamorphic grade. Carbonic fluid‐present melting of the deep continental crust represents, together with hydrate‐breakdown melting reactions, an important process in the origin of crustal anatectic granitoids.     

Experimental constraints on the origins of primitive potassic lavas from the Trans-Mexican Volcanic Belt

Primitive magmas in the Trans-Mexican Volcanic Belt (TMVB) span a wide geochemical range that includes calc-alkaline basalt and basaltic andesite, potassic shoshonites, and intraplate alkaline basalts, indicating that the subarc mantle wedge is chemically heterogeneous. The aim of this study is to experimentally constrain the origins of potassic lavas that have erupted along the volcanic front in the TMVB. We used a piston-cylinder apparatus to determine the P–T–H₂O near-liquidus phase relations for two primitive potassic lavas: a hornblende trachybasalt (shoshonite) from Cerro La Pilita in the central TMVB and a high-K calc-alkaline basalt from Ayutla in the western TMVB. Experiments were conducted at mantle pressures (0.8–2.5 GPa) and temperatures (1,100–1,400 °C) with 1.5–6 wt% H₂O. Results show that both samples were last equilibrated with an olivine + clinopyroxene assemblage at upper mantle pressures. Integrating our results with trace element characteristics, we conclude that the potassic magmas formed by a complex, multistage process in which melts from the hottest part of the mantle wedge either reequilibrated with clinopyroxene-rich veins in the shallow upper mantle or caused melting of such veins by advective heating. We combine our results with previous experiments on TMVB lavas to provide an along-arc perspective of melt equilibration depths in the mantle wedge. The results suggest that although melts may initially form deep in the wedge, they commonly reequilibrate with heterogeneous mantle at shallower depths. Primitive, medium-K basaltic andesites in the TMVB form by reequilibration with harzburgite, which we infer to be a common lithology in the upper mantle, whereas some potassic magmas like the ones studied here form through reequilibration with or melting of veins of olivine + clinopyroxene ± phlogopite. Though somewhat rare at the volcanic front relative to the more abundant medium-K volcanic rocks, the potassic magmas are an important lava type for revealing mantle chemical heterogeneities.     

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

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 equilibrium with the most calcic plagioclase (An₉₄) found 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. Received: 31 August 1993 / Accepted: 20 May 1994     

The upper mantle under La Palma,Canary Islands: formation of Si−K−Na-rich melt and its importance as a metasomatic agent

 Mantle xenoliths hosted by the Historic Volcan de San Antonio, La Palma, Canary Islands, fall into two main group. Group I consists of spinel harzburgites, rare spinel lherzolites and spinel dunites, whereas group II comprises spinel wehrlites, amphibole wehrlites, and amphibole clinopyroxenites. We here present data on group I xenoliths, including veined harzburgites and dunites which provide an excellent basis for detailed studies of metasomatic processes. The spinel harzburgite and lherzolite xenoliths have modal ol−opx−cpx ratios and mineral and whole rock major element chemistry similar to those found in Lanzarote and Hierro, and are interpreted as highly refractory, old oceanic lithospheric mantle. Spinel dunites are interpreted as old oceanic peridotite which has been relatively enriched in olivine and clinopyroxene (and highly incompatible elements) through reactions with basaltic Canarian magmas, with relatively high melt/peridotite ratio. Group I xenoliths from La Palma differ from the Hierro and Lanzarote ones by a frequent presence of minor amounts of phlogopite (and amphibole). Metasomatic processes are also reflected in a marked enrichment of strongly incompatible relative to moderately incompatible trace elements, and in a tendency for Fe−Ti enrichment along grain boundaries in some samples. The veins in the veined xenoliths show a gradual change in phase assemblage and composition of each phase, from Fe−Ti-rich amphibole+augite+Fe−Ti-oxides+apatite+basaltic glass, to Ti-poor phlogopite+Cr-diopside±chromite+ Si−Na−K-rich glass+fluid. Complex reaction zones between veins and peridotite include formation of clinopyroxene±olivine+glass at the expense of orthopyroxene in harzburgite, and clinopyroxene+spinel±amphibole±glass at the expense of olivine in dunite. The dramatic change in glass composition from the broadest to the narrowest veins includes increasing SiO₂ from 44 to 67 wt%, decreasing TiO₂/Al₂O₃ ratio from >0.24 to about 0.02, and increasing K₂O and Na₂O from 1.8 to >7.0 wt% and 3.8 to 6.7 wt%, respectively. The petrographic observations supported by petrographic mixing calculations indicate that the most silicic melts in the veined xenoliths formed as the result of reaction between infiltrating basaltic melt and peridotite wall-rock. The highly silicic, alkaline melt may represent an important metasomatic agent. Pervasive metasomatism by highly silicic melts (and possibly fluids unmixed from these) may account for the enriched trace element patterns and frequent presence of phlogopite in the upper mantle under La Palma. Received: 15 January 1996 / Accepted 30 May 1996     

A suggested origin of MARID xenoliths in kimberlites by high pressure crystallization of an ultrapotassic rock such as lamproite

Chemical, mineralogical and isotopic studies have been made on nodules of the MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) xenolith suite in southern African kimberlites. All are ultramafic and ultrapotassic (MgO= 20–25%, K₂O=4–9%), with bulk compositions reflecting the wide variation in relative proportions of the five minerals amongst the nodules. They are comparable in major element compositions to magnesian lamproites, in particular the ultrabasic olivine-lamproites of Western Australia. In a number of high pressure experimental studies on ultra-potassic rocks, the phases produced between 25–30 kbar from compositions comparable to those of MARID rocks (in the presence of additional water), were predominantly phlogopite and diopside (±K-richterite, ±ilmenite, ±rutile). Furthermore the compositions of experimental minerals produced in the synthetic-biotite-mafurite-H₂O system by Edgar et al. (1976) are similar to those in MARID rocks.It is suggested on the basis of these observations and the textural appearance of MARID rocks that they are magmatic compositional equivalents of MgO-rich lamproites that crystallized at high pressures. While lamproites have higher average concentrations of incompatible elements, (including REE), some MARID rocks have comparable abundances. It is suggested that late stage vapour-rich melts carrying substantial REE and other incompatible elements escaped from crystallizing MARID magmas into surrounding subcontinental lithosphere, thus resulting in lower levels of these elements in most MARID rocks. In contrast faster crystallization of lamproitic rocks under volcanic/ hypabyssal conditions would prevent similar losses.The MARID proto-magmas are thought to be either partial melts of metasomatised phlogopite peridotite, or small volume asthenospheric melts which are modified and further enriched by incorporation of small partial melts of enriched subcontinental lithosphere during magma ascent.     

Post-collisional ultrapotassic rocks and mantle xenoliths in the Sailipu volcanic field of Lhasa terrane,south Tibet: Petrological and geochemical constraints on mantle source and geodynamic setting

Post-collisional ultrapotassic magmatic rocks (15.2–18.8 Ma), containing mantle xenoliths, are extensively distributed in the Sailipu volcanic field of the Lhasa terrane in south Tibet. They could be subdivided into high-MgO and low-MgO subgroups based on their petrological and geochemical characteristics. The high-MgO subgroup has olivine-I (Fo_87–92), phlogopite and clinopyroxene as phenocryst phases, while the low-MgO subgroup consists mainly of phlogopite, clinopyroxene and olivine-II (Fo_77–89). These ultrapotassic magmatic rocks have high MgO (4.6–14.5 wt%), Ni (145–346 ppm), Cr (289–610 ppm) contents, and display enrichment in light rare earth element (REE) over heavy REE and enriched large ion lithophile elements (LILE) relative to high field strength elements (HFSE) with strongly negative Nb-Ta-Ti anomalies in primitive mantle-normalized trace element diagrams. They have extremely radiogenic (⁸⁷Sr/⁸⁶Sr)_i (0.7167–0.7274) and unradiogenic (¹⁴³Nd/¹⁴⁴Nd)_i (0.5118–0.5120), high (²⁰⁷Pb/²⁰⁴Pb)_i (15.740–15.816) and (²⁰⁸Pb/²⁰⁴Pb)_i (39.661–39.827) at a given (²⁰⁶Pb/²⁰⁴Pb)_i (18.363–18.790) with high δ¹⁸O values (7.3–9.7‰). Strongly linear correlations between depleted mid-ocean ridge basalt-source mantle (DMM) and the Indian continental crust (HHCS) in Sr-Nd-Pb-O isotopic diagrams indicate that the geochemical features could result from reaction between mantle peridotite and enriched components (fluids and melts) released by the eclogitized Indian continental crust (HHCS) in the mantle wedge. The high-MgO (13.7–14.5 wt%) subgroup displays higher (¹⁴³Nd/¹⁴⁴Nd)_i, lower (⁸⁷Sr/⁸⁶Sr)_i and (²⁰⁶Pb/²⁰⁴Pb)_i ratios and lower δ¹⁸O values compared with the low-MgO (4.6–8.8 wt%) subgroup. High Ni (850–4862 ppm) contents of olivine phenocrysts and high whole-rock SiO₂, NiO, low CaO contents indicate that the low-MgO ultrapotassic magmatic rocks are derived from partial melting of olivine-poor mantle pyroxenite. However, lower Ni concentrations of olivine phenocryst and lower whole-rock SiO₂, NiO, higher CaO contents of the high-MgO ultrapotassic rocks may indicate their peridotite mantle source. This could be attributed to different amounts of silicate-rich components added into the mantle sources of the parental magmas in the mantle wedge caused by the northward subduction of the Indian continental lithosphere. The reaction-formed websterite xenoliths, reported for the first time in this study, are made up of anhedral and interlocking clinopyroxene (45–65 vol%) and orthopyroxene (30–50 vol%) with minor phlogopite (< 3 vol%) and quartz (< 2 vol%) and are suggested to be formed by silicate metasomatism of the mantle peridotite. The harzburgites, another major type of mantle xenolith in south Tibet, have a mineral assemblage of olivine (60–75 vol%), orthopyroxene (20–35 vol%), clinopyroxene (< 3 vol%), phlogopite (< 2 vol%) and spinel (< 2 vol%) and may have experienced subduction-related metasomatism. Combined with two types of ultrapotassic magmas, we propose that compositions of mantle wedge beneath south Tibet may gradually evolve from harzburgite through lherzolite to websterite with strong metasomatism of silicate-rich components in their mantle source region. Partial melting of the enriched mantle sources could be triggered by rollback of Indian continental slab during 25–8 Ma in south Tibet.     

Implications of experimental petrology to the evolution of ultrapotassic rocks

The contributions of experimental studies pertinent to ultrapotassic rocks of Groups I (lamproites) and II (kamafugites and related rocks) are discussed in terms of synthetic systems, ultrapotassic rock compositions, experiments on characteristic minerals in these rocks and experiments designed to model mantle metasomatism. These studies indicate that the majority of ultrapotassic magmas are derived by partial melting of a metasomatically enriched mantle source at depths of 100 km or greater, and under fluid conditions represented by the C---O---H system with fluorine that may be reduced or oxidized relative to other compositions. Many lamproitic magmas may be derived from a phlogopite-harzburgite with volatiles that are predominantly H₂O and F₁ whereas kamafugitic type ultrapotassic magmas may be products of partial melts of a more wehrlitic mantle source in which the main volatiles are H₂O, CO₂ and possibly F. Experimental and theoretical considerations of mantle metasomatism suggest that it occurs at of f_O2 in the range of the FMQ buffer. Metasomatism involves low density mantle fluids (melts?) in which H₂O and CO₂ are the important volatiles, buffered by amphibole, phlogopite and carbonates. Results of recent experiments suggest that the reactions causing metasomatism may be decoupled and cyclic and occur at different depths.     

Revisiting the compositions and volatile contents of olivine-hosted melt inclusions from the Mount Shasta region: implications for the formation of high-Mg andesites

