Crystallization and Breakdown of Metasomatic Phases in Graphite-bearing Peridotite Xenoliths from Marsabit (Kenya)

Mantle-derived xenoliths from the Marsabit shield volcano (easternflank of the Kenya rift) include porphyroclastic spinel peridotitescharacterized by variable styles of metasomatism. The petrographyof the xenoliths indicates a transition from primary clinopyroxene-bearingcryptically metasomatized harzburgite (light rare earth element,U, and Th enrichment in clinopyroxene) to modally metasomatizedclinopyroxene-free harzburgite and dunite. The metasomatic phasesinclude amphibole (low-Ti Mg-katophorite), Na-rich phlogopite,apatite, graphite and metasomatic low-Al orthopyroxene. Transitionalsamples show that metasomatism led to replacement of clinopyroxeneby amphibole. In all modally metasomatized xenoliths melt pockets(silicate glass containing silicate and oxide micro-phenocrysts,carbonates and empty vugs) occur in close textural relationshipwith the earlier metasomatic phases. The petrography, majorand trace element data, together with constraints from thermobarometryand fO₂ calculations, indicate that the cryptic and modal metasomatismare the result of a single event of interaction between peridotiteand an orthopyroxene-saturated volatile-rich silicate melt.The unusual style of metasomatism (composition of amphibole,presence of graphite, formation of orthopyroxene) reflects lowP –T conditions (850–1000°C at < 1·5GPa) in the wall-rocks during impregnation and locally low oxygenfugacities. The latter allowed the precipitation of graphitefrom CO₂. The inferred melt was possibly derived from alkalinebasic melts by melt–rock reaction during the developmentof the Tertiary–Quaternary Kenya rift. Glass-bearing meltpockets formed at the expense of the early phases, mainly throughincongruent melting of amphibole and orthopyroxene, triggeredby infiltration of a CO₂-rich fluid and heating related to themagmatic activity that ultimately sampled and transported thexenoliths to the surface. KEY WORDS: graphite; peridotite xenoliths; Kenya Rift; modal metasomatism; silicate glass     

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     

Iron isotope variations in spinel peridotite xenoliths from North China Craton: implications for mantle metasomatism

Iron isotopes, together with mineral elemental compositions of spinel peridotite xenoliths and clinopyroxenites from Hannuoba and Hebi Cenozoic alkaline basalts, were analyzed to investigate iron isotopic features of the lithospheric mantle beneath the North China Craton. The results show that the Hannuoba spinel peridotite xenoliths have small but distinguishable Fe isotopic variations. Overall variations in δ⁵⁷Fe are in a range of ?0.25 to 0.14‰ for olivine, ?0.17 to 0.17‰ for orthopyroxene, ?0.21 to 0.27‰ for clinopyroxene, and ?0.16 to 0.26‰ for spinel, respectively. Clinopyroxene has the heaviest iron isotopic ratio and olivine the lightest within individual sample. No clear linear relationships between the mineral pairs on “δ-δ” plot suggest that iron isotopes of mineral separates analyzed have been affected largely by some open system processes. The broadly negative correlations between mineral iron isotopes and metasomatic indexes such as spinel Cr#, (La/Yb)_N ratios of clinopyroxenes suggest that iron isotopic variations in different minerals and peridotites were probably produced by mantle metasomatism. The Hebi phlogopite-bearing lherzolite, which is significantly modified by metasomatic events, appears to be much heavier isotopically than clinopyroxene-poor lherzolite. This study further confirms previous conclusions that the lithospheric mantle has distinguishable and heterogeneous iron isotopic variations at the xenoliths scale. Mantle metasomatism is the most likely cause for the iron isotope variations in mantle peridotites.     

Carbonatite metasomatized peridotite xenoliths from southern Patagonia: implications for lithospheric processes and Neogene plateau magmatism

The mineral chemistry, major and trace element, and Sr–Nd isotopic composition of Cr-diopside, spinel peridotite xenoliths from the Estancia Lote 17 locality in southern Patagonia document a strong carbonatitic metasomatism of the backarc continental lithosphere. The Lote 17 peridotite xenolith suite consists of hydrous spinel lherzolite, wehrlite, and olivine websterite, and anhydrous harzburgite and lherzolite. Two-pyroxene thermometry indicates equilibration temperatures ranging from 870 to 1015 °C and the lack of plagioclase or garnet suggests the xenoliths originated from between ˜40 and 60 km depth. All of the xenoliths are LILE- and LREE-enriched, but have relatively low ⁸⁷Sr/⁸⁶Sr (0.70294 to 0.70342) and high ɛ_Nd (+3.0 to +6.6), indicating recent trace element enrichment (∼25 Ma, based on the low ⁸⁷Sr/⁸⁶Sr and high Rb concentrations of phlogopite separates) in the long-term, melt-depleted Patagonian lithosphere. Lote 17 peridotite xenoliths are divided into two basic groups. Group 1 xenoliths consist of fertile peridotites that contain hydrous phases (amphibole ± phlogopite ± apatite). Group 1 xenoliths are further subdivided into three groups (a, b, and c) based on distinctive textures and whole-rock chemistry. Group 1 xenolith mineralogy and chemistry are consistent with a complex metasomatic history involving variable extents of recent carbonatite metasomatism (high Ca/Al, Nb/La, Zr/Hf, low Ti/Eu) that has overprinted earlier metasomatic events. Group 2 xenoliths consist of infertile, anhydrous harzburgites and record cryptic metasomatism that is attributed to CO₂-rich fluids liberated from Group 1 carbonatite metasomatic reactions. Extremely variable incompatible trace element ratios and depleted Sr–Nd isotopic compositions of Lote 17 peridotite xenoliths indicate that the continental lithosphere was neither the primary source nor an enriched lithospheric contaminant for Neogene Patagonian plateau lavas. Neogene plateau magmatism associated with formation of asthenospheric slab windows may have triggered this occurrence of “intraplate-type” carbonatite metasomatism in an active continental backarc setting. Received: 26 January 2000 / Accepted: 1 March 2000     

Erratum to: Iron isotope variations in spinel peridotite xenoliths from North China Craton: implications for mantle metasomatism

Iron isotopes, together with mineral elemental compositions of spinel peridotite xenoliths and clinopyroxenites from Hannuoba and Hebi Cenozoic alkaline basalts, were analyzed to investigate iron isotopic features of the lithospheric mantle beneath the North China Craton. The results show that the Hannuoba spinel peridotite xenoliths have small but distinguishable Fe isotopic variations. Overall variations in δ⁵⁷Fe are in a range of −0.25 to 0.14‰ for olivine, −0.17 to 0.17‰ for orthopyroxene, −0.21 to 0.27‰ for clinopyroxene, and −0.16 to 0.26‰ for spinel, respectively. Clinopyroxene has the heaviest iron isotopic ratio and olivine the lightest within individual sample. No clear linear relationships between the mineral pairs on “δ-δ” plot suggest that iron isotopes of mineral separates analyzed have been affected largely by some open system processes. The broadly negative correlations between mineral iron isotopes and metasomatic indexes such as spinel Cr#, (La/Yb)_N ratios of clinopyroxenes suggest that iron isotopic variations in different minerals and peridotites were probably produced by mantle metasomatism. The Hebi phlogopite-bearing lherzolite, which is significantly modified by metasomatic events, appears to be much heavier isotopically than clinopyroxene-poor lherzolite. This study further confirms previous conclusions that the lithospheric mantle has distinguishable and heterogeneous iron isotopic variations at the xenoliths scale. Mantle metasomatism is the most likely cause for the iron isotope variations in mantle peridotites.     

Metasomatism of sub-arc mantle peridotites below southernmost South America: reduction of<Emphasis Type="Italic"> f</Emphasis>O<Subscript>2</Subscript> by slab-melt

Quaternary basalts in the Cerro del Fraile area contain two types of mantle xenoliths; coarse-grained (2–5 mm) C-type spinel harzburgites and lherzolites, and fine-grained (0.5–2 mm) intensely metasomatized F-type spinel lherzolites. C-type xenoliths have high Mg in olivine (Fo = 90–91) and a range in Cr# [Cr/ (Cr + Al) = 0.17–0.34] in spinel. Two C-type samples contain websterite veinlets and solidified patches of melt that is now composed of minute quenched grains of plagioclase + Cr-spinel + clinopyroxene + olivine. These patches of quenched melts are formed by decompression melting of pargasitic amphibole. High Ti contents and common occurrence of relic Cr-spinel in the quenched melts indicate that the amphibole is formed from spinel by interaction with the Ti-rich parental magma of the websterite veinlets. The fO₂ values of these two C-type xenoliths range from ΔFMQ −0.2 to −0.4, which is consistent with their metasomatism by an asthenospheric mantle-derived melt. The rest of the C-type samples are free of “melt,” but show cryptic metasomatism by slab-derived aqueous fluids, which produced high concentrations of fluid-mobile elements in clinopyroxenes, and higher fO₂ ranging from ΔFMQ +0.1 to +0.3. F-type lherzolites are intensely metasomatized to form spinel with low Cr# (∼0.13) and silicate minerals with low MgO, olivine (Fo = ∼84), orthpyroxene [Mg# = Mg/(Mg + ΣFe) = ∼0.86] and clinopyroxene (Mg# = ∼0.88). Patches of “melt” are common in all F-type samples and their compositions are similar to pargasitic amphibole with low TiO₂ (<0.56 wt%), Cr₂O₃ (<0.55 wt%) and MgO (<16.3 wt%). Low Mg# values of silicate minerals, including the amphibole, suggest that the metasomatic agent is most likely a slab melt. This is supported by high ratios of Sr/Y and light rare earth elements (REE)/heavy REE in clinopyroxenes. F-type xenoliths show relatively low fO₂ (ΔFMQ −0.9 to −1.1) compared to C-type xenoliths and this is explained by the fusion of organic-rich sediments overlying the slab during the slab melt. Trench-fill sediments in the area are high in organic matter. The fusion of such wet sediments likely produced CH₄-rich fluids and reduced melts that mixed with the slab melt. High U and Th in bulk rocks and clinopyroxene in F-type xenoliths support the proposed interpretation.     

Crystal chemistry of amphiboles: implications for oxygen fugacity and water activity in lithospheric mantle beneath Victoria Land,Antarctica

Amphibole is the hydrous metasomatic phase in spinel-bearing mantle xenoliths from Baker Rocks, Northern Victoria Land, Antarctica. It occurs in veins or in disseminated form in spinel lherzolites. Both types derive from reaction between metasomatic melts and the pristine paragenesis of the continental lithospheric mantle beneath Northern Victoria Land. To determine the effective role of water circulation during the metasomatic process and amphibole formation, six amphibole samples were fully characterized. Accurate determination of the site population and the state of dehydrogenation in each of these amphiboles was carried out using single-crystal X-ray diffraction, electron microprobe and secondary ion mass spectroscopy on the same single crystal. The Fe³⁺/ΣFe ratio was determined by X-ray absorption near edge spectroscopy on amphibole powder. The degree of dehydrogenation determined by SIMS is 0.870–0.994 O3(O^2?) a.p.f.u., primary and ascribed to the Ti-oxy component of the amphibole, as indicated by atom site populations; post-crystallization H loss is negligible. Estimates of aH₂O (0.014–0.054) were determined from the dehydration equilibrium among end-member components assuming that amphiboles are in equilibrium with the anhydrous peridotitic phases. A difference up to 58 % in determination of aH₂O can be introduced if the chemical formula of the amphiboles is calculated based on 23 O a.p.f.u. without knowing the effective amount of dehydrogenation. The oxygen fugacity of the Baker Rocks amphibole-bearing mantle xenoliths calculated based upon the dissociation constant of water (by oxy-amphibole equilibrium) is between ?2.52 and ?1.32 log units below the fayalite–magnetite–quartz (FMQ) buffer. These results are systematically lower and in a narrow range of values relative to those obtained from anhydrous olivine–orthopyroxene–spinel equilibria (fO₂ between ?1.98 and ?0.30 log units). A comparative evaluation of the two methods suggests that when amphibole is present in mantle peridotites, the application of oxy-amphibole equilibrium is preferred, because ol–opx–sp oxy-calibrations are not “sensitive” enough in recording the effects (if any) of amphibole in the peridotite matrix. Amphibole acts as the main H acceptor among the peridotite minerals and may prevent fluid circulation and buffer oxygen fugacity. The important conclusion of this study is that amphibole within the lithospheric mantle does not always means high water activity and oxidizing conditions.     

Melt- versus fluid-induced metasomatism in spinel to garnet wedge peridotites (Ulten Zone, Eastern Italian Alps): clues from trace element and Li abundances

The peridotite bodies of the Ulten Zone (Upper Austroalpine, Italian Eastern Alps) are enclosed in Variscan migmatites and derive from a mantle wedge environment. They display the progressive transformation of porphyroclastic spinel peridotites (T=1,200°C; P=1.5 GPa) into fine-grained garnet–amphibole peridotites (T=850°C; P=3 GPa). Detailed bulk-rock and mineral trace element analyses of a sample suite documenting the entire metamorphic evolution of the peridotites revealed several stages of metasomatism. The spinel peridotites derive from a depleted mantle that became enriched in some large ion lithophile element (LILE) and light rare earth elements (LREE). The same signature pertains to clinopyroxene and orthopyroxene, indicating that this metasomatic signature was acquired at the recorded temperature of 1,200°C. Such a temperature is considerably above the wet peridotite solidus and hence the metasomatic agent must have been a hydrous melt. Moreover, the Li-enrichment of the spinel-facies pyroxenes (up to 24 ppm Li) reflects disequilibrium distribution after exchange with a presumably mafic melt. ^cpx/opx D _Li=3–7 and ^cpx/ol D _Li=2.7–8 indicate that the spinel-facies clinopyroxene hosts higher Li amounts than the coexisting minerals. LREE fractionation, variable LREE enrichment, LILE enrichment with respect to HFSE (average clinopyroxene Pb _N /Nb _N =16–90) in spinel lherzolites can be related to chromatographic effects of porous melt flow. The significant enrichment of pyroxenes from the spinel lherzolites in Pb, U and Li indicates that the metasomatic melt was subduction-related. All these features suggest that the spinel lherzolites formed a mantle wedge layer percolated by melts carrying recycled crustal components and rising from a deeper source of subduction magmas. The garnet + amphibole peridotites equilibrated at temperatures well below the wet solidus in the presence of an aqueous fluid. Bulk-rock trace element patterns display pronounced positive anomalies in Cs, Ba, Pb and U and moderate enrichment in Li, indicating addition of a crustal component to the mantle rocks. Amphibole hosts most of these trace elements. Clinopyroxene displays high LILE/HFSE (Pb _N /Nb _N =300–600), low Ce/Pb (1.4–2.7 in garnet-facies clinopyroxene compared with 2.6–24.5 in the spinel-facies one) and variable LILE and LREE enrichments. The coupled increase of modal amphibole, Sr and Pb, together with positive Pb–Sr and Pb–U correlations, further indicate that incompatible element influx in these samples was fluid-mediated. In the garnet-facies samples, amphibole and, interestingly, olivine have similarly high Li concentrations as clinopyroxene, leading to ^cpx/amph D _Li=0.7 and ^cpx/ol D _Li=0.7–0.8, the latter being up to ten times lower than in the spinel-facies rocks. Due to its high modal abundance, olivine is the main host of Li in the garnet–amphibole peridotites. The observed metasomatic features provide evidence for the infiltration of an aqueous fluid in the mantle wedge above a subducting slab. This fluid most likely derived from subducted crustal rocks that underwent partial melting. Successive retrograde re-equilibration during exhumation of the garnet peridotite is accompanied by garnet and clinopyroxene breakdown and amphibole formation. This process produced minor changes, such as an increase of HREE and Li in amphibole, and an increase of Li in olivine. The general trace element signature remains essentially unchanged during retrogression and further hydration, indicating that fluids with a similar composition to the one present at the garnet–amphibole peridotite formation, were responsible for increased amphibole formation. The combined evidence from the metamorphic and metasomatic evolution indicates that the peridotites experienced first corner flow in a mantle wedge, followed by subduction and finally entrapment and exhumation within a crustal slab. During their entire history the Ulten peridotites were percolated first by melts and then by aqueous fluids, which added recycled crustal components to the mantle wedge.     

Evolution and composition of the lithospheric mantle underneath the western Arabian peninsula: constraints from Sr−Nd isotope systematics of mantle xenoliths

On the basis of their textures and mineral compositions spinel-peridotite xenoliths of the Cr-diopside group (group I) from Cenozoic volcanic fields of Arabia can be classified into different subtypes. Type IA is of lherzolitic to harzburgitic composition; mineral compositions are similar to those of group I mantle xenoliths from worldwide occurrences. Type IB xenoliths have lherzolitic to wehrlitic compositions; Mg/(Mg+Fe) ratios of the clinopyroxenes (0.862–0.916) and olivines (0.872–0.914) are similar too or slightly lower than those of typical IA minerals. Texturally, type IB xenoliths are distinguished from type IA rocks by the presence of intragranular spinel, intragranular relict Cr-pargasite, and subordinate intergranular Ba-phlogopite (11.1% BaO). The hydrous minerals in type IB xenoliths are interpreted to document an earlier metasomatism 1 which did not affect type IA lithospheric mantle. Subsequent recrystallization caused the partial replacement of Cr-pargasite in type IB materials and resulted in the formation of less hydrous mineral assemblages. Some of the type IA xenoliths are characterized by secondary intergranular amphibole which must have formed recently. The absence or presence of this intergranular amphibole is used to distinguish an anhydrous subtype IA1 from a hydrous subtype IA2. Type IB xenoliths may also contain secondary intergranular amphibole (similar to the one in subtype IA2) or they contain abundant formermelt patches now consisting of glass and phenocrysts of olivine, clinopyroxene, amphibole, and spinel. The secondary intergranular amphiboles and the former melt patches, both are interpreted as results of a second metasomatism (metasomatism 2). In their trace element and isotopic characteristics, type IA1 and type IA2 clinopyroxenes do not exhibit any systematic differences. Furthermore, type IA2 clinopyroxenes are in Sr isotopic disequilibrium with intergranular amphiboles. This suggests that type IA2 clinopyroxenes were not modified during the second metasomatism 2. All type IA clinopyroxenes have low Sr contents (100 ppm); most of them show Sm/Nd ratios higher than inferred for bulk earth. In their ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios, type IA clinopyroxenes exhibit a large spread from 0.70226–0.70376 and from 0.51375–0.51251, respectively. Highly variable Sr/Nd ratios (5.0–79.3) and variable T_UR and T_CHUR model age relationships require different evolutions of the respective mantle portions. Nevertheless, all but two type IA clinopyroxenes form a linear array in a Sm–Nd isochron diagram which probably can not be explained by mixing. If taken as an isochron the slope of the array corresponds to an age of around 700 Ma. The mean initial _Nd of 5.8±1.7 (1) is similar to values for juvenile Pan-African (i.e. 850–650 Ma old) crust of the Arabian-Nubian shield. It is suggested that type IA lithospheric mantle and the juvenile Pan-African crust are two counterparts fractionated from a common source during the earlier stages of the Pan-African. Type IB clinopyroxenes have high Sr contents (200 ppm), variable Sr/Nd ratios (9–111) and Sm/Nd ratios generally below that inferred for bulk earth, and show a small spread in their Sr and Nd isotopic compositions (0.70299–0.70318 and 0.51285–0.51278, respectively). In a Sm–Nd isochron diagram the data points form a linear, horizontal array indicating a close-to-zero age for the earlier metasomatism 1 and suggesting a close genetic relationship to mantle processes related to the formation of the Red Sea.     

Multi-stage metasomatism of diamondiferous eclogite xenoliths from the Udachnaya kimberlite pipe,Yakutia, Siberia

The primary garnet (pyrope-almandine)-omphacite (Cpx 1, 6.5–7 wt% Na₂O)-sulfide (Fe-Ni-Co mss) assemblage of the two diamondiferous eclogite xenoliths studied (U33/1 and UX/1) experienced two mantle metasomatic events. The metasomatic event I is recorded by the formation of platy phlogopite (~ 10 wt% K₂O), prior to incorporation of the xenoliths in the kimberlite. The bulk of the metasomatic alteration, consisting of spongy-textured clinopyroxene (Cpx 2A, 1–3 wt% Na₂O), coarser-grained clinopyroxene (Cpx 2B, 2–5 wt% Na₂O), pargasitic amphibole (~ 0.8 wt% K₂O; 3–3.5 wt% Na₂O), kelyphite (Cpx 3, mostly <1 wt% Na₂O; and zoned Mg-Fe-Al spinel), sodalite, calcite, K-feldspar, djerfisherite (K_5.95Na_0.02Fe_18.72Ni_2.36Co_0.01Cu_4.08S₂₆Cl ) and a small amount of K-Ca-Fe-Mg glass, is ascribed to the metasomatic event II that occurred also in the upper mantle, but after the xenoliths were incorporated in the kimberlite. A pervasive chloritic alteration (mainly clinochlore + magnetite) that overprints earlier assemblages probably took place in the upper crustal environment. The diamonds are invariably associated with secondary clinopyroxene and chlorite, but the diamonds formed before the entrainment of the xenoliths in the Udachnaya kimberlite.Editorial Responsibility: T.L. Grove     

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

 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. Received: 2 March 1995 / Accepted: 12 June 1995     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Mantle metasomatism and magma formation in continental lithosphere: Data on xenoliths in alkali basalts from the Makhtesh Ramon,Negev desert,Israel

Mantle xenoliths (lherzolites, clinopyroxene dunites, wehrlites, and clinopyroxenites) in the Early Cretaceous volcanic rocks of Makhtesh Ramon (alkali olivine basalts, basanites, and nephelinites) represent metasomatized mantle, which served as a source of basaltic melts. The xenoliths bear signs of partial melting and previous metasomatic transformations. The latter include the replacement of orthopyroxene by clinopyroxene in the lherzolites and, respectively, the wide development of wehrlites and olivine clinopyoroxenites. Metasomatic alteration of the peridotites is accompanied by a sharp decrease in Mg, Cr, and Ni, and increase of Ti, Al, Ca contents and ³⁺Fe/²⁺Fe ratio, as well as the growth of trace V, Sc, Zr, Nb, and Y contents. The compositional features of the rocks such as the growth of ³⁺Fe/²⁺Fe and the wide development of Ti-magnetite in combination with the complete absence of sulfides indicate the high oxygen fugacity during metasomatism and the low sulfur concentration, which is a distinctive signature of fluid mode during formation of the Makhtesh Ramon alkali basaltic magma. Partial melting of peridotites and clinopyroxenites is accompanied by the formation of basanite or alkali basaltic melt. Clino- and orthopyroxenes are subjected to melting. The crystallization products of melt preserved in the mantle rock are localized in the interstices and consist mainly of fine-grained clinopyroxene, which together with Ti-magnetite, ilmenite, amphibole, rhenite, feldspar, and nepheline, is cemented by glass corresponding to quartz–orthopyroxene, olivine–orthopyroxene, quartz–feldspar, or nepheline–feldspar mixtures of the corresponding normative minerals. The mineral assemblages of xenoliths correspond to high temperatures. The high-Al and high-Ti clinopyroxene, calcium olivine, feldspar, and feldspathoids, amphibole, Ti-magnetite, and ilmenite are formed at 900–1000°. The study of melt and fluid inclusions in minerals from xenoliths indicate liquidus temperatures of 1200–1250°C, solidus temperatures of 1000–1100°C, and pressure of 5.9–9.5 kbar. Based on the amphibole–plagioclase barometer, amphibole and coexisting plagioclase were crystallized in clinopyroxenites at 6.5–7.0 kbar.     

Magmatic modification of the uppermost mantle beneath the Basin and Range to Colorado Plateau Transition Zone; Evidence from xenoliths, Wikieup, Arizona

Upper mantle xenoliths from Wikieup, AZ, provide abundant evidence for magmatic modification of the uppermost mantle beneath the Transition Zone between the Colorado Plateau and the southern Basin and Range province. Upper mantle lithologies in this xenolith suite are represented by spinel peridotite, wehrlite, plagioclase peridotite, and Al-augite group pyroxenites. Isotopic data for these xenoliths yield relatively uniform values and suggest a common petrogenesis. Al-augite-bearing gabbro and pyroxenite xenoliths from this locality are interpreted to have formed by crystal fractionation processes from parent alkali basalts similar to the Wikieup host basalt. Mineral and whole rock compositions show consistent trends of increasing incompatible element contents (Fe, Al, Ca, Na, K, LIL, and LREE), and decreasing compatible element contents (Mg, Cr, Ni) from spinel peridotite to wehrlite to plagioclase peridotite to the host basalt composition. These compositional trends are interpreted as resulting from varying degrees of magma-mantle wall rock interaction as ascending mafic magmas infiltrated upper mantle peridotite. Small degrees of melt infiltration resulted in slightly modified spinel peridotite compositions while moderate degrees metasomatized spinel peridotite to wehrlite, and the highest degrees metasomatized it to plagioclase peridotite. Whole rock compositions and clinopyroxene, plagioclase, and whole rock isotopic data suggest that the infiltrating magmas were the same as those from which the gabbros and pyroxenites crystallized, and that they were alkalic in composition, similar to the Wikieup host alkali olivine basalts. Relatively uniform ¹⁴³Nd/¹⁴⁴Nd for the mineral separates and whole rocks in spite of the significantly wide range in their ¹⁴⁷Sm/¹⁴⁴Nd (0.71–0.23 in clinopyroxene) suggests that the Wikieup xenoliths including gabbro, pyroxenite, peridotite, wehrlite, and plagioclase peridotite, are all relatively young rocks formed or metasomatized by a relatively recent magmatic episode. Received: 21 May 1996 / Accepted: 23 December 1996     

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

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.     

Silicic melts produced by reaction between peridotite and infiltrating basaltic melts: ion probe data on glasses and minerals in veined xenoliths from La Palma, Canary Islands

Mantle xenoliths hosted by the historic Volcan de San Antonio, La Palma, Canary Islands include veined spinel harzburgites and spinel dunites. Glasses and associated minerals in the vein system of veined xenoliths show a gradual transition in composition from broad veins to narrow veinlets. Broad veins contain alkali basaltic glass with semi-linear trace element patterns enriched in strongly incompatible elements. As the veins become narrower, the SiO₂-contents in glass increase (46 → 67 wt% SiO₂ in harzburgite, 43 → 58 wt% in dunite) and the trace element patterns change gradually to concave patterns depleted in moderately incompatible elements (e.g. HREE, Zr, Ti) relative to highly incompatible ones. The highest SiO₂-contents (ca. 68% SiO₂, low Ti-Fe-Mg-Ca-contents) and most extreme concave trace element patterns are exhibited by glass in unveined peridotite xenoliths. Clinopyroxenes shift from LREE-enriched augites in basaltic glass, to REE-depleted Cr-diopside in highly silicic glass. Estimates indicate that the most silicic glasses represent melts in, or near, equilibrium with their host peridotites. The observed trace element changes are compatible with formation of the silicic melts by processes involving infiltration of basaltic melts into mantle peridotite followed by reactions and crystallization. The Fe-Mg interdiffusion profiles in olivine porphyroclasts adjacent to the veins indicate a minimum period of diffusion of 600 years, implying that the reaction processes have taken place in situ in the upper mantle. The CaO-TiO₂-La/Nd relationships of mantle rocks may be used to discriminate between metasomatism caused by carbonatitic and silicic melts. Unveined mantle xenoliths from La Palma and Hierro (Canary Islands) show a wide range in La/Nd ratios with relatively constant, low-CaO contents which is compatible with metasomatism of “normal” abyssal peridotite by silicic melts. Peridotite xenoliths from Tenerife show somewhat higher CaO and TiO₂ contents than those from the other islands and may have been affected by basaltic or carbonatitic melts. The observed trace element signatures of ultramafic xenoliths from La Palma and other Canary Islands may be accounted for by addition of small amounts (1–7%) of highly silicic melt to unmetasomatized peridotite. Also ultramafic xenoliths from other localities, e.g. eastern Australia, show CaO-TiO₂-La/Nd relationships compatible with metasomatism by silicic melts. These results suggest that silicic melts may represent important metasomatic agents. Received: 15 November 1998 / Accepted: 17 May 1999     

A redox profile of the Slave mantle and oxygen fugacity control in the cratonic mantle

The authors report a redox profile based on Mössbauer data of spinel and garnet to a depth of 210 km from mantle xenoliths of the northern (N) and southeastern (SE) Slave craton (northern Canada). The profile transects three depth facies of peridotites that form segments of different bulk composition, represented by spinel peridotite, spinel–garnet peridotite, low-temperature garnet peridotite, high-temperature garnet peridotite, and pyroxenite. The shallow, more depleted N Slave spinel peridotite records lower oxygen fugacities compared to the deeper, less depleted N Slave spinel–garnet peridotite, consistent with their different spinel Fe³⁺ concentrations. Garnet peridotites show a general reduction in log fO₂ (FMQ)s with depth, where values for garnet peridotites are lower than those for spinel–garnet peridotites. There is a strong correlation between depletion and oxygen fugacity in the spinel peridotite facies, but little correlation in the garnet peridotite facies. The strong decrease in log fO₂ (FMQ) with depth that arises from the smaller partial molar volume of Fe³⁺ in garnet, and the observation of distinct slopes of log fO₂ (FMQ) with depth for spinel peridotite compared to spinel–garnet peridotite strongly suggest that oxygen fugacity in the cratonic peridotitic mantle is intrinsically controlled by iron equilibria involving garnet and spinel.

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Composition and evolution of lithosphere beneath the Carpathian–Pannonian Region: a review

Our knowledge of the lithosphere beneath the Carpathian–Pannonian Region (CPR) has been greatly improved through petrologic, geochemical and isotopic studies of upper mantle xenoliths hosted by Neogene–Quaternary alkali basalts. These basalts occur at the edge of the Intra-Carpathian Basin System (Styrian Basin, Nógrád-Gömör and Eastern Transylvanian Basin) and its central portion (Little Hungarian Plain, Bakony-Balaton Highland).The xenoliths are mostly spinel lherzolites, accompanied by subordinate pyroxenites, websterites, wehrlites, harzburgites and dunites. The peridotites represent residual mantle material showing textural and geochemical evidence for a complex history of melting and recrystallization, irrespective of location within the region. The lithospheric mantle is more deformed in the center of the studied area than towards the edges. The deformation may be attributed to a combination of extension and asthenospheric upwelling in the late Tertiary, which strongly affected the central part of CPR subcontinental lithosphere.The peridotite xenoliths studied show bulk compositions in the following range: 35–48 wt.% MgO, 0.5–4.0 wt.% CaO and 0.2–4.5 wt.% Al₂O₃ with no significant differences in regard to their geographical location. On the other hand, mineral compositions, particularly of clinopyroxene, vary according to xenolith texture. Clinopyroxenes from less deformed xenoliths show higher contents of ‘basaltic’ major elements compared to the more deformed xenoliths. However, clinopyroxenes in more deformed xenoliths are relatively enriched in strongly incompatible trace elements such as light rare earth elements (LREE).Modal metasomatic products occur as both hydrous phases, including pargasitic and kearsutitic amphiboles and minor phlogopitic micas, and anhydrous phases — mostly clinopyroxene and orthopyroxene. Vein material is dominated by the two latter phases but may also include amphibole. Amphibole mostly occurs as interstitial phases, however, and is more common than phlogopite. Most metasomatized peridotites show chemical and (sometimes) textural evidence for re-equilibration between metasomatic and non-metasomatic phases. However, amphiboles in pyroxenites are sometimes enriched in K, Fe and LREE. The presence of partially crystallized melt pockets (related to amphiboles and clinopyroxenes) in both peridotites and pyroxenites is an indication of decompression melting and, rarely, incipient partial melting triggered by migrating hydrous melts or fluids. Metasomatic contaminants may be ascribed to contemporaneous subduction beneath the Carpathian–Pannonian Region between the Eocene and Miocene.Sulfide inclusions are more abundant in protogranular and porphyroclastic xenoliths relative to equigranular types. In mantle lithologies, sulfide bleb compositions vary between pentlandite and pyrrhotite correlating with the chemistry and texture of the host xenoliths. While sulfides in peridotites are relatively rich in Ni, those in clinopyroxene-rich xenoliths are notably Fe-rich.     

Petrology of ultramafic nodules from São Tomé Island, Cameroon Volcanic Line (oceanic sector)

Ultramafic xenoliths were found in recent alkali basalts from São Tomé Island. These include spinel peridotites (lherzolites, harzburgites and dunites) and pyroxenites (orthopyroxenites and clinopyroxenites). Textures and mineral compositions indicate that pyroxenites originated from crystal/liquid separation processes operating on magmas similar to those giving rise to their present host rocks whereas spinel peridotite xenoliths had an accidental origin; Fo (>89) and Ni (>0.36 wt.%) contents in olivines, Mg# (91–95) of orthopyroxenes and low Ti in clinopyroxene (primary crystals: TiO₂<0.06 wt.%) and in spinel (TiO₂<0.1 wt.%) are within the range reported for abyssal peridotites, indicating São Tomé spinel peridotites represent refractory residues of melting. Nevertheless, the lack of correlation between mineral chemistry and modal composition suggests that spinel peridotite xenoliths are not simple residues and were affected by infiltration of fluid/melts within the mantle. The wide temperature range obtained for spinel peridotites (700 to >1150 °C) is compatible with a long period of pre-entrainment cooling supporting Fitton's [Tectonophysics 94 (1983) 473] hypothesis that proposes oceanic lithosphere uprising in the Cameroon Volcanic Line prior to the initiation of the current thermal regime, related to São Tomé magmatism. The association of upper mantle (peridotite) xenoliths with igneous cumulates (pyroxenites) suggests that the spinel peridotite suite originated in the uppermost mantle above the São Tomé magma storage zone(s), probably in a region of high strain rate, near the boundary between the mantle and the overlying oceanic crust.     

Mechanisms and Sources of Mantle Metasomatism: Major and Trace Element Compositions of Peridotite Xenoliths from Spitsbergen in the Context of Numerical Modelling

Mineral and whole-rock chemical data for peridotite xenolithsin basaltic lavas on Spitsbergen are examined to reassess mechanismsof melt–fluid interaction with peridotites and their relativerole versus melt composition in mantle metasomatism. The enrichmentpatterns in the xenoliths on primitive mantle-normalized diagramsrange from Th–La–Ce ‘inflections’ inweakly metasomatized samples (normally without amphibole) toa continuous increase in abundances from Ho to Ce typical foramphibole-bearing xenoliths. Numerical modelling of interactionbetween depleted peridotites and enriched melts indicates thatthese patterns do not result from simple mixing of the two end-membersbut can be explained by chromatographic fractionation duringreactive porous melt flow, which produces a variety of enrichmentpatterns in a single event. Many metasomatized xenoliths havenegative high field strength element and Pb anomalies and Srspikes relative to rare earth elements of similar compatibility,and highly fractionated Nb/Ta and Zr/Hf. Although amphiboleprecipitation can produce Nb–Ta anomalies, some of thesefeatures cannot be attributed to percolation-related fractionationalone and have to be a signature of the initial melt (possiblycarbonate rich). In general, chemical and mineralogical fingerprintsof a metasomatic medium are strongest near its source (e.g.a vein) whereas element patterns farther in the metasomatic‘column’ are increasingly controlled by fractionationmechanisms. KEY WORDS: Spitsbergen; lithospheric mantle; metasomatism; trace elements; theoretical modelling