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     

Records of Crustal Metasomatism in the Garnet Peridotites of the Ulten Zone (Upper Austroalpine, Eastern Alps)

Peridotites in the Ulten Zone (Upper Austroalpine, Eastern Alps),occur as small bodies within lower-crustal rocks (gneisses andmigmatites) subducted at eclogite-facies conditions during theVariscan orogeny. They record a complex metamorphic and deformationevolution as indicated by the transition from coarse-grainedspinel-bearing peridotites to fine-grained garnet + amphibole-bearingperidotites, and are interpreted as portions of mantle wedgethat were incorporated in a downgoing slab of cold continentalcrust. The transition from spinel- to garnet-bearing assemblagewas accompanied by significant input of metasomatic agents,as shown by the crystallization of abundant amphibole. Herewe present trace-element mineral chemistry data for selectedUlten peridotites, with the aim of unravelling the nature ofthe metasomatic processes. Amphiboles display significant lightrare earth element (LREE) enrichment [Ce_N/Yb_N = 3·90–11·50;LREE up to (20–50) x C1], high Sr (150–250 ppm),K (1910–7280 ppm) and Ba (280–800 ppm) contents,and low concentrations of high field strength elements (HFSE)(Zr = 14–25 ppm, Y = 6·7–16 ppm, Ti = 1150–2500ppm, Nb = 2–7 ppm). On the basis of (1) the evidence formodal orthopyroxene decrease as a result of the garnet-formingreaction rather than abundant orthopyroxene crystallization,(2) the high modal amounts of amphibole (up to 23%) in the mostmetasomatized peridotites and (3) the strong large ion lithophileelement (LILE)/HFSE fractionation in amphiboles, we infer thatthe metasomatic agent was an H₂O–CO₂ fluid with a lowCO₂/H₂O ratio. Petrological investigations and geochronologicaldata indicate that the host metapelites experienced in situpartial melting and migmatization concomitantly with the garnet+ amphibole-facies recrystallization in the enclosed peridotites.We infer that the metasomatizing hydrous fluids could representthe residual fluids left after the crystallization of leucosomes,starting from water-undersaturated melts produced during migmatizationof the host gneisses. KEY WORDS: garnet peridotite; crustal metasomatism; amphibole; hydrous fluids     

Volatile Components, Magmas, and Critical Fluids in Upwelling Mantle

The phase diagram for lherzolite–CO₂–H₂O providesa framework for interpreting the distribution of phase assemblagesin the upper mantle with various thermal structures, in differenttectonic settings. Experiments show that at depths >80 km,the near-solidus partial melts from lherzolite–CO₂–H₂Oare dolomitic, changing through carbonate–silicate liquidswith rising temperatures to mafic liquids; vapor, if it coexists,is aqueous. Experimental data from simple systems suggest thata critical end-point (K) occurs on the mantle solidus at anundetermined depth. Isobaric (T–X) phase diagrams forvolatile-bearing systems with K elucidate the contrasting phaserelationships for lherzolite–CO₂–H₂O at depths belowand above a critical end-point, arbitrarily placed at 250 km.At levels deeper than K, lherzolite can exist with dolomiticmelt, aqueous vapor, or with critical fluids varying continuouslybetween these end-members. Analyses of fluids in microinclusionsof fibrous diamonds reveal this same range of compositions,supporting the occurrence of a critical end-point. Other evidencefrom diamonds indicates that the minimum depth for this end-pointis 125 km; maximum depth is not constrained. Constructed cross-sectionsshowing diagrammatically the phase fields intersected by upwellingmantle indicate how rising trace melts may influence trace elementconcentrations within a mantle plume. KEY WORDS: mantle solidus; critical end-point; dolomitic magma; diamond inclusions; critical fluids     

Metasomatism and Melting in Carbonated Peridotite Xenoliths from the Mantle Wedge: The Gobernador Gregores Case (Southern Patagonia)

Spinel-facies mantle xenoliths occur in a diatreme cutting throughthe Neogene Southern Patagonia Plateau at Gobernador Gregores(Santa Cruz Province, Argentina). This plateau is in a back-arcposition with respect to the Chile trench. Xenoliths differin their whole-rock composition from other South America occurrences,having higher CaO/Al₂O₃ ratios and, in some samples, TiO₂ enrichment,whereas the Na₂O/Al₂O₃ variation range is similar. Three assemblagescan be distinguished. Assemblage 1, in anhydrous protogranularlherzolites and harzburgites, contains clinopyroxene with adepleted major and trace element composition, indicating pre-metasomaticdepletion processes. This assemblage fully recrystallized toAssemblage 2 (amphibole ± phlogopite ± Cl-apatite-bearing)during a metasomatic episode. This causes clinopyroxene to acquiregeochemical characteristics often attributed to carbonate-meltmetasomatism. Noticeably, amphibole is markedly enriched inNb (up to 298 ppm), especially when depleted in Ti. A furtherevent, related to decompression during xenolith uplift to thesurface, induces closed-system (perhaps with the exception ofCO₂ addition) disequilibrium melting of Assemblage 2, dominantlyof amphibole. It is found in pockets (where amphibole is a residualphase) consisting of Na–Si-rich glass and carbonate (Mg-richcalcite) drops, and in veins originating from the pockets (Assemblage3). Euhedral olivine, clinopyroxene and spinel crystallize onlyin the silicate glass. So do new, euhedral apatite crystalswhen glass is in contact with previous Assemblage 2 apatite.Textural evidence and comparison with experimental work suggestthat silicate glass and carbonates are the result of unmixingof a former homogeneous melt. Because of the different flowrates of carbonate and silicate melt, the xenoliths become enrichedin carbonate, which is found in the veins during their migration.Thus, the high CaO/Al₂O₃ ratio of whole rocks provides inconclusiveevidence of carbonatite metasomatism. This factor, and otherminor deviations from the expected results of carbonatite metasomatism,lead us to hypothesize an aqueous, Cl-rich fluid, possibly slabderived, as an alternative agent. Amphibole, resulting fromreactive porous flow of this agent in the mantle, could fullyexplain the observed geochemical features, as indicated by estimatesof its partition coefficients. KEY WORDS: carbonated xenoliths; Gobernador Gregores; LAM–ICP-MS; mantle metasomatism; silicate glass     

Mantle Xenoliths from Tenerife (Canary Islands): Evidence for Reactions between Mantle Peridotites and Silicic Carbonatite Melts inducing Ca Metasomatism

Mantle xenoliths from Tenerife show evidence of metasomatismand recrystallization overprinting the effects of extensivepartial melting. The evidence includes: recrystallization ofexsolved orthopyroxene porphyroclasts highly depleted in incompatibletrace elements into incompatible-trace-element-enriched, poikiliticorthopyroxene with no visible exsolution lamellae; formationof olivine and REE–Cr-rich, strongly Zr–Hf–Ti-depletedclinopyroxene at the expense of orthopyroxene; the presenceof phlogopite; whole-rock CaO/Al₂O₃ >> 1 (Ca metasomatism) inrecrystallized rocks; and enrichment in incompatible elementsin recrystallized rocks, relative to rocks showing little evidenceof recrystallization. The ‘higher-than-normal’ degreeof partial melting that preceded the metasomatism probably resultsfrom plume activity during the opening of the Central AtlanticOcean. Sr–Nd isotopic compositions are closely similarto those of Tenerife basalts, indicating resetting from theexpected original mid-ocean ridge basalt composition by themetasomatizing fluids. Metasomatism was caused by silicic carbonatitemelts, and involved open-system processes, such as trappingof elements compatible with newly formed acceptor minerals,leaving residual fluids moving to shallower levels. The compositionsof the metasomatizing fluids changed with time, probably asa result of changing compositions of the melts produced in theCanary Islands plume. Spinel dunites and wehrlites representrocks where all, or most, orthopyroxene has been consumed throughthe metasomatic reactions. KEY WORDS: Canary Islands; Tenerife; mantle xenoliths; geochemistry; Ca metasomatism; open-system processes; lithosphere; ocean islands     

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     

Ultra-calcic Magmas Generated from Ca-depleted Mantle: an Experimental Study on the Origin of Ankaramites

Ultra-calcic ankaramitic magmas or melt inclusions are ubiquitousin arc, ocean-island and mid-ocean ridge settings. They areprimitive in character (X_Mg > 0·65) and have highCaO contents (>14 wt %) and CaO/Al₂O₃ (>1·1). Experimentson an ankaramite from Epi, Vanuatu arc, demonstrate that itsliquidus surface has only clinopyroxene at pressures of 15 and20 kbar, with X_CO2 in the volatile component from 0 to 0·86.The parental Epi ankaramite is thus not an unfractionated magma.However, forcing the ankaramite experimentally into saturationwith olivine, orthopyroxene and spinel results in more magnesian,ultra-calcic melts with CaO/Al₂O₃ of 1·21–1·58.The experimental melts are not extremely Ca-rich but high inCaO/Al₂O₃ and in MgO (up to 18.5 wt %), and would evolve tohigh-CaO melts through olivine fractionation. Fractionationmodels show that the Epi parent magma can be derived from suchultra-calcic experimental melts through mainly olivine fractionation.We show that the experimental ultra-calcic melts could formthrough low-degree melting of somewhat refractory mantle. Thelatter would have been depleted by previous melt extraction,which increases the CaO/Al₂O₃ in the residue as long as someclinopyroxene remains residual. This finding corrects the commonassumption that ultra-calcic magmas must come from a Ca-richpyroxenite-type source. The temperatures necessary for the generationof ultra-calcic magmas are     

Bulk-rock Major and Trace Element Compositions of Abyssal Peridotites: Implications for Mantle Melting, Melt Extraction and Post-melting Processes Beneath Mid-Ocean Ridges

This paper presents the first comprehensive major and traceelement data for 130 abyssal peridotite samples from the Pacificand Indian ocean ridge–transform systems. The data revealimportant features about the petrogenesis of these rocks, mantlemelting and melt extraction processes beneath ocean ridges,and elemental behaviours. Although abyssal peridotites are serpentinized,and have also experienced seafloor weathering, magmatic signaturesremain well preserved in the bulk-rock compositions. The betterinverse correlation of MgO with progressively heavier rare earthelements (REE) reflects varying amounts of melt depletion. Thismelt depletion may result from recent sub-ridge mantle melting,but could also be inherited from previous melt extraction eventsfrom the fertile mantle source. Light REE (LREE) in bulk-rocksamples are more enriched, not more depleted, than in the constituentclinopyroxenes (cpx) of the same sample suites. If the cpx LREErecord sub-ridge mantle melting processes, then the bulk-rockLREE must reflect post-melting refertilization. The significantcorrelations of LREE (e.g. La, Ce, Pr, Nd) with immobile highfield strength elements (HFSE, e.g. Nb and Zr) suggest thatenrichments of both LREE and HFSE resulted from a common magmaticprocess. The refertilization takes place in the ‘cold’thermal boundary layer (TBL) beneath ridges through which theascending melts migrate and interact with the advanced residues.The refertilization apparently did not affect the cpx relicsanalyzed for trace elements. This observation suggests grain-boundaryporous melt migration in the TBL. The ascending melts may notbe thermally ‘reactive’, and thus may have affectedonly cpx rims, which, together with precipitated olivine, entrappedmelt, and the rest of the rock, were subsequently serpentinized.Very large variations in bulk-rock Zr/Hf and Nb/Ta ratios areobserved, which are unexpected. The correlation between thetwo ratios is consistent with observations on basalts that D_Zr/D_Hf< 1 and D_Nb/D_Ta < 1. Given the identical charges (5⁺ forNb and Ta; 4⁺ for Zr and Hf) and essentially the same ionicradii (R_Nb/R_Ta = 1·000 and R_Zr/R_Hf = 1·006–1·026),yet a factor of 2 mass differences (M_Zr/M_Hf = 0·511 andM_Nb/M_Ta = 0·513), it is hypothesized that mass-dependentD values, or diffusion or mass-transfer rates may be importantin causing elemental fractionations during porous melt migrationin the TBL. It is also possible that some ‘exotic’phases with highly fractionated Zr/Hf and Nb/Ta ratios may existin these rocks, thus having ‘nugget’ effects onthe bulk-rock analyses. All these hypotheses need testing byconstraining the storage and distribution of all the incompatibletrace elements in mantle peridotite. As serpentine containsup to 13 wt % H₂O, and is stable up to 7 GPa before it is transformedto dense hydrous magnesium silicate phases that are stable atpressures of 5–50 GPa, it is possible that the serpentinizedperidotites may survive, at least partly, subduction-zone dehydration,and transport large amounts of H₂O (also Ba, Rb, Cs, K, U, Sr,Pb, etc. with elevated U/Pb ratios) into the deep mantle. Thelatter may contribute to the HIMU component in the source regionsof some oceanic basalts. KEY WORDS: abyssal peridotites; serpentinization; seafloor weathering; bulk-rock major and trace element compositions; mantle melting; melt extraction; melt–residue interaction; porous flows; Nb/Ta and Zr/Hf fractionations; HIMU mantle sources     

Melting of a Hydrous Mantle: II. Geochemistry of Crystals and Liquids Formed by Anatexis of Mantle Peridotite at High Pressures and High Temperatures as a Function of Controlled Activities of Water, Hydrogen, and Carbon Dioxide

The system peridotite-H₂O–CO₂ serves as a simplified modelfor the phase relations of mantle peridotite involving morethan one volatile component. Run products obtained in a studyof phase relations of four mantle peridotites in the presenceof H₂O- and (H₂O+CO₂)- bearing vapors and with controlled hydrogenfugacity (f_H2) at high pressures and temperatures have beensubjected to a detailed chemical investigation, principallyby the electron microprobe. Mg/(Mg+Fe) of all phases generally increases with increasingtemperature and with increasing Mg/(Mg+Fe) of the starting material.This ratio appears to decrease with increasing pressure forolivine, and for amphibole coexisting with garnet. Decreasingf_H2 from that of IW buffer to that of MH buffer decreases Mg/(Mg+Fe)of the partial melt from approximately 0-85 to approximately0.50, whereas the Fo content of coexisting olivine increasesslightly less than 3 per cent and the Mg/(Mg+Fe) of clinopyroxeneincreases about 4 per cent. However, the variations in Fo contentof olivines are within those observed in olivines from naturalmantle peridotite. The chemistry of other silicate mineralsdoes not significantly reflect variations of f_H2. Consequently,the peridotite mineralogy and/or chemistry is not a good indicatorfor the f_H2 conditions during crystallization. All crystalline phases, except amphibole, and to some extentgarnet, show increasing Cr content with increasing temperatureand increasing Cr content of the starting material, resultingin a positive correlation with Mg/(Mg+Fe). Partial melts aredepleted in Cr₂O₃ relative to the crystalline phases. High Mg/Mg+Fe)and Cr₂O₃ are thus expected in crystal residues after partialmelting. The absolute values depend on degree of melting andthe composition of the parent peridotite. Liquids formed by anatexis of mantle peridotite are andesiticunder conditions of X_H2O^v > 0.6 to at least 25 kb total pressureand to more than 200?C above the peridotite solidus. This observationsupports numerous suggestions that andesite genesis in islandarcs may result from partial melting of underlying peridotitemantle. In contrast to basaltic rocks, the absence of amphibole(paragasitic hornblende) does not affect the silica-saturatednature of the liquids. Increasing K₂O content of the startingmaterial (up to 1 wt. per cent K₂O) results in increasing potassiumcontent of the amphibole (1 wt. per cent K₂O) as well as theappearance of phlogopite. The liquid under these conditionsis relatively K₂0-poor (less than 1 wt. per cent K₂O). Partial melts are olivine normative with X_H2O 0.5, and initialliquids contain normative ol and ne at X_H2O 0.4. The alkalinityof these liquids increases with decreasing X_H2O below valuesof 0.5. The (ol+opx)-normative liquids resemble oceanic basaltswhereas (ol+ne)-normative liquids resemble olivine nepheliniteand melilite basalt. Low aHlo and high a_Co2 conditions may bethose under which kimberlites and related rocks are formed inthe mantle.     

Volatiles in Basaltic Glasses from Loihi Seamount, Hawaii: Evidence for a Relatively Dry Plume Component

New H₂O, CO₂ and S concentration data for basaltic glasses fromLoihi seamount, Hawaii, allow us to model degassing, assimilation,and the distribution of major volatiles within and around theHawaiian plume. Degassing and assimilation have affected CO₂and Cl but not H₂O concentrations in most Loihi glasses. Waterconcentrations relative to similarly incompatible elements inHawaiian submarine magmas are depleted (Loihi), equivalent (Kilauea,North Arch, Kauai–Oahu), or enriched (South Arch). H₂O/Ceratios are uncorrelated with major element composition or extentor depth of melting, but are related to position relative tothe Hawaiian plume and mantle source region composition, consistentwith a zoned plume model. In front of the plume core, overlyingmantle is metasomatized by hydrous partial melts derived fromthe Hawaiian plume. Downstream from the plume core, lavas tapa depleted source region with H₂O/Ce similar to enriched Pacificmid-ocean ridge basalt. Within the plume core, mantle components,thought to represent subducted oceanic lithosphere, have waterenrichments equivalent to (KEA) or less than (KOO) that of Ce.Lower H₂O/Ce in the KOO component may reflect efficient dehydrationof the subducting oceanic crust and sediments during recyclinginto the deep mantle. KEY WORDS: basalt; Hawaii; mantle; plumes; volatiles     

Ultramafic Xenoliths from the Bearpaw Mountains, Montana, USA: Evidence for Multiple Metasomatic Events in the Lithospheric Mantle beneath the Wyoming Craton

Ultramafic xenoliths in Eocene minettes of the Bearpaw Mountainsvolcanic field (Montana, USA), derived from the lower lithosphereof the Wyoming craton, can be divided based on textural criteriainto tectonite and cumulate groups. The tectonites consist ofstrongly depleted spinel lherzolites, harzburgites and dunites.Although their mineralogical compositions are generally similarto those of spinel peridotites in off-craton settings, somecontain pyroxenes and spinels that have unusually low Al₂O₃contents more akin to those found in cratonic spinel peridotites.Furthermore, the tectonite peridotites have whole-rock majorelement compositions that tend to be significantly more depletedthan non-cratonic mantle spinel peridotites (high MgO, low CaO,Al₂O₃ and TiO₂) and resemble those of cratonic mantle. Thesecompositions could have been generated by up to 30% partialmelting of an undepleted mantle source. Petrographic evidencesuggests that the mantle beneath the Wyoming craton was re-enrichedin three ways: (1) by silicate melts that formed mica websteriteand clinopyroxenite veins; (2) by growth of phlogopite fromK-rich hydrous fluids; (3) by interaction with aqueous fluidsto form orthopyroxene porphyroblasts and orthopyroxenite veins.In contrast to their depleted major element compositions, thetectonite peridotites are mostly light rare earth element (LREE)-enrichedand show enrichment in fluid-mobile elements such as Cs, Rb,U and Pb on mantle-normalized diagrams. Lack of enrichment inhigh field strength elements (HFSE; e.g. Nb, Ta, Zr and Hf)suggests that the tectonite peridotites have been metasomatizedby a subduction-related fluid. Clinopyroxenes from the tectoniteperidotites have distinct U-shaped REE patterns with strongLREE enrichment. They have ¹⁴³Nd/¹⁴⁴Nd values that range from0·5121 (close to the host minette values) to 0·5107,similar to those of xenoliths from the nearby Highwood Mountains.Foliated mica websterites also have low ¹⁴³Nd/¹⁴⁴Nd values (0·5113)and extremely high ⁸⁷Sr/⁸⁶Sr ratios in their constituent phlogopite,indicating an ancient (probably mid-Proterozoic) enrichment.This enriched mantle lithosphere later contributed to the formationof the high-K Eocene host magmas. The cumulate group rangesfrom clinopyroxene-rich mica peridotites (including abundantmica wehrlites) to mica clinopyroxenites. Most contain >30%phlogopite. Their mineral compositions are similar to thoseof phenocrysts in the host minettes. Their whole-rock compositionsare generally poorer in MgO but richer in incompatible traceelements than those of the tectonite peridotites. Whole-rocktrace element patterns are enriched in large ion lithophileelements (LILE; Rb, Cs, U and Pb) and depleted in HFSE (Nb,Ta Zr and Hf) as in the host minettes, and their Sr–Ndisotopic compositions are also identical to those of the minettes.Their clinopyroxenes are LREE-enriched and formed in equilibriumwith a LREE-enriched melt closely resembling the minettes. Thecumulates therefore represent a much younger magmatic event,related to crystallization at mantle depths of minette magmasin Eocene times, that caused further metasomatic enrichmentof the lithosphere. KEY WORDS: ultramafic xenoliths; Montana; Wyoming craton; metasomatism; cumulates; minette     

Sr-Nd-Pb Isotopic Compositions of Peridotite Xenoliths from Spitsbergen: Numerical Modelling Indicates Sr-Nd Decoupling in the Mantle by Melt Percolation Metasomatism

Several spinel peridotite xenoliths from Spitsbergen have Sr–Ndisotopic compositions that plot to the right of the ‘mantlearray’ defined by oceanic basalts and the DM end-member(depleted mantle, with low ⁸⁷Sr/⁸⁶Sr and high ¹⁴³Nd/¹⁴⁴Nd).These xenoliths also show strong fractionation of elements withsimilar compatibility (e.g. high La/Ce), which cannot be producedby simple mixing of light rare earth element-depleted peridotiteswith ocean island basalt-type or other enriched mantle melts.Numerical simulations of porous melt flow in spinel peridotitesapplied to Sr–Nd isotope compositions indicate that thesefeatures of the Spitsbergen peridotites can be explained bychemical fractionation during metasomatism in the mantle. ‘Chromatographic’effects of melt percolation create a transient zone where thehost depleted peridotites have experienced enrichment in Sr(with a radiogenic isotope composition) but not in Nd, thusproducing Sr–Nd decoupling mainly controlled by partitioncoefficients and abundances of Sr and Nd in the melt and theperidotite. Therefore, Sr–Nd isotope decoupling, earlierreported for some other mantle peridotites worldwide, may bea signature of metasomatic processes rather than a source-relatedcharacteristic, contrary to models that invoke mixing with hypotheticalSr-rich fluids derived from subducted oceanic lithosphere. Pbisotope compositions of the Spitsbergen xenoliths do not appearto be consistently affected by the metasomatism. KEY WORDS: Spitsbergen; lithospheric mantle; metasomatism; radiogenic isotopes; theoretical modelling     

Na Metasomatism in the Island-Arc Mantle by Slab Melt--Peridotite Interaction: Evidence from Mantle Xenoliths in the North Kamchatka Arc

The Pliocene (7 Ma) Nb-enriched arc basalts of the ValovayamVolcanic Field (VVF) in the northern segment of the Kamchatkaarc, Russia, host abundant mantle xenoliths, including spinelIherzolites. Textural and microstructural evidence for high-temperature,multi-stage, creep-related deformations in spinel Iherzolitessupports a sub-arc mantle derivation. Pyroxene chemistry indicatesthe existence of two compositional suites: (1) a Cr-diopsidesuite with low-Tt, moderate-Al clinopyroxene compositions, and(2) an Al-augite suite with high Al and Tt, and low Cr concentrationsin clinopyroxene. Some spinel lherzolite xenoliths contain metasomaticAl-augite-type clinopyroxene, Al-Tt spinel, and felsic veinssimilar to trondhjemite melt. The Al-augite series xenolithstypically contain high-Na plagioclase, Cr-poor, Al-Fe-Mg andAl-Tt-Fe spinels, with occasional almandine-grossularite garnetand high-Al and -Na pargasitic amphibole. Pyroxene and spinel compositional trends suggest that the Crdiopsideseries xenoliths from the VVF Nb-enriched arc basalts representan island-arc mantle affected by a metasomatic event. Occurrenceof high-Na plagioclase and trondhjemitic veins favors the additionof a metasomatic component with high Na, Al and Si to the northernKamchatka arc mantle. Trondhjemitic veins, representing siliceousslab melts, compositionally exemplify the metasomatic component.Na metasomatism by peridotite-slab melt interaction is an importantmantle hybridization process responsible for arc-related alkalinemagma generation from a veined sub-arc mantle. KEY WORDS: metasomatism; island arc; mantle xenoliths; Kamchatka; mantle     

Trace Element Residence and Partitioning in Mantle Xenoliths Metasomatized by Highly Alkaline, Silicate- and Carbonate-rich Melts (Kerguelen Islands, Indian Ocean)

Mantle xenoliths in alkaline lavas of the Kerguelen Islandsconsist of: (1) protogranular, Cr-diopside-bearing harzburgite;(2) poikilitic, Mg-augite-bearing harzburgite and cpx-poor lherzolite;(3) dunite that contains clinopyroxene, spinel phlogopite, andrarely amphibole. Trace element data for rocks and mineralsidentify distinctive signatures for the different rock typesand record upper-mantle processes. The harzburgites reflectan initial partial melting event followed by metasomatism bymafic alkaline to carbonatitic melts. The dunites were firstformed by reaction of a harzburgite protolith with tholeiiticto transitional basaltic melts, and subsequently developed metasomaticassemblages of clinopyroxene + phlogopite ± amphiboleby reaction with lamprophyric or carbonatitic melts. We measuredtwo-mineral partition coefficients and calculated mineral–meltpartition coefficients for 27 trace elements. In most samples,calculated budgets indicate that trace elements reside in theconstituent minerals. Clinopyroxene is the major host for REE,Sr, Y, Zr and Th; spinel is important for V and Ti; orthopyroxenefor Ti, Zr, HREE, Y, Sc and V; and olivine for Ni, Co and Sc. KEY WORDS: mantle xenoliths; mantle metasomatism; partition coefficients; Kerguelen Islands; trace elements     

Similar V/Sc Systematics in MORB and Arc Basalts: Implications for the Oxygen Fugacities of their Mantle Source Regions

V/Sc systematics in peridotites, mid-ocean ridge basalts andarc basalts are investigated to constrain the variation of fO₂in the asthenospheric mantle. V/Sc ratios are used here to ‘seethrough’ those processes that can modify barometric fO₂determinations in mantle rocks and/or magmas: early fractionalcrystallization, degassing, crustal assimilation and mantlemetasomatism. Melting models are combined here with a literaturedatabase on peridotites, arc lavas and mid-ocean ridge basalts,along with new, more precise data on peridotites and selectedarc lavas. V/Sc ratios in primitive arc lavas from the Cascadesmagmatic arc are correlated with fluid-mobile elements (e.g.Ba and K), indicating that fluids may subtly influence fO₂ duringmelting. However, for the most part, the average V/Sc-inferredfO₂s of arc basalts, MORB and peridotites are remarkably similar(–1·25 to +0·5 log units from the FMQ buffer)and disagree with the observation that the barometric fO₂s ofarc lavas are several orders of magnitude higher. These observationssuggest that the upper part of the Earth's mantle may be stronglybuffered in terms of fO₂. The higher barometric fO₂s of arclavas and some arc-related xenoliths may be due respectivelyto magmatic differentiation processes and to exposure to large,time-integrated fluid fluxes incurred during the long-term stabilityof the lithospheric mantle. KEY WORDS: vanadium; scandium; oxygen fugacity; mantle; arcs     

Upper Mantle Amphiboles and Micas and TiO2, K2O, and P2O5 Abundances and 100 Mg/(Mg+Fe2+ Ratios of Common Basalts and Andesites: Implications for Modal Mantle Metasomatism and Undepleted Mantle Compositions

Modal mantle metasomatism, involving the re-enrichment of depletedmantle by the introduction or production of new hydrous phases,apatite and other minerals, has been proposed as a criticalprecursor to alkaline volcanism. The merits of the modal metasomatismmodel are evaluated by examining whole-rock 100 Mg/(Mg+Fe²⁺)ratios and the abundances of TiO₂, K₂O and P₂O₅ in mafic volcanicsspanning the mafic alkaline-subalkaline compositional spectrum.Upper mantle amphiboles and micas are also discussed becausethey would be major donors of Ti, Fe, and K to melts duringanatexis of either modally metasomatized depleted mantle orundepleted mantle. Compared with tholeiitic and calc-alkaline basalts and andesites,basanites and alkali basalts and alkali andesites are neitherdistinctive nor unique by virtue of persistant or well-definedhigher abundances of TiO₂, K₂O, and P₂O₅ or lower 100 Mg/(Mg+Fe₂₊)ratios, features which might reflect precursor modal metasomatismof the alkaline sources. Some basanites and alkali basalts dohave higher abundances of TiO₂, K₂O, and P₂O₅ than some tholeiitesbut these abundances may be the result of lower degrees of meltingof similar undepleted mantle sources for both magma types. The most widespread mantle phases of inferred metasomatic originare interstitial amphiboles and micas in Group I spinel peridotitexenoliths. These have high 100 Mg/(Mg+Fe) ratios ({small tilde}90) and high Cr₂O₃ and low TiO₂ abundances, and the K₂O/Na₂Oratios of the amphiboles (chromian pargasites) are low, generallyless than 0?3. Interstitial amphiboles and micas developed asa result of near-isochemical hydration reactions which largelyinvolved Cr-spinel and Cr-diopside. Their formation was probablyinduced in many instances by fluids derived from crystallizingmafic magmas. Metasomatized Group I xenoliths with interstitialhydrous phases remain depleted in TiO₂, K₂O, and P₂O₅, and theyretain the high 100 Mg/(Mg+Fe) ratios characterizing depletedGroup I xenoliths. Together with the low K₂O/Na₂O ratios, thesefeatures preclude such peridotites as suitable sources of mostalkaline (and subalkaline) volcanics. It is suggested that modalmetasomatism plays an insignificant role in the genesis of mostmantle-derived mafic volcanics. Compared with the interstitial phases, kaersutitic amphibolesand titaniferous micas from vein, Group II inclusion and megacrystupper mantle parageneses have lower 100 Mg/(Mg+Fe) ratios andCr₂O₃ contents, and much higher TiO₂ abundances. K₂O/Na₂O ratiosof the Ti-amphiboles are also much more wide-ranging (0?3 togreater than 1?0). These Fe, Ti-rich amphiboles and micas areneither widespread nor pervasive phases in metasomatized mantle.They are directly related to alkaline magmatism in the uppermantle where they may be associated with incompatible elementenrichment of peridotite wallrocks in the immediate vicinityof frozen conduits of alkaline mafic magmas. The varying K₂O/Na₂O ratios of mafic volcanics (MORB constitutea major exception) indicate that the principal K-bearing phasesin undepleted mantle are kaersutitic amphibole and titaniferousmica, in varying proportions. The former is probably the majorsource of Ti and K for low K/Na volcanics (K₂O/Na₂O < 0?5)and also many medium K/Na types (0?5 < K₂O/Na₂O < 1?0),whereas mica is more likely to be the major K-bearing phasein the source regions of high K/Na extrusives (K₂O/Na₂ >1?0). Experimental data indicate that kaersutitic amphibole,mica and apatite probably coexist in undepleted spinel- andgarnet lherzolites at pressures up to 25 kb, with mica persistingto pressures as high as 50 kb. It is proposed that undepleted asthenospheric mantle is heterogeneouswith respect to its amphibole, mica, and apatite contents (andhence TiO₂, K₂O, and P₂O₅ abundances and K₂O/Na₂O ratios), andalso with respect to 100 Mg/(Mg+Fe²⁺ ) ratios which may be significantlyless than the ratios generally assigned to undepleted mantle,namely 88–90.     

The Role of Advective Fluid Flow and Diffusion during Localized, Solid-State Dehydration: Sondrum Stenhuggeriet, Halmstad, SW Sweden

A localized dehydration zone, Söndrum stone quarry, Halmstad,SW Sweden, consists of a central, 1 m wide granitic pegmatoiddyke, on either side of which extends a 2·5–3 mwide dehydration zone (650–700°C; 800 MPa; orthopyroxene–clinopyroxene–biotite–amphibole–garnet)overprinting a local migmatized granitic gneiss (amphibole–biotite–garnet).Whole-rock chemistry indicates that dehydration of the graniticgneiss was predominantly isochemical. Exceptions include [Y+ heavy rare earth elements (HREE)], Ba, Sr, and F, which aremarkedly depleted throughout the dehydration zone. Systematictrends in the silicate and fluorapatite mineral chemistry acrossthe dehydration zone include depletion in Fe, (Y + HREE), Na,K, F, and Cl, and enrichment in Mg, Mn, Ca, and Ti. Fluid inclusionchemistry is similar in all three zones and indicates the presenceof a fluid containing CO₂, NaCl, and H₂O components. Water activitiesin the dehydration zone average 0·36, or X_H2O = 0·25.All lines of evidence suggest that the formation of the dehydrationzone was due to advective transport of a CO₂-rich fluid witha minor NaCl brine component originating from a tectonic fracture.Fluid infiltration resulted in the localized partial breakdownof biotite and amphiboles to pyroxenes releasing Ti and Ca,which were partitioned into the remaining biotite and amphibole,as well as uniform depletion in (Y + HREE), Ba, Sr, Cl, andF. At some later stage, H₂O-rich fluids (H₂O activity >0·8)gave rise to localized partial melting and the probable injectionof a granitic melt into the tectonic fracture, which resultedin the biotite and amphibole recording a diffusion profile forF across the dehydration zone into the granitic gneiss as wellas a diffusion profile in Fe, Mn, and Mg for all Fe–Mgsilicate minerals within 100 cm of the pegmatoid dyke. KEY WORDS: charnockite; fluids; CO₂; brines; localized dehydration; Söndrum     

Magma Genesis and Mantle Heterogeneity in the Manus Back-Arc Basin, Papua New Guinea

Geochemical data from back-arc volcanic zones in the Manus Basinare used to define five magma types. Closest to the New Britainarc are medium-K lavas of the island arc association and back-arcbasin basalts (BABB). Mid-ocean ridge basalts (MORB), BABB andmildly enriched T-MORB (transitional MORB) occur along the ManusSpreading Center (MSC) and Extensional Transform Zone (ETZ).The MSC also erupted extreme back-arc basin basalts (XBABB),enriched in light rare earth elements, P, and Zr. Compared withnormal MORB, Manus MORB are even more depleted in high fieldstrength elements and slightly enriched in fluid-mobile elements,indicating slight, prior enrichment of their source with subduction-relatedcomponents. Chemical variations and modeling suggest systematic,coupled relationships between extent of mantle melting, priordepletion of the mantle source, and enrichment in subduction-relatedcomponents. Closest to the arc, the greatest addition of subduction-relatedcomponents has occurred in the mantle with the greatest amountof prior depletion, which has melted the most. Variations inK₂O/H₂O indicate that the subduction-related component is bestdescribed as a phlogopite and/or K-amphibole-bearing hybridizedperidotite. Magmas from the East Manus Rifts are enriched inNa and Zr with radiogenic ⁸⁷Sr/⁸⁶Sr, possibly indicating crustalinteraction in a zone of incipient rifting. The source for XBABBand lavas from the Witu Islands requires a mantle componentsimilar to carbonatite melt. KEY WORDS: Manus back-arc basin, mantle metasomatism, magma generation     

Melting of a Hydrous Mantle: II. Geochemistry of Crystals and Liquids Formed by Anatexis of Mantle Peridotite at High Pressures and High Temperatures as a Function of Controlled Activities of Water, Hydrogen, and Carbon Dioxide

The system peridotite-H₂O-CO₂ serves as a simplified model forthe phase relations of mantle peridotite involving more thanone volatile component. Run products obtained in a study ofphase relations of four mantle peridotites in the presence ofH₂O- and (H₂O+CO₂)-bearing vapors and with controlled hydrogenfugacity (f_H2) at high pressures and temperatures have beensubjected to a detailed chemical investigation, principallyby the electron microprobe. Mg/(Mg+Fe) of all phases generally increases with increasingtemperature and with increasing Mg/(Mg+Fe) of the starting material.This ratio appears to decrease with increasing pressure forolivine, and for amphibole coexisting with garnet. DecreasingfH₂from that of IW buffer to that of MH buffer decreases Mg/(Mg+Fe)of the partial melt from approximately 0?85 to approximately0?50, whereas the Fo content of coexisting olivine increasesslightly less than 3 per cent and the Mg/(Mg+Fe) of clinopyroxeneincreases about 4 per cent. However, the variations in Fo contentof olivines are within those observed in olivines from naturalmantle peridotite. The chemistry of other silicate mineralsdoes not significantly reflect variations of fH₂. Consequently,the peridotite mineralogy and/or chemistry is not a good indicatorfor the fH₂ conditions during crystallization. All crystalline phases, except amphibole, and to some extentgarnet, show increasing Cr content with increasing temperatureand increasing Cr content of the starting material, resultingin a positive correlation with Mg/(Mg+Fe). Partial melts aredepleted in Cr₂O₃ relative to the crystalline phases. High Mg/(Mg+Fe)and Cr₂O₃ are thus expected in crystal residues after partialmelting. The absolute values depend on degree of melting andthe composition of the parent peridotite.     

Melting of Amphibole-bearing Wehrlites: an Experimental Study on the Origin of Ultra-calcic Nepheline-normative Melts

Olivine + clinopyroxene ± amphibole cumulates have beenwidely documented in island arc settings and may constitutea significant portion of the lowermost arc crust. Because ofthe low melting temperature of amphibole (1100°C), suchcumulates could melt during intrusion of primary mantle magmas.We have experimentally (piston-cylinder, 0·5–1·0GPa, 1200–1350°C, Pt–graphite capsules) investigatedthe melting behaviour of a model amphibole–olivine–clinopyroxenerock, to assess the possible role of such cumulates in islandarc magma genesis. Initial melts are controlled by pargasiticamphibole breakdown, are strongly nepheline-normative and areAl₂O₃-rich. With increasing melt fraction (T > 1190°Cat 1·0 GPa), the melts become ultra-calcic while remainingstrongly nepheline-normative, and are saturated with olivineand clinopyroxene. The experimental melts have strong compositionalsimilarities to natural nepheline-normative ultra-calcic meltinclusions and lavas exclusively found in arc settings. Theexperimentally derived phase relations show that such naturalmelt compositions originate by melting according to the reactionamphibole + clinopyroxene = melt + olivine in the arc crust.Pargasitic amphibole is the key phase in this process, as itlowers melting temperatures and imposes the nepheline-normativesignature. Ultra-calcic nepheline-normative melt inclusionsare tracers of magma–rock interaction (assimilative recycling)in the arc crust. KEY WORDS: experimental melting; subduction zone; ultra-calcic melts; wehrlite