Primitive chemical characteristics of high-Mg andesites (HMA) suggest equilibration with mantle wedge peridotite, and they may form through either shallow, wet partial melting of the mantle or re-equilibration of slab melts migrating through the wedge. We have re-examined a well-studied example of HMA from near Mt. Shasta, CA, because petrographic evidence for magma mixing has stimulated a recent debate over whether HMA magmas have a mantle origin. We examined naturally quenched, glassy, olivine-hosted (Fo_87–94) melt inclusions from this locality and analyzed the samples by FTIR, LA-ICPMS, and electron probe. Compositions (uncorrected for post-entrapment modification) are highly variable and can be divided into high-CaO (>10 wt%) melts only found in Fo > 91 olivines and low-CaO (<10 wt%) melts in Fo 87–94 olivine hosts. There is evidence for extensive post-entrapment modification in many inclusions. High-CaO inclusions experienced 1.4–3.5 wt% FeO^T loss through diffusive re-equilibration with the host olivine and 13–28 wt% post-entrapment olivine crystallization. Low-CaO inclusions experienced 1–16 wt% olivine crystallization with <2 wt% FeO^T loss experienced by inclusions in Fo > 90 olivines. Restored low-CaO melt inclusions are HMAs (57–61 wt% SiO₂; 4.9–10.9 wt% MgO), whereas high-CaO inclusions are primitive basaltic andesites (PBA) (51–56 wt% SiO₂; 9.8–15.1 wt% MgO). HMA and PBA inclusions have distinct trace element characteristics. Importantly, both types of inclusions are volatile-rich, with maximum values in HMA and PBA melt inclusions of 3.5 and 5.6 wt% H₂O, 830 and 2,900 ppm S, 1,590 and 2,580 ppm Cl, and 500 and 820 ppm CO₂, respectively. PBA melts are comparable to experimental hydrous melts in equilibrium with harzburgite. Two-component mixing between PBA and dacitic magma (59:41) is able to produce a primitive HMA composition, but the predicted mixture shows some small but significant major and trace element discrepancies from published whole-rock analyses from the Shasta locality. An alternative model that involves incorporation of xenocrysts (high-Mg olivine from PBA and pyroxenes from dacite) into a primary (mantle-derived) HMA magma can explain the phenocryst and melt inclusion compositions but is difficult to evaluate quantitatively because of the complex crystal populations. Our results suggest that a spectrum of mantle-derived melts, including both PBA and HMA, may be produced beneath the Shasta region. Compositional similarities between Shasta parental melts and boninites imply similar magma generation processes related to the presence of refractory harzburgite in the shallow mantle.     

An experimental study of partitioning of fluorine between K-richterite,apatite, phlogopite,and melt at 20 kbar

Phase relations have been determined at 20 kbar and primarily under suprasolidus conditions in the Fe−Ti-free F-bearing K-richterite—phlogopite and K-richterite—apatite systems in order to assess the partitioning of F among phlogopite, K-richterite, apatite, and melt under upper-mantle conditions. Both systems are pseudoternary because they contain forsterite, enstatite and a diopside-rich clinopyroxene from the breakdown of the mica and K-richterite. The F-bearing K-richterite systems have lower minimum melting temperatures than the F-bearing phlogopite —apatite system at the same pressure. However in the systems studied, F in phlogopite appears the most effective component in altering minimum liquid compositions whereas comparison between the present study and previous systems suggests that the presence of P₂O₅ during melting may result in more K-enriched melts. Variations in the compositions of the F-bearing phases are primarily controlled by the bulk compositions of the end-member minerals and by temperature, although buffering by non-F bearing minerals (e.g. clinopyroxene) may be effective. Distribution coefficients (as wt% ratios) between F-bearing minerals and coexisting liquids have been determined as functions of bulk composition and temperature for products of experiments. Distribution coefficients between K-richterite—liquid, apatite—liquid, and phlogopite—liquid are ≥1 to slightly <1 for most bulk compositions, indicating thatF is generally a compatible element. This conclusion is in agreement with the sequence ofF distribution for similar phases in ultrapotassic rocks. These results preclude F-bearing mineral reservoirs in the mantle, at depths corresponding to 20 kbar, being capable of producing F-enrichment in ultrapotassic magmas, or being effective in redox melting processes. Editorial responsibility: K. Hodges     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Fractional crystallization and mantle-melting controls on calc-alkaline differentiation trends

The phase relations of primitive magnesian andesites and basaltic andesites from the Mt. Shasta region, N California have been determined over a range of pressure and temperature conditions and H₂O contents. The experimental results are used to explore the influence of H₂O and pressure on fractional crystallization and mantle melting behavior in subduction zone environments. At 200-MPa H₂O-saturated conditions the experimentally determined liquid line of descent reproduces the compositional variation found in the Mt. Shasta region lavas. This calc-alkaline differentiation trend begins at the lowest values of FeO*/MgO and the highest SiO₂ contents found in any arc magma system and exhibits only a modest increase in FeO*/MgO with increasing SiO₂. We propose a two-stage process for the origin of these lavas. (1) Extensive hydrous mantle melting produces H₂O-rich (>4.5--6 wt% H₂O) melts that are in equilibrium with a refractory harzburgite (olivine + orthopyroxene) residue. Trace elements and H₂O are contributed from a slab-derived fluid and/or melt. (2) This mantle melt ascends into the overlying crust and undergoes fractional crystallization. Crustal-level differentiation occurs under near-H₂O saturated conditions producing the distinctive high SiO₂ and low FeO*/MgO characteristics of these calc-alkaline andesite and dacite lavas. In a subset of Mt. Shasta region lavas, magnesian pargasitic amphibole provides evidence of high pre-eruptive H₂O contents (>10 wt% H₂O) and lower crustal crystallization pressures (800 MPa). Igneous rocks that possess major and trace element characteristics similar to those of the Mt. Shasta region lavas are found at Adak, Aleutians, Setouchi Belt, Japan, the Mexican Volcanic Belt, Cook Island, Andes and in Archean trondhjemite--tonalite--granodiorite suites (TTG suites). We propose that these magmas also form by hydrous mantle melting.Editorial responsibility: J. Hoefs     

Rare-earth and other trace element contents and the origin of minettes (mica-lamprophyres)

Instrumental neutron activation and X-ray fluorescence analyses of minettes from New Brunswick, Canada, indicate that these rocks are strongly enriched in REE, especially the LREE, and other incompatible elements as well as Cr and Co. The geochemistry of minettes precludes their formation by anatexis or assimilation of crustal rocks, contamination of mantle-derived basalts by non-crystalline residua of granite crystallization, or any process involving fractional crystallization of feldspar. Their peculiar geochemical characteristics must be a direct function of their origin in the mantle.Ultrapotassic rocks, kimberlites, and, to a lesser extent, carbonatites are strikingly similar to minettes in their rare earth and other trace element contents, suggesting genetic links among these rock types. It is difficult to explain the temporal and spatial constancy of this similarity by post-anatectic late enrichment of diversely produced magmas by volatile transport. We tentatively propose that the process best able to account for their unique geochemistry is limited partial melting of the subcontinental mantle following and dependent on the metasomatic introduction of K, Ti, Fe, REE, halogens, P, and other elements as well as H₂O and/or CO₂. If the enriched mantle is H₂O-rich, minette magma is produced; if it is CO₂-rich or has an intermediate $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, carbonatitic-kimberlitic and/or ultrapotassic magmas result.     

Fluorine geochemistry of basaltic rocks from continental and oceanic regions and petrogenetic application

Fluorine contents in about 300 samples of various types of basalts and related rocks from continental (southwestern U.S.A.; Zaire; Deccan and South Africa) and oceanic regions (Hawaii and Mid-Atlantic Ridge between 23° N and 40° N) were determined by a selective ion-electrode method.Of all of the major components in these basaltic rocks, F shows good correlation only with K₂O. It increases regularly from tholeiite to perpotassic basalt on continents, and from tholeiite to nephelinite on Hawaii. In the F-K₂O diagram all the basaltic rocks from continents and Hawaii plot between the origin of the coordinate axes and the field of phlogopite in peridotite xenoliths in South African kimberlites. Accordingly, the major proportions of F, K₂O and also H₂O in these basaltic magmas are derived from phlogopite at the source regions in the upper mantle. On the other hand, F in abyssal tholeiites is relatively higher than that of the other tholeiites at equal K₂O content, and it is suggested that most of F, K₂O and H₂O are derived from pargasites.When it is assumed that the upper mantle phlogopite contains about 10% K₂O, 0.4% (0.3–0.5%) F and 4% H₂O, H₂O content in basaltic magmas from continental including island arc and oceanic island regions can be qualitatively estimated based on their proportions of K₂OFH₂O. Similarly, H₂O content in abyssal basaltic rocks is also estimated on the basis of FH₂O in pargasites (Table 2).A suite of Deccan tholeiites shows remarkable F enrichment with increasing K₂O due to separation of anhydrous and K-free minerals during fractionation. F in tholeiitic and alkali basalt magmas in Hawaii also increases regularly with K₂O during progressive fractionation until the later stages, where rhyodacite and trachyte exhibit a relative decrease owing to the effective subtraction of F-bearing amphibole and apatite in addition to anhydrous minerals.     

Fluid inclusions in rocks from the amphibolite-facies gneiss to charnockite progression in southern Karnataka, India: direct evidence concerning the fluids of granulite metamorphism

Abstract Fluid inclusion studies of rocks from the late Archaean amphibolite-facies to granulite-facies transition zone of southern India provide support for the hypothesis that CO₂,-rich H₂O-poor fluids were a major factor in the origin of the high-grade terrain. Charnockites, closely associated leucogranites and quartzo-feldspathic veins contain vast numbers of large CO₂-rich inclusions in planar arrays in quartz and feldspar, whereas amphibole-bearing gray gneisses of essentially the same compositions as adjacent charnockites in mixed-facies quarries contain no large fluid inclusions. Inclusions in the northernmost incipient charnockites, as at Kabbal, Karnataka, occasionally contain about 25 mol. % of immiscible H₂O lining cavity walls, whereas inclusions from the charnockite massif terrane farther south do not have visibile H₂O Microthermometry of CO₂ inclusions shows that miscible CH₄ and N₂ must be small, probably less than 10mol.%combined. Densities of CO₂ increase steadily from north to south across the transitional terrane. Entrapment pressures calculated from the CO₂ equation of state range from 5 kbar in the north to 7.5 kbar in the south at the mineralogically inferred average metamorphic temperature of 750°C, in quantitative agreement with mineralogic geobarometry. This agreement leads to the inference that the fluid inclusions were trapped at or near peak metamorphic conditions. Calculations on the stability of the charnockite assemblage biotite-orthopyroxene-K-feldspar-quartz show that an associated fluid phase must have less than 0.35 H₂O activity at the inferred P and T conditions, which agrees with the petrographic observations. High TiO₂ content of biotite stabilizes it to lower H₂O activities, and the steady increase of biotite TiO₂ southward in the area suggests progressive decrease of aH₂O with increasing grade. Oxygen fugacities calculated from orthopyroxene-magnetite-quartz are considerably higher than the graphite CO₂-O₂ buffer, which explains the absence of graphite in the charnockites. The present study quantifies the nature of the vapours in the southern India granulite metamorphism. It remains to be determined whether CO₂-flushing of the crust can, by itself, create large terranes of largeion lithophile-depleted granulites, or whether removal of H₂O-bearing anatectic melts is essential.     

Meimechites, porphyritic alkaline picrites, and melanephelinites of Siberia: Conditions of crystallization, parental magmas, and sources

The investigation of rocks, minerals, and melt inclusions showed that porphyritic alkaline picrites and meimechites crystallized from different parental magmas. At a similar ultrabasic composition, the alkaline picrite melts were enriched in K₂O relative to Na₂O, and contained up to 0.12–0.13 wt % F and less Cr, Ni, and H₂O (only 0.01–0.16 wt % H₂O, versus 0.6–1.6 wt % in the meimechite melts) compared with the meimechite magmas. The crystallization of alkaline picrite melts occurred under stable conditions at relatively low temperatures without abrupt changes: olivine and clinopyroxene crystallized at 1340–1285 and 1230–1200°C, respectively, as compared with 1600–1450 and 1230–1200°C in the meimechites. The alkaline picrite melts evolved toward melanephelinite, nephelinite, tephrite, and trachydolerite; whereas the meimechite magmas gave rise to subalkaline picritic rocks. The partitioning of vanadium between olivine and melt suggests that the meimechite magma crystallized under more oxidizing conditions compared with the alkaline picrite melts: the K_DV values for the meimechite melts (0.011–0.016) were three times lower than those for the alkaline picrite melts (0.045–0.052). The parental magmas of the alkaline picrites and meimechites were enriched in trace elements relative to mantle levels by factors of tens to hundreds. The alkaline picrite magma showed lower LILE and LREE contents compared with the meimechite magma. The magmas had also different indicator ratios of incompatible elements, including those immobile in aqueous fluids. It was concluded that the meimechite and alkaline picrite melts were derived from different mantle sources. The former were generated at lower degrees of melting of an undepleted mantle source, and the meimechite melts were produced by high-degree melting of a probably lherzolite-harzburgite source.