Zirconium and hafnium fractionation in differentiation of alkali carbonatite magmatic systems

Zirconium and hafnium are valuable strategic metals which are in high demand in industry. The Zr and Hf contents are elevated in the final products of magmatic differentiation of alkali carbonatite rocks in the Polar Siberia region (Guli Complex) and Ukraine (Chernigov Massif). Early pyroxene fractionation led to an increase in the Zr/Hf ratio in the evolution of the ultramafic–alkali magmatic system due to a higher distribution coefficient of Hf in pyroxene with respect to Zr. The Rayleigh equation was used to calculate a quantitative model of variation in the Zr/Hf ratio in the development of the Guli magmatic system. Alkali carbonatite rocks originated from rare element-rich mantle reservoirs, in particular, the metasomatized mantle. Carbonated mantle xenoliths are characterized by a high Zr/Hf ratio due to clinopyroxene development during metasomatic replacement of orthopyroxene by carbonate fluid melt.     

Symplectite in spinel lherzolite xenoliths from the Little Hungarian Plain, Western Hungary: A key for understanding the complex history of the upper mantle of the Pannonian Basin

Two spinel lherzolite xenoliths from Hungary that contain pyroxene–spinel symplectites have been studied using EPMA, Laser ablation ICP-MS and universal stage. Based on their geochemical and structural characteristics, the xenoliths represent two different domains of the shallow subcontinental lithospheric mantle beneath the Pannonian Basin. The occurrence of symplectites is attributed to the former presence and subsequent breakdown of garnets due to significant pressure decrease related to lithospheric thinning. This implies that both mantle domains were once part of the garnet lherzolitic upper mantle and had a similar history during the major extension that formed the Pannonian Basin.

Garnet breakdown resulted in distinct geochemical characteristics in the adjacent clinopyroxene crystals in both xenoliths. This is manifested by enrichment in HREE, Y, Zr and Hf towards the clinopyroxene porphyroclast rims and also in the neoblasts with respect to porphyroclast core compositions. This geochemical feature, together with the development and preservation of the texturally very sensitive symplectites, enables us to determine the relative timing of mantle processes. Our results indicate that garnets had been metastable in the spinel lherzolite environment and their breakdown to pyroxene and spinel is one of the latest processes that took place within the upper mantle before the xenoliths were brought to the surface.     

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.     

Metasomatism and sulfide mobility in lithospheric mantle beneath eastern Australia: Implications for mantle Re–Os chronology

Spinel lherzolite xenoliths from Tertiary basaltic host magmas at Allyn River, eastern Australia reveal two distinct petrographic and geochemical types. One group is distinguished by xenoliths with undeformed, equilibrated microstructures and interstitial melt patches; The second group shows deformation and contains abundant fluid inclusions but no melt patches. Trace-element signatures of clinopyroxene in these xenoliths provide evidence for metasomatism by a silicate agent with hydrous component and by a carbonate-rich agent respectively.

Melt patches in the undeformed xenoliths contain secondary minerals including clinopyroxene, olivine, feldspar, Mg- and Ca-rich carbonate, apatite, ilmenite and spinel. They are interpreted to represent volatile-rich melt captured shortly prior to entrainment in the host basalt. Sulfide globules, now recrystallised to discrete sulfide phases but inferred to be molten at lithospheric mantle T and P, are closely associated with the melt patches. The close association between sulfide and highly mobile, volatile-bearing fluid has important implications for the mobility of Re and Os, the use of their isotopes in dating mantle events, and the possible effect of volatile-bearing metasomatic agents on their composition.     

Spinel peridotite xenoliths from the Atsagin-Dush volcano, Dariganga lava plateau, Mongolia: a record of partial melting and cryptic metasomatism in the upper mantle

Spinel peridotite xenoliths from the Atsagin-Dush volcanic centre, SE Mongolia range from fertile lherzolites to clinopyroxene(cpx)-bearing harzburgites. The cpx-poor peridotites typically contain interstitial fine-grained material and silicate glass and abundant fluid inclusions in minerals, some have large vesicular melt pockets that apparently formed after primary clinopyroxene and spinel. No volatile-bearing minerals (amphibole, phlogopite, apatite, carbonate) have been found in any of the xenoliths. Fifteen peridotite xenoliths have been analysed for major and trace elements; whole-rock Sr isotope compositions and O isotope composition of all minerals were determined for 13 xenoliths. Trace element composition and Sr-Nd isotope compositions were also determined in 11 clinopyroxene and melt pocket separates. Regular variations of major and moderately incompatible trace elements (e.g. heavy-rare-earth elements) in the peridotite series are consistent with its formation as a result of variable degrees of melt extraction from a fertile lherzolite protolith. The Nd isotope compositions of LREE (light-rare-earth elements)-depleted clinopyroxenes indicate an old (≥ 1 billion years) depletion event. Clinopyroxene-rich lherzolites are commonly depleted in LREE and other incompatible trace elements whereas cpx-poor peridotites show metasomatic enrichment that can be related to the abundance of fine-grained interstitial material, glass and fluid inclusions in minerals. The absence of hydrous minerals, ubiquitous CO₂-rich microinclusions in the enriched samples and negative anomalies of Nb, Hf, Zr, and Ti in primitive mantle-normalized trace element patterns of whole rocks and clinopyroxenes indicate that carbonate melts may have been responsible for the metasomatic enrichment. Low Cu and S contents and high δ³⁴S values in whole-rock peridotites could be explained by interaction with oxidized fluids that may have been derived from subducted oceanic crust. The Sr-Nd isotope compositions of LREE-depleted clinopyroxenes plot either in the MORB (mid-ocean-ridge basalt) field or to the right of the mantle array, the latter may be due to enrichment in radiogenic Sr. The LREE-enriched clinopyroxenes and melt pockets plot in the ocean island-basalt field and have Sr-Nd isotope signatures consistent with derivation from a mixture of the DMM (depleted MORB mantle) and EM (enriched mantle) II sources. Received: 18 January 1996 / Accepted: 23 August 1996     

Slab melt and intraplate metasomatism in Kapfenstein mantle xenoliths (Styrian Basin, Austria)

Anhydrous and amphibole-bearing mantle peridotite xenoliths from Kapfenstein (Styrian Basin) have been studied with the aim of understanding both the processes responsible for amphibole formation and the nature of metasomatizing agents which affected this portion of lithosphere. This area of the Pannonian Basin underwent a subduction event which was followed after about 15 Ma, by alkaline intraplate magmatism. Primary clinopyroxene (cpx1) in four-phase lherzolite xenoliths is characterized by LREE-depleted to slightly LREE-enriched patterns. LREE-depleted cpx1 have low Th and U contents and Zr (and Hf) anomalies varying from slightly negative to positive. LREE-enriched cpx have high Th and U contents and remarkable positive anomalies of Zr and Hf. Primary clinopyroxenes in amphibole-bearing lherzolites present a comparable compositional variation from LREE (and Th, U, Zr, Hf)-depleted type to LREE (and Th, U, Zr, Hf)-enriched type. LREE-depleted cpx1, with strong negative Zr and Ti anomalies, are also recognized in the peridotite matrix of a composite sample cut by a large amphibole vein. Textural and geochemical evidence indicates that amphibole disseminated within the matrix grew at the expense of primary spinel and clinopyroxene, mimicking the trace element patterns of the latter. As a consequence, the geochemical features of amphibole vary in relation to those of clinopyroxene, from enriched to depleted. On the other hand, the composition of vein amphibole in the composite xenolith compares well with amphibole megacrysts and microphenocrysts, suggesting that it represents a fractionation product of alkaline melt that passed through the lithosphere. Two kinds of metasomatism, superimposed on a slightly depleted lithospheric mantle, were identified. A slab-derived melt (proto-adakite?) metasomatic agent was responsible for the first enrichment in Th, U, Zr and Hf observed in clinopyroxene, whereas an alkaline within-plate metasomatic agent caused the formation of the Nb (and Ta)- rich disseminated amphibole. The final process was the alkaline magmatism, which was responsible for the formation of the large amphibole vein and megacrysts. It is proposed that the Nb-poor and Nb-rich amphiboles record the transition between the suprasubduction slab melt-related and the intraplate alkaline metasomatism.

These geochemical features are consistent with a lithospheric portion enriched in slab melt components which was subsequently metasomatized by alkaline melt. Alternatively an asthenospheric uprising could have scavenged a previously slab melt-enriched region of the lithosphere.     

Carbonate-bearing mantle peridotite xenoliths from Spitsbergen: phase relationships,mineral compositions and trace-element residence

 Carbonates of mantle origin have been found in xenoliths from Quaternary basaltic volcanoes in NW Spitsbergen. The carbonates range from dolomite to Mg-bearing calcite and have high Mg-numbers [Mg/(Mg+Fe)=(0.92–0.99)]. In some samples they occur interstitially, e.g. at triple junctions of silicate minerals and appear to be in textural and chemical equilibrium with host lherzolite. Most commonly, however, the carbonates make up fine-grained aggregates together with (Ca,Mg)-rich olivine and (Al,Cr,Ti)-rich clinopyroxene that typically replace spinel, amphibole, and orthopyroxene as well as primary clinopyroxene and olivine. Some lherzolites contain amphibole and apatite that appear to have formed before precipitation of the carbonates. In situ analyses by proton microprobe show very high contents of Sr in the clinopyroxene, carbonates and apatite; the apatite is also very rich in LREE, U, Th, Cl, Br. Disseminated amphibole in carbonate-bearing rocks is very poor in Nb and Zr, in contrast to vein amphibole and mica from carbonate-free rocks that are rich in Nb and Zr. Overall, the Spitsbergen xenoliths provide evidence both for the occurrence of primary carbonate in apparent equilibrium with the spinel lherzolites (regardless of the nature of events that emplaced them) and for the formation of carbonate-bearing pockets consistent with metasomatism by carbonate melts. Calcite and amorphous carbonate-rich materials occur in com- posite carbonate-fluid inclusions, veins and partial melting zones that appear to be related to fluid action in the mantle, heating of the xenoliths during their entrainment in basaltic magma, and to decompression melting of the carbonates. Magnesite is a product of secondary, post-eruption alteration of the xenoliths. Received: 6 October 1995/Accepted: 17 June 1996     

LA-ICP-MS study of apatite- and K feldspar-hosted primary carbonatite melt inclusions in clinopyroxenite xenoliths from lamprophyres, Hungary: Implications for significance of carbonatite melts in the Earth’s mantle

We report the results of LA-ICP-MS analyses of rock forming minerals in clinopyroxene-apatite-K feldspar-phlogopite (CAKP) metasomatic xenoliths and primary carbonatite melt inclusions (CMI) hosted in apatite (Ap) and K feldspar (Kfs). The xenoliths are from the Cretaceous lamprophyre dikes of the Transdanubian Central Range, Hungary. The CMI in Ap have phosphorus dolomitic composition as opposed to CMI in Kfs, which display dolomitic alkali-aluminosiliceous character. The melts found in CMI in Ap and in Kfs likely formed by liquid-liquid separation from an originally carbonate- and phosphorous-rich melt. Primitive mantle (PM) normalized trace element distributions of both Ap- and Kfs-hosted CMI (n = 60 and 20, respectively) reveal a strong negative Ti-anomaly, and an extreme enrichment in incompatible elements (U, Th, LILE and LREE) relative to HREE, Sc, V, Ni and Cr. Rarely, apatites contain unique CMI, which show major- and trace-element signature transitional to K feldspar-hosted CMI. This is due to heterogeneous entrapment of an immiscible phosphorous-bearing carbonatite melt and a carbonate-bearing alkali aluminosiliceous melt, which is a further evidence for their co-existence. CMI reveal that U, Th, Pb, Nb, Ta, P, Sr, Y and REE partitioned into the phosphorous-bearing carbonatite melt, whereas Cs, Rb, Na, K, B, Al, Zr and Hf preferred the silicate-bearing liquid.PM normalized REE pattern (high LREE/HREE), elevated Zr and Hf contents and negative Ti anomaly of clinopyroxene (Cpx) indicate that its formation is genetically linked to carbonatite metasomatism attested by CMI. Trace element partitioning between the studied Cpx and CMI is in accordance with experimentally determined trace element distributions between Cpx and carbonatite melt. Cpx, which occur in samples with high modal proportion of apatite represent mantle section, which interacted with a higher amount of “initial” carbonatite melt than Cpx from apatite-poor xenoliths. This is confirmed by higher Cr, Ni, V, Sc, Ti and lower Zr, as well as Hf concentration in Cpx from xenoliths with low modal abundance of Ap. CMI reveal that Ti, V, Ni and Cr were in lower concentration in the “initial” carbonatite melt than in PM. Contrarily, Zr and Hf were more abundant in this melt than in PM. Consequently, a continuously migrating “initial” carbonatite melt, increased Zr and Hf concentration, and decreased Ti, Sc, V, Ni and especially Cr in the clinopyroxenes. Our findings suggest that the studied CAKP rocks were formed by carbonatite melt metasomatism, which occurred in an open system in the upper mantle.     

Pyroxenite xenoliths from an alkali trachybasalt in the Glen Innes area,northeastern New South Wales

Pyroxenite xenoliths are relatively common in an alkali trachybasalt in the Glen Innes area in northeastern New South Wales where they coexist with peridotite xenoliths, probably lherzolitic. The pyroxenites vary widely in modal composition. Several pyroxenite xenoliths are characterised by megacrystals of subcalcic clinopyroxene and enstatite, the former comprising a unique group of high pressure pyroxenes in which exsolution of orthopyroxene has proceeded on a megascopic scale. Garnet is absent from all mineral assemblages. Mineralogical and experimental data suggest that the subcalcic clinopyroxene and orthopyroxene megacrystals equilibrated initially at temperatures and pressures of the order of 1350–1450° C and 10–23 kb respectively. The most common xenoliths, namely diopsideorthopyroxene assemblages in which there is evidence of subsolidus annealing, equilibrated at comparable pressures but a significantly lower temperatures (ca. 1000° C). It is suggested that the pyroxenites and associated peridotite xenoliths are samples of essentially unmodified layered upper mantle.     

Constraints from eclogite and MARID xenoliths on origins of mantle Zr/Hf–Nb/Ta variability

New trace-element data of rutile in kimberlite-borne ~1.85 Ga eclogite and pyroxenite xenoliths from the central Slave craton, as well as ~110 Ma MARID xenoliths from the Kaapvaal craton, provide constraints on the origins of lithospheric and sublithospheric mantle variability in high field strength element ratios. Rutiles in eclogites and pyroxenites have Zr/Hf ranging from 20 to 62 and Nb/Ta ranging from 10 to 40. Rutiles in MARID xenoliths have Zr/Hf from 24 to 33 and Nb/Ta from 10 to 41. Calculated whole-rock Zr/Hf is suprachondritic for eclogites with suggested gabbroic protoliths and subchondritic for boninite-like eclogites; the latter is consistent with cpx-controlled depletion in the protolith source. Within each eclogite type, positive correlations of Zr/Hf with La/Lu and negative correlations with Lu/Hf likely reflect fractionation of cpx and/or plagioclase during crystallisation of the protoliths. Zr/Hf–Nb/Ta relationships of some MARID-type rocks, which are products of lithospheric mantle metasomatism, and eclogite xenoliths plot on a silicate differentiation trend, whereas other samples have higher Nb/Ta at a given Zr/Hf. Fractionation of a few percent rutile from an HFSE-rich mafic melt can generate a trend towards strongly increased Nb/Ta at minimally changed Zr/Hf in the residual melt. Superposition of rutile fractionation on the effects of silicate differentiation, which fractionates Zr/Hf more strongly than Nb/Ta, can explain the Zr/Hf–Nb/Ta relationships of most eclogites from the central Slave craton as well as those of MARID rocks, metasomatised peridotites and group II kimberlites. By contrast, Zr/Hf–Nb/Ta relationships suggest that Group I kimberlites are mixtures between depleted peridotite and carbonatite. Thus, high Nb/Ta is a signature of lithospheric processes and may not be important in deeply subducted eclogites that bypass extended residence in the lithosphere. Conversely, considerable primary Zr/Hf variability was inherited by the eclogites, which is indicative of the compositional diversity of ancient subducted oceanic crust, which is expected to have generated substantial heterogeneity in sublithospheric basalt sources.     

中国东部岩石圈地幔的演化——地幔岩捕虏体微量元素的证据

对中国东部赋存于新生代玄武岩中的地幔岩捕虏体的全岩和单斜辉石等作了主元素和微量元素分析，证实了二辉橄榄岩及其单斜辉石在主元素有连续变化的趋势，反映了具部分熔融后残留相的性质。方辉橄榄岩及其中的单斜辉石的主元素，Ｎｄ／Ｙｂ，Ｔｉ／Ｚｒ和Ｓｒ／Ｚｒ值与二辉橄榄岩的同类矿物是不连续过渡。     

Equivocal carbonatite markers in the mantle xenoliths of the Patagonia backarc: the Gobernador Gregores case (Santa Cruz Province,Argentina)

Amphibole ± phlogopite ± apatite-bearing mantle xenoliths at Gobernador Gregores display modal, bulk-rock and phase geochemical characteristics held as indicators of carbonatitic metasomatism. However, part of these xenoliths has high TiO₂/Al₂O₃ and those displaying the most pronounced carbonatitic geochemical markers modally trend towards harzburgite. Bulk-rock, clinopyroxene and amphibole show Zr, Hf and Ti negative anomalies, which increase at decreasing Na₂O and high field strength elements (HFSE) concentrations. Steady variation trends between xenoliths which have and do not have carbonatitic characteristics suggest a control by reactive porous flow of only one agent, inferred to be initially a ne-normative hydrous basalt (because of the presence of wehrlites) evolving towards silica saturation. Variation trends exhibit cusps when amphibole appears in the mode. Appearance of amphibole may explain the Ti anomaly variations, but not those of Zr and Hf. Numerical modelling [Plate Model (Vernières et al. in J Geophys Res 102:24771–24784, 1997)] gives results consistent with the observed geochemical features by assuming the presence of loveringite. Modest HFSE anomalies in the infiltrating melt may be acquired during percolation in the garnet-facies.In memory of Carlo Rivalenti     

Distribution of high field strength and rare earth elements in mantle and lower crustal xenoliths from the Southwestern United States: The role of grain-boundary phases

Spinel lherzolite and harzburgite xenoliths from the Basin and Range and Colorado Plateau Provinces in the southwestern United States (SWUS) show a broad range in incompatible element distributions from depleted to enriched, both within and between sites. The most fertile xenoliths occur in the Basin and Range Province and the most refractory in the Colorado Plateau or Transition Zone. Mass balance calculations indicate that up to 80% of the high field strength (Nb, Ta, Zr, Hf, Th, Ti) and rare earth elements (50% for Yb) in these xenoliths occur in phases along grain boundaries (or in microfractures). In lower crustal and eclogite xenoliths, up to 90% of these elements occur in grain-boundary phases. Nb/Ta, Zr/Hf, La/Sm and Nb/Th ratios and Nb-Ta anomalies in both types of xenoliths are also controlled by grain-boundary phases. To interpret these ratios in whole-rock analyses, it is critical to understand the timing and origin of the grain-boundary components in the xenoliths. Most of the enriched mantle xenoliths appear to have been enriched by metasomatic fluids related to silicate magmas and not to carbonatite magmas.Because of a complex multi-event history that affected the composition of the xenoliths, there is no simple geochemical relationship between magmatic or metamorphic history of the lower crust and upper mantle in the SWUS as reflected by the xenolith populations.     

Peridotite xenoliths in alkali basalts from the Sikhote-Alin, southeastern Siberia, Russia: trace-element signatures of mantle beneath a convergent continental margin

Abundant spinel peridotite xenoliths occur in late Cenozoic alkali basaltic rocks in the Sikhote-Alin region at the Pacific margin of the Asian continent. Major- and trace-element compositions of representative peridotite xenolith are documented for four occurrences located in different structural units of the continental margin. In each locality, the majority of xenoliths have distinctive microstructures, modal and chemical compositions that are typical for a given xenolith suite. Significant textural and compositional differences between the four xenolith suites suggest that the upper mantle beneath the Sikhote-Alin consists of distinct domains with contrasting composition. The inferred large-scale mantle heterogeneities may be due to juxtaposition of lithospheric blocks of different provenance during accretion of the Sikhote-Alin to the Asian continent.

Trace-element patterns of the xenoliths and their minerals obtained ICP-MS technique provide evidence of depletion and enrichment events and indicate contrasting behaviour of REE, HFSE and other incompatible trace elements. The HFSE behave non-concordantly, in particular, some xenoliths have highly fractionated Zr/Hf, Ti/Zr, Nb/Ta, La/Nb and U/Th ratios relative to their values in the primitive mantle. The fractionated compositions may be related to the interaction of evolved subduction-related fluids and melts with lithospheric mantle at the Mesozoic-early Cenozoic active continental margin or to metasomatism during later continental rifting.     

The late Cretaceous lithospheric mantle beneath the Central Andes: Evidence from phase equilibria and composition of mantle xenoliths

Temperature estimates and chemical composition of mantle xenoliths from the Cretaceous rift system of NW Argentina (26°S) constrain the rift evolution and chemical and physical properties of the lithospheric mantle at the eastern edge of the Cenozoic Andean plateau. The xenolith suite comprises mainly spinel lherzolite and subordinate pyroxenite and carbonatized lherzolite. The spinel lherzolite xenoliths equilibrated at high-T (most samples >1000 °C) and P below garnet-in. The Sm–Nd systematics of compositionally unzoned clino- and orthopyroxene indicate a Cretaceous minimum age for the high-T regime, i.e., the asthenosphere/lithosphere thermal boundary was at ca. 70 km depth in the Cretaceous rift. Major elements and Cr, Ni, Co and V contents of the xenoliths range between values of primitive and depleted mantle. Calculated densities based on the bulk composition of the xenoliths are <3280 kg/m³ for the estimated P–T conditions and indicate a buoyant, stable upper mantle lithosphere. The well-equilibrated metamorphic fabric and mineral paragenesis with the general lack of high-T hydrous phases did not preserve traces of metasomatism in the mantle xenoliths. Late Mesozoic metasomatism, however, is obvious in the gradual enrichment of Sr, U, Th and light to medium REE and changes in the radiogenic isotope composition of an originally depleted mantle. These changes are independent of the degree of depletion evidenced by major element composition. ¹⁴³Nd/¹⁴⁴Nd_i ratios of clinopyroxene from the main group of xenoliths decrease with increasing Nd content from >0.5130 (depleted samples) to ca. 0.5127 (enriched samples). ⁸⁷Sr/⁸⁶Sr_i ratios (0.7127–0.7131, depleted samples; 0.7130–0.7134, enriched samples) show no variation with variable Sr contents. Pb_i isotope ratios of the enriched samples are rather radiogenic (²⁰⁶Pb/²⁰⁴Pb_i 18.8–20.6, ²⁰⁷Pb/²⁰⁴Pb_i 15.6–15.7, ²⁰⁸Pb/²⁰⁴Pb_i 38.6–47) compared with the Pb isotope signature of the depleted samples. The large scatter and high values of ²⁰⁸Pb/²⁰⁴Pb_i ratios of many xenoliths indicates at least two Pb sources that are characterized by similar U/Pb but by different Th/Pb ratios. The dominant mantle type in the investigated system is depleted mantle according to its Sr and Nd isotopic composition with relatively radiogenic Pb isotope ratios. This mantle is different from the Pacific MORB source and old subcontinental mantle from the adjacent Brazilian Shield. Its composition probably reflects material influx into the mantle wedge during various episodes of subduction that commenced in early Paleozoic or even earlier. Old subcontinental mantle was already replaced in the Paleozoic, but some inheritance from old mantle lithosphere is represented by rare xenoliths with isotope signatures indicating a Proterozoic origin.     

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.     

The Evolution of the Upper Mantle beneath the Canary Islands: Information from Trace Elements and Sr isotope Ratios in Minerals in Mantle Xenoliths

Laser ablation microprobe data are presented for olivine, orthopyroxeneand clinopyroxene in spinel harzburgite and lherzolite xenolithsfrom La Palma, Hierro, and Lanzarote, and new whole-rock trace-elementdata for xenoliths from Hierro and Lanzarote. The xenolithsshow evidence of strong major, trace element and Sr isotopedepletion (⁸⁷Sr/⁸⁶Sr 0·7027 in clinopyroxene in themost refractory harzburgites) overprinted by metasomatism. Thelow Sr isotope ratios are not compatible with the former suggestionof a mantle plume in the area during opening of the AtlanticOcean. Estimates suggest that the composition of the originaloceanic lithospheric mantle beneath the Canary Islands correspondsto the residues after 25–30% fractional melting of primordialmantle material; it is thus significantly more refractory than‘normal’ mid-ocean ridge basalt (MORB) mantle. Thetrace element compositions and Sr isotopic ratios of the mineralsleast affected by metasomatization indicate that the upper mantlebeneath the Canary Islands originally formed as highly refractoryoceanic lithosphere during the opening of the Atlantic Oceanin the area. During the Canarian intraplate event the uppermantle was metasomatized; the metasomatic processes includecryptic metasomatism, resetting of the Sr–Nd isotopicratios to values within the range of Canary Islands basalts,formation of minor amounts of phlogopite, and melt–wall-rockreactions. The upper mantle beneath Tenerife and La Palma isstrongly metasomatized by carbonatitic or carbonaceous meltshighly enriched in light rare earth elements (REE) relativeto heavy REE, and depleted in Zr–Hf and Ti relative toREE. In the lithospheric mantle beneath Hierro and Lanzarote,metasomatism has been relatively weak, and appears to be causedby high-Si melts producing concave-upwards trace element patternsin clinopyroxene with weak negative Zr and Ti anomalies. Ti–Al–Fe-richharzburgites/lherzolites, dunites, wehrlites and clinopyroxenitesformed from mildly alkaline basaltic melts (similar to thosethat dominate the exposed parts of the islands), and appearto be mainly restricted to magma conduits; the alkali basaltmelts have caused only local metasomatism in the mantle wall-rocksof such conduits. The various metasomatic fluids formed as theresults of immiscible separations, melt–wall-rock reactionsand chromatographic fractionation either from a CO₂-rich basalticprimary melt, or, alternatively, from a basaltic and a siliceouscarbonatite or carbonaceous silicate melt. KEY WORDS: mantle xenoliths; mantle minerals; trace elements; depletion; carbonatite metasomatism     

Petrogenesis of Garnet Pyroxenite and Spinel Peridotite Xenoliths of the Tell-Danun Alkali Basalt Volcano,Harrat As Shamah,Syria

A suite of samples, including kaersutite and ilmenite megacrysts, spinel peridotites, garnet pyroxenites, and the alkali basalts that host them, have been studied in an effort to better constrain the mineralogy and chemistry of the subcontinental mantle beneath the central portion of the Arabian plate. Kaersutite megacrysts are classified as Type-A high-pressure precipitates of the alkali basalt host, which transported these xenoliths to the surface and extruded them during formation of the Tell-Danun volcano, southwestern Syria. Ilmenite megacrysts are classified as Type-B megacrysts and could not have precipitated from the alkali basalts presently sampled. Instead, they were derived from a magma that was enriched in the rare-earth elements (REE) by ca. four times and depleted in Zr and Hf, compared to the alkali basalts.

Garnet pyroxenites from the Tell-Danun volcanic field yield temperatures and pressures of 946-1045° C and 8-10 kbar, respectively. These xenoliths likely were precipitated as dikes or along walls of conduits at depths of 24-30 km in the lower crust and/or upper mantle beneath the Arabian plate. Spinel peridotites last were equilibrated at temperatures of 755-1080° C and pressures from 10-20 kbar (30-60 km depth) and could represent samples of a mantle that has been depleted by a prior partial melting event. Many spinel peridotites also contain evidence (specifically in concave-upward REE patterns) of a subsequent enrichment event. However, the age and timing of this depletion, and of the subsequent enrichment event, are not known. This event could have occurred as a consequence of the entrainment of the xenoliths in the LREE- enriched alkali basalts or could have occurred prior to alkali basalt volcanism via metasomatic processes.     

Origin of Phlogopite in Mantle Xenoliths from Kostal Lake, Wells Gray Park, British Columbia

Phlogopite has been recognized for the first time in ultramaficxenoliths from the Canadian Cordillera. The phlogopite-bearingxenoliths are hosted in post-glacial basanitoid flows and ejectaof the Kostal Lake volcanic center, British Columbia. The xenolithassemblage consists of 60% cumulate-textured wehrlites, and40% coarse-textured lherzolites, harzburgites, dunites, andolivine websterites. The phlogopite occurs: (1) as sub-euhedral grains along grainboundaries in dunite and lherzolite xenoliths; or (2) alongorthopyroxene lamellae exsolved from intercumulus clinopyroxenein the wehrlite xenoliths; or (3) as grains hosted in 10–100pm diameter fluid inclusions in clinopyroxene of all xenoliths.The phlogopites do not show any reaction relationships withother phases in any of the xenoliths studied. Phlogopites ina given xenolith have Mg/Mg + Fe²⁺ similar to that of coexistingolivine, clinopyroxene, and orthopyroxene. The partitioningof Fe and Mg between phlogopite and coexisting olivine and clinopyroxeneis similar to that observed in other phlogopite-bearing mantlexenoliths, and in high-pressure melting experiments on rockswith similar bulk compositions. This indicates that the phlogopitesin xenoliths from Kostal Lake have equilibrated with these coexistingphases. The occurrence of phlogopites in fluid inclusions containingNa, K, Cl, P, and S, suggests that incompatible element-enrichedhydrous fluids/melts fluxed this part of the upper mantle beneatheastern British Columbia. Metasomatism of the upper mantle beneathKostal Lake probably occurred prior to Quaternary alkaline magmatism(7550–400 B.P.) and after the initial volcanism whichformed the wehrlite cumulates (3–5 Ma). Metasomatism causedoverall oxidation of the upper mantle beneath this area butwas not responsible for the anomalously Fe-rich nature of somexenoliths from the Kostal Lake eruptive center.     

Roles of Melting and Metasomatism in the Formation of the Lithospheric Mantle beneath the Leizhou Peninsula, South China

This study characterizes the nature of fluid interaction andmelting processes in the lithospheric mantle beneath the Yingfenglingand Tianyang volcanoes, Leizhou Peninsula, South China, usingin situ trace-element analyses of clinopyroxene, amphibole andgarnet from a suite of mantle-derived xenoliths. Clinopyroxenesfrom discrete spinel lherzolites exhibit large compositionalvariations ranging from extremely light rare earth element (LREE)-depