Volatiles in amphiboles from xenoliths,Vulcan's Throne,Grand Canyon,Arizona, USA

Analyses of major element and volatile components of amphiboles from Vulcan's Throne, a Recent volcano on the north rim of the Grand Canyon, Arizona, USA, have been performed by using the electron microprobe and high temperature mass spectrometry. The amphiboles occur as megacrysts, as oikocrysts in peridotite and pyroxenite xenoliths, in amphibole-rich selvages on lherzolite xenoliths, and as grains in hornblendite xenoliths. Total volatiles range from 1.27 to 1.75 wt.%. In all samples, H₂O is the principal volatile species. Lesser amounts of structurally bound fluorine, chlorine, and oxygen were also released. The amphiboles studied are hydroxyl-deficient. The O(3) site is probably partially occupied by O^2?, which was detected as O₂ during degassing of the amphibole. Ti shows a strong positive correlation with the amount of hydroxyl deficiency in the amphiboles except for one oxidized sample. Thus, Ti probably is significant in charge balancing the substitution of O^2? for OH^? and the substitution probably occurred during crystallization rather than by dehydrogenation. Small amounts of both oxidized and reduced carbon and sulfur-bearing volatile species (e.g., CO₂, CO, CH₄, SO₂, H₂S) were detected in all samples. The observation of reduced carbon species supports the hypothesis that the oxygen fugacity of at least portions of the upper mantle is probably less than the quartz-fayalite-magnetite buffer.     

华北克拉通中生代拆沉陆壳物质对岩石圈地幔的改造:来自橄榄岩捕虏体中角闪石的成分制约

对鲁西和太行山南段早白垩世高镁闪长岩中橄榄岩捕虏体中的角闪石进行了主量元素和痕量元素分析,并讨论了角闪石成分与改造岩石圈地幔熔体的性质与来源之间的关系。研究结果表明,橄榄岩类捕虏体中的角闪石主要为交代成因。在化学上,它们属于钙质角闪石。太行山南段符山橄榄岩捕虏体中的角闪石属于镁质普通角闪石和浅闪石或浅闪石质普通角闪石;鲁西铁铜沟橄榄岩捕虏体中的角闪石为韭闪石质普通角闪石、浅闪石质普通角闪石和镁绿钙闪石质普通角闪石。与板内橄榄岩捕虏体中的角闪石相比,鲁西和太行山南段早白垩世高镁闪长岩橄榄岩捕虏体中的角闪石具有相对高的Mg#(鲁西:86.0~90.8;太行山:90.7~94.2)和SiO2(鲁西:44.04%~46.98%;太行山:47.09%~49.79%)以及相对低的Na2O(1.92%~2.51%)、TiO2(0.01%~1.46%)、Nb(0.29×10-6~1.98×10-6)和Zr(1.61×10-6~5.34×10-6),这与来自俯冲带之上地幔楔橄榄岩捕虏体中的角闪石相类似。综合橄榄岩捕虏体的地球化学特征,可以判定华北克拉通早白垩世岩石圈地幔遭受了起源于拆沉陆壳物质熔融熔体的改造。     

Ultramafic Xenoliths in Plio-Pleistocene Alkali Basalts from the Eastern Transylvanian Basin: Depleted Mantle Enriched by Vein Metasomatism

Ultramafic xenoliths from alkali basalts in the Perjani Mountainsin the Eastern Transylvanian Basin (ETB) of Romania are mainlyspinel Iherzolites, although spinel harzburgites, websterites,clinopyroxenites and amphibole pyroxenites are also present.Amphibole veins cut some spinel peridotite samples. All arederived from the shallow lithospheric upper mantle. In general,textural variations are restricted to protogranular and porphyroclastictypes, compared with the more varied textures found in mantlexenoliths from the alkali basalts of the neighbouring PannonianBasin. Also, ETB peridotites are richer in amphibole. Thus,the mantle beneath the edge of the ETB is less deformed butmore strongly metasomatized than the mantle closer to the centreof the Pannonian Basin.Mineralogical and bulk-rock geochemicalvariations resemble those of spinel Iherzolites from other sub-continentalshallow mantle xenolith suites. There is no apparent correlationbetween deformation and geochemistry, and much of the majorand trace element variation is due to variable extraction ofpicritic melts. The REE patterns of separated clinopyroxenesfrom the peridotite xenoliths are mostly LREE depleted, althoughclinopyroxenes from regions adjacent to amphibole veins haveexperienced an enrichment in La and Ce and a change in theirSr and Nd isotopic values towards those of the vein, while stillretaining an overall LREE depletion. Clinopyroxenes from thewebsterites and clinopyroxenites are more variable. Amphibolein the hydrous pyroxenites and amphibole veins is strongly LREEenriched and is considered to be metasomatic in origin. ⁸⁷Sr/⁸⁶Srand ¹⁴³Nd/^l44Nd isotopic ratios of the xenoliths vary between07018 and 07044, and 051355 and 0 51275, respectively. Thesevalue are more depleted than those obtained for xenoliths fromthe Pannonian Basin. The lower ^l43Nd/^l44Nd and higher ⁸⁷Sr/Sr⁸⁶values are found in anhydrous pyroxenites, metasomatic amphibolesin veins and amphibole pyroxenites, and in the only exampleof an equigranular spinel Iherzolite in the suite.The ETB xenolithswere brought to the surface in alkaline vokanism which post-dateda period of Miocene to Pliocene subduction-related cak-alkalinevolcanism. However, the effects of the passage of either slab-derivedfluids or cak-alkaline magmas through the ETB lithospheric mantlecannot be discerned in the chemistry of the xenoliths. The metasomaticamphibole has ⁸⁷Sr/Sr⁸⁶ and ¹⁴³Sr/Sr¹⁴⁴ ratios similar to thehost alkali basalts, but the least evoked cak-alkaline magmasalso have similar Sr and Nd isotope compositions. The REE patternsof the amphibole resembk those of amphiboles considered to havecrystallized from alkaline melts. No preferential enrichmentin elements typically associated with slab-derivedfluids (K,Rb and Sr) relative to elements typically depleted in cak-alkalinemagmas (Ti, 2jr and Nb) has been observed in the vein amphiboles,although some interstitial amphibole is depleted in all incompatibletrace elements, including LREE. Thus, despite its position closeto the calc-alkaline volcanic arc of the Eastern Carpathians,we cannot readily detect any interaction between the lithosphericupper mantle beneath the ETB and subduction-related magmas orfluids. Metasomatism in the lithospheric mantle is instead largelyrelated to the passage of a primitive alkaline magma similarto the host alkali basal ^*corresponding author     

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.     

Fractionation of Nb and Ta from Zr and Hf at Mantle Depths: the Role of Titanian Pargasite and Kaersutite

Selective enrichment or depletion in either Zr and Hf (HFSE⁴⁺)or Nb and Ta (HFSE⁵⁺) is a feature commonly observed in manymantle-derived melts and amphiboles occurring as either disseminatedminerals in mantle xenoliths and peridotite massifs or in veinassemblages cutting these rocks. The fractionation of Nb fromZr seen in natural mantle amphiboles suggests that their incorporationis governed by different crystal-chemical mechanisms. An extensiveset of new partitioning experiments between pargasite–kaersutiteand melt under upper-mantle conditions shows that HFSE incorporationand fractionation depends on amphibole major-element compositionand the presence or absence of dehydrogenation. Multiple regressionanalysis shows that ^Amph/LD_Nb/Zr is strongly dependent on themg-number of the amphibole as a result of a combination of amphiboleand melt structure effects, so that the following generalizationsapply: (1) high-mg-number amphiboles crystallized from unmodifiedmantle melts more easily incorporate Zr relative to Nb leadingto an increase of the Nb/Zr ratio in the residual melt; (2)low-mg-number amphiboles, such as those found in veins cuttingperidotites, may strongly deplete the residual melt in Nb andcause very low Nb/Zr in residual melts. Implications and applicationsto mantle environments are discussed. KEY WORDS: trace elements; high field strength elements; partition coefficients; amphibole; upper mantle     

Metasomatism of the Pan-African lithospheric mantle beneath the Damara Belt,Namibia, by the Tristan mantle plume: geochemical evidence from mantle xenoliths

In situ trace element analyses of constituent minerals in mantle xenoliths occurring in an alnöite diatreme and in nephelinite plugs emplaced within the central zone of the Damara Belt have been determined by laser ablation ICP-MS. Primitive mantle-normalized trace element patterns of clinopyroxene and amphibole indicate the presence of both depleted MORB-like mantle and variably enriched mantle beneath this region. Clinopyroxenes showing geochemical depletion have low La/Sm_n ratios (0.02–0.2), whereas those showing variable enrichment have La/Sm_n ranging up to 3.8 and La/Yb_n to 9.1. The most enriched clinopyroxenes coexist with amphibole showing similar REE patterns (La/Sm_n = 1.3–4.1; La/Yb_n = 4.5–9). Primitive mantle-normalized trace element patterns allow further groups to be distinguished amongst the variably enriched clinopyroxenes: one having strong relative depletion in Rb–Ba, Ta–Nb and relative enrichment in Th–U; another with similar characteristics but with additional strong relative depletion in Zr–Hf; and one showing no significant anomalies. Amphiboles show similar normalized trace element patterns to co-existing clinopyroxene. Clinopyroxene and amphiboles showing LREE_N enrichment have high Sr and low Nd isotope ratios compared to clinopyroxene with LREE-depleted patterns. Numerical simulation of melt percolation through the mantle via reactive porous flow is used to show that the chromatographic affect associated with such a melt migration process is able to account for the fractionation seen in La–Ce–Nd in cryptically metasomatized clinopyroxenes in Type 1 xenoliths, where melt–matrix interactions occur near the percolation front, whereas REE patterns in clinopyroxenes proximal to the source of metasomatic melt/fluid match those found in modally metasomatized Type 2 xenoliths. The strong fractionation between Rb–Ba, Th–U and Ta–Nb shown by some cryptically metasomatized xenoliths can be also accounted for by reactive porous flow, provided amphibole crystallizes from the percolating melt/fluid close to its source. The presence of amphibole in vein-like structures in some xenoliths is consistent with this interpretation. The strong depletion in Zr–Hf in clinopyroxene and amphibole in some xenoliths cannot be accounted for by melt migration processes and requires metasomatism by a separate carbonate-rich melt/fluid. When taken together with published isotope data on these same xenoliths, the source of metasomatic enrichment of the previously depleted (MORB-like) sub-Damaran lithospheric mantle is attributed to the upwelling Tristan plume head at the time of continental breakup.     

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     

Mathiasite-loveringite and priderite in mantle xenoliths from the Alto Paranaíba Igneous Province,Brazil: genesis and constraints on mantle metasomatism

Alkali-bearing Ti oxides were identified in mantle xenoliths enclosed in kimberlite-like rocks from Limeira 1 alkaline intrusion from the Alto Paranaíba Igneous Province, southeastern Brazil. The metasomatic mineral assemblages include mathiasite-loveringite and priderite associated with clinopyroxene, phlogopite, ilmenite and rutile. Mathiasite-loveringite (55–60 wt.% TiO₂; 5.2–6.7 wt.% ZrO₂) occurs in peridotite xenoliths rimming chromite (～50 wt.% Cr₂O₃) and subordinate ilmenite (12–13.4 wt.% MgO) in double reaction rim coronas. Priderite (Ba/(K+Ba)< 0.05) occurs in phlogopite-rich xenoliths as lamellae within Mg-ilmenite (8.4–9.8 wt.% MgO) or as intergrowths in rutile crystals that may be included in sagenitic phlogopite. Mathiasite-loveringite was formed by reaction of peridotite primary minerals with alkaline melts. The priderite was formed by reaction of peridotite minerals with ultrapotassic melts. Disequilibrium textures and chemical zoning of associated minerals suggest that the metasomatic reactions responsible for the formation of the alkali-bearing Ti oxides took place shortly prior the entrainment of the xenoliths in the host magma, and is not connected to old (Proterozoic) mantle enrichment events.     

Significance of ancient sulfide PGE and Re–Os signatures in the mantle beneath Calatrava,Central Spain

Spinel lherzolite and wehrlite xenoliths from the Cenozoic Calatrava volcanic field carry the geochemical imprint of metasomatic agents that have affected the subcontinental lithospheric mantle beneath Central Iberia. Some xenoliths (mainly wehrlites) were enriched in REE, Sr, P, and CO₂ by silicic-carbonate-rich metasomatic melts/fluids, while others record the effects of subduction-related hydrous silicate fluids that have precipitated amphibole and induced high Ti/Eu in primary clinopyroxene. The petrographic observations and geochemical data suggest that interstitial glass in the xenoliths represent the quenched products of Si-rich melts that infiltrated the mantle peridotite shortly before the entrainment of the xenoliths in the host magmas that erupted ca 2 million years ago. During their infiltration, the metasomatic melts reacted with peridotite, resulting in silica enrichment, while remobilizing grains of iron-rich monosulfide solid solution (Fe-rich Mss) initially enclosed in, or intergranular to, primary olivine and pyroxenes. In situ laser ablation inductively coupled plasma-mass spectrometry analysis of single sulfide grains reveals that the Fe-rich Mss in glass shows platinum-group element (PGE) patterns and ¹⁸⁷Os/¹⁸⁸Os compositions identical to the Fe-rich Mss occurring as inclusions in, or at grain boundaries of primary silicates. Moreover, independent of its microstructural position, Fe-rich Mss exhibits PGE and ¹⁸⁷Os/¹⁸⁸Os signatures typical of Mss either residual after partial melting or crystallized directly from sulfide melts. Our findings reveal that young metasomatic melt(s)/fluid(s) may carry remobilized sulfides with PGE and Os-isotopic signatures identical to those of texturally older sulfides in the peridotite xenolith. These sulfides thus still provide useful information about the timing and nature of older magmatic events in the subcontinental mantle.     

Metasomatic oxidation of upper mantle periodotite

Examination of Fe³⁺ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe³⁺ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (Fe_T) as Fe³⁺ (Fe³⁺/Fe_T=0.33); orthopyroxenes contain 0.06–0.09 Fe³⁺/Fe_T; spinels contain 0.30–0.40 Fe³⁺/Fe_T; olivines contain 0.01–0.06 Fe³⁺/Fe_T; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe³⁺/Fe_T. In each mineral, Fe³⁺ and Fe²⁺ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe³⁺/Fe_T ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe³⁺/Fe_T ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe³⁺/Fe_T ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe³⁺ into existing mineral grains rather than by oxidation of existing Fe²⁺ in peridotite mineral grains. The very high Fe³⁺/Fe_T ratio in the metasomatic amphibole may be a function of the high Fe³⁺/Fe_T of the metasomatic fluid, crystal chemical limitations on the amount of Fe³⁺ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe₂O₃. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe²⁺ and Fe³⁺ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe³⁺. With increasing distance from the dike, the ratio of added Fe³⁺ to added Fe²⁺ increases. The high Fe³⁺/Fe_T of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe³⁺/added Fe²⁺ in pyroxenes and spinel suggest that the Fe³⁺/Fe_T ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe³⁺ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe³⁺/Fe_T.     

Water in Mantle-derived Xenoliths in the Hannuoba Basalt

Minerals of various mantle-derived xenoliths from the Hannuoba basalt in Hebei Province have been studied by means of IR spectroscopy. The results show that all xenoliths from the mantle at depths <75 km contain trace amounts of water (0.45%-11.6×10-2 % H2O). The data of about 0.1% H2O contained in primary pyrolite estimated by earlier studies may be on the high side. The water might enter the frameworks of olivine, pyroxene and garnet earlier than it entered those of amphibole and phlogopite. The presence of water in amphibole and phlogopite may be a local phenomenon of water enrichment, which is related to relatively small-scale magmatic or metasomatic events although they can contain a hundred times more water than pyroxene contains. There is a little more water (1.11%-3.01×10-2 % of H2O mostly) in xenoliths from the Hannuoba basalt than in those from mid-ocean ridge basalt and kimberlites of South Africa (less than 1×10-2 % of H2O mostly). This indicates the heterogeneity of water in time and spa     

Phlogopite in mantle xenoliths and kimberlite from the Grib pipe,Arkhangelsk province,Russia:Evidence for multi-stage mantle metasomatism and origin of phlogopite in kimberlite

We present petrography and mineral chemistry for both phlogopite,from mantle-derived xenoliths(garnet peridotite,eclogite and clinopyroxene-phlogopite rocks)and for megacryst,macrocryst and groundmass flakes from the Grib kimberlite in the Arkhangelsk diamond province of Russia to provide new insights into multi-stage metasomatism in the subcratonic lithospheric mantle(SCLM)and the origin of phlogopite in kimberlite.Based on the analysed xenoliths,phlogopite is characterized by several generations.The first generation(Phil)occurs as coarse,discrete grains within garnet peridotite and eclogite xenoliths and as a rock-forming mineral within clinopyroxene-phlogopite xenoliths.The second phlogopite generation(Phl2)occurs as rims and outer zones that surround the Phil grains and as fine flakes within kimberlite-related veinlets filled with carbonate,serpentine,chlorite and spinel.In garnet peridotite xenoliths,phlogopite occurs as overgrowths surrounding garnet porphyroblasts,within which phlogopite is associated with Cr-spinel and minor carbonate.In eclogite xenoliths,phlogopite occasionally associates with carbonate bearing veinlet networks.Phlogopite,from the kimberlite,occurs as megacrysts,macrocrysts,microcrysts and fine flakes in the groundmass and matrix of kimberlitic pyroclasts.Most phlogopite grains within the kimberlite are characterised by signs of deformation and form partly fragmented grains,which indicates that they are the disintegrated fragments of previously larger grains.Phil,within the garnet peridotite and clinopyroxene-phlogopite xenoliths,is characterised by low Ti and Cr contents(TiO_21 wt.%,Cr_2 O_31 wt.% and Mg# = 100 × Mg/(Mg+ Fe)92)typical of primary peridotite phlogopite in mantle peridotite xenoliths from global kimberlite occurrences.They formed during SCLM metasomatism that led to a transformation from garnet peridotite to clinopyroxene-phlogopite rocks and the crystallisation of phlogopite and high-Cr clinopyroxene megacrysts before the generation of host-kimberlite magmas.One of the possible processes to generate low-Ti-Cr phlogopite is via the replacement of garnet during its interaction with a metasomatic agent enriched in K and H_2O.Rb-Sr isotopic data indicates that the metasomatic agent had a contribution of more radiogenic source than the host-kimberlite magma.Compared with peridotite xenoliths,eclogite xenoliths feature low-Ti phlogopites that are depleted in Cr_2O_3 despite a wider range of TiO_2 concentrations.The presence of phlogopite in eclogite xenoliths indicates that metasomatic processes affected peridotite as well as eclogite within the SCLM beneath the Grib kimberlite.Phl2 has high Ti and Cr concentrations(TiO_22 wt.%,Cr_2O_31 wt.% and Mg# = 100× Mg/(Mg + Fe)92)and compositionally overlaps with phlogopite from polymict brecc:ia xenoliths that occur in global kimberlite formations.These phlogopites are the product of kimberlitic magma and mantle rock interaction at mantle depths where Phl2 overgrew Phil grains or crystallized directly from stalled batches of kimberlitic magmas.Megacrysts,most macrocrysts and microcrysts are disintegrated phlogopite fragments from metasomatised peridotite and eclogite xenoliths.Fine phlogopite flakes within kimberlite groundmass represent mixing of high-Ti-Cr phlogopite antecrysts and high-Ti and low-Cr kimberlitic phlogopite with high Al and Ba contents that may have formed individual grains or overgrown antecrysts.Based on the results of this study,we propose a schematic model of SCLM metasomatism involving phlogopite crystallization,megacryst formation,and genesis of kimberlite magmas as recorded by the Grib pipe.     

Experimental reactions between olivine and orthopyroxene with phonolite melt: implications for the origins of hydrous amphibole + phlogopite + diopside bearing metasomatic veins

Amphibole + phlogopite + diopside bearing veins are observed in a large number of upper mantle xenoliths, but the composition of the melt that forms them is poorly constrained. Recent data from the Heldburg Phonolite, Central Germany, has shown that phonolite melt will react with olivine and orthopyroxene xenocrysts to form reaction rims of amphibole + phlogopite + diopside at mid-lower crustal pressures. This is the first example of where a melt has reacted with peridotite to form the mineralogy of the metasomatic veins. It is therefore necessary to explore whether a phonolite melt could be the parent melt that forms amphibole + phlogopite + diopside metasomatic veins. Experimental reactions between single crystals of olivine and orthopyroxene with phonolite melt were conducted at upper mantle conditions of 1.0–1.5 GPa and 900–1,000 °C. Melt water contents were varied from anhydrous to >12 wt. H₂O. Olivine reacts to form phlogopite reaction rims with overgrowths of diopside <1,000 °C or rims of secondary olivine >1,000 °C. Orthopyroxene reacts to form amphibole with epitaxial diopside overgrowths <1,000 °C. No reaction rims form when the bulk melt H₂O is lower than ~3.8 wt%. Pressure has little effect over the small range tested. These experiments reproduce reaction rims on olivine and orthopyroxene observed in the Heldburg Phonolite, Central Germany, and suggest that a relatively narrow range of temperatures and melt water contents is required for rim formation. The compositions of rim amphibole, phlogopite and diopside from the experiments have very similar compositions to those from Heldburg but do not match those from metasomatic veins. Phenocrysts from Heldburg are similar to the metasomatic veins, suggesting that a phonolite could potentially form the veins if vein formation is dominated by crystallization rather than reaction and replacement of wall rock phases.     

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.     

Redox state of deep off-craton lithospheric mantle: new data from garnet and spinel peridotites from Vitim, southern Siberia

Oxygen fugacity (fO₂) affects melting, metasomatism, speciation of C–O–H fluids and carbon-rich phases in the upper mantle. fO₂ of deep off-craton mantle is poorly known because garnet-peridotite xenoliths are rare in alkali basalts. We examine the redox and thermal state of the lithospheric mantle between the Siberian and North China cratons using new Fe³⁺/ΣFe ratios in garnet and spinel obtained by M?ssbauer spectroscopy, major element data and P–T estimates for 22 peridotite xenoliths as well as published data for 15 xenoliths from Vitim, Russia. Shallow spinel-facies mantle is more oxidized than deep garnet peridotites (average, ?0.1 vs. ?2.5 ΔlogfO₂(FMQ)). For intermediate garnet–spinel peridotites, fO₂ estimates from spinel-based oxybarometers are 1.5–3.2 ΔlogfO₂(FMQ) lower than those from garnet-based oxybarometers. These rocks may be out of phase and chemical inter-mineral equilibrium because the spinel–garnet reaction and concomitant changes in mineral chemistry do not keep up with P–T changes (e.g., lithospheric heating by recent volcanism) due to slow diffusion of trivalent cations and because gar-, gar-spl and spl-facies rocks may coexist on centimeter–meter scale. The spinel-based fO₂ estimates may not be correct while garnet-based fO₂ values provide conditions before the heating. The T (780–1,100?°C) and fO₂ ranges of the Vitim xenoliths overlap those of coarse garnet and spinel cratonic peridotites. However, because of a higher geothermal gradient, the deepest Vitim garnet peridotites are more reduced (by 0.5–2.0 ΔlogfO₂(FMQ)) than cratonic garnet peridotites at similar depths, and the “water maximum” conditions (>80?% H₂O) in the off-craton mantle exist in a more shallow and narrow depth range (60–85?km) than in cratonic roots (100–170?km). The base of the off-craton lithospheric mantle (≥90?km) at 2.5?GPa and 1,150?°C has fO₂ of ?3.0 ?logfO₂(FMQ), with dominant CH₄ and H₂O and minor H₂ in the fluid. Melting near the base of off-craton mantle lithosphere may be induced by increasing water share in migrating fluids due to oxidation of methane.     

The Olivine--Orthopyroxene--Spinel Oxygen Geobarometer, the Nickel Precipitation Curve, and the Oxygen Fugacity of the Earth's Upper Mantle

The common upper mantle assemblage olivine-orthopyroxene-spinelmay be used to calculate the oxygen fugacity at which mantle-derivedperidotites have equilibrated. The equilibrium has been calibratedusing the large amount of existing data on the thermodynamicproperties of each phase in this assemblage. A by-product ofthis procedure is a new calibration of the olivine-spinel Mg-Fe²⁺exchange geothermometer. Application of the equilibrium to avariety of peridotite xenoliths indicates that the oxygen fugacityof the upper mantle lies between the quartz-fayalite-magnetite(QFM) and w?stite-magnetite (WM) oxygen buffers; the few apparentexceptions to this rule may be due to analytical error, particularlyin the Fe³⁺ content of the spinet phase. In fact, the determinationof Fe³⁺ in spinet is at present the limiting factor in the accurateapplication of the method: within this limitation, the presentlyavailable evidence suggests that the oxygen fugacity of themantle may be laterally homogeneous over wide regions, but mayalso show small differences between these regions. The fluidspecies in the system C-H-O at such oxygen fugacities are predominantlyCO₂ and/or H₂O, and not CH₄/H₂ The minimum possible oxygen fugacity of the mantle is givenby the nickel content of olivine in equilibrium with orthopyroxene;for typical mantle compositions this minimum curve is virtuallycoincident with the iron-w?stite (IW) oxygen buffer.     

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     

Characterising modal metasomatic processes in young continental lithospheric mantle: a microsampling isotopic and trace element study on xenoliths from the Middle Atlas Mountains,Morocco

Clinopyroxene is a major host for lithophile elements in the mantle lithosphere, and therefore it is critical whether we are to understand the constraints that this mineral puts on mantle evolution and melt generation. This study presents a detailed in situ trace element and Sr isotope study of clinopyroxene, amphibole and melt from two spinel lherzolites from the Middle Atlas Mountains, Morocco. The results show that there is limited, but discernable, Sr isotopic variation between clinopyroxene crystals within these xenoliths [⁸⁷Sr/⁸⁶Sr ranging from 0.703416 (±11 2SE) to 0.703681 (±12 2SE)]. Trace element patterns show similar interelement fractionation with LREE enrichment, but there is a considerable range in terms of elemental concentration (e.g. over 100 ppm in Sr concentrations). Observed modal clinopyroxene is far more abundant than that predicted from estimates of melt depletion. This along with isotope and trace element variability found in these xenoliths supports a multistage metasomatic process in which clinopyroxene and amphibole are recent secondary additions to the lithospheric mantle. Elemental systematics indicate that the metasomatic mineral assemblage has most recently equilibrated with a carbonatitic melt prior to inclusion in the host basalt. The clinopyroxene from this study is typical of global off-craton clinopyroxene in terms of Sr isotope composition, suggesting that the majority of clinopyroxene in off-craton settings may have a recent metasomatic origin. These findings indicate that caution is required when using peridotite xenoliths to estimate the degree of elemental enrichment in the subcontinental lithosphere.     

Sr and Nd isotope composition of deformed peridotite xenoliths from Udachnaya kimberlite pipe

New results of Rb–Sr and Sm–Nd isotope analyses have been obtained on samples of deformed peridotite xenoliths collected from the Udachnaya kimberlite pipe (Yakutia). The data obtained imply two main stages of metasomatic alteration of the lithospheric mantle base matter in the central part of the Siberian Craton. Elevated ratios of Sr isotopes may be considered as evidence of an ancient stage of metasomatic enrichment by a carbonatite melt. The acquired Nd isotope composition together with the geochemistry of the deformed peridotite xenoliths suggests that the second stage of metasomatic alteration took place shortly before formation of the kimberlite melt. The metasomatic agent of this stage had a silicate character and arrived from an asthenosphere source, common for the normal OIB type (PREMA) and the Group-I kimberlite.

     

Dolomite-bearing orogenic garnet peridotites witness fluid-mediated carbon recycling in a mantle wedge (Ulten Zone,Eastern Alps,Italy)

We document the presence of dolomite ± apatite in orogenic peridotites from the Ulten Zone (UZ, Italian Alps), the remnants of a Variscan mantle wedge tectonically coupled with eclogitized continental crust. These dolomite peridotites are associated with dominant carbonate-free amphibole peridotites, which formed in response to infiltration of aqueous subduction fluids lost by the associated crustal rocks during high-pressure (HP) metamorphism and retrogression. Dolomite-free and dolomite-bearing peridotites share the same metamorphic evolution, from garnet- (HP) to spinel-facies (low-pressure, LP) conditions. Dolomite and the texturally coexisting phases display equilibrium redistribution of rare earth elements and of incompatible trace elements during HP and LP metamorphism; clinopyroxene and amphiboles from carbonate-free and carbonate-bearing peridotites have quite similar compositions. These features indicate that the UZ mantle rocks equilibrated with the same metasomatic agents: aqueous CO₂-bearing fluids enriched in incompatible elements released by the crust. The P–T crystallization conditions of the dolomite peridotites (outside the field of carbonatite melt + amphibole peridotite coexistence), a lack of textures indicating quench of carbonic melts, a lack of increase in modal clinopyroxene by reaction with such melts and the observed amphibole increase at the expense of clinopyroxene, all suggest that dolomite formation was assisted by aqueous CO₂-bearing fluids. A comparison of the trace element compositions of carbonates and amphiboles from the UZ peridotites and from peridotites metasomatized by carbonatite and/or carbon-bearing silicate melts does not help to unambiguously discriminate between the different agents (fluids or melts). The few observed differences (lower trace element contents in the fluid-related dolomite) may ultimately depend on the solute content of the metasomatic agent (CO₂-bearing fluid versus carbonatite melt). This study provides strong evidence that C–O–H subduction fluids can produce ‘carbonatite-like’ assemblages in mantle rocks, thus being effective C carriers from the slab to the mantle wedge at relatively low P–T. If transported beyond the carbonate and amphibole solidus by further subduction, dolomite-bearing garnet + amphibole peridotites like the ones from Ulten can become sources of carbonatite and/or C-bearing silicate melts in the mantle wedge. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. In memory of Lauro Morten 1941–2006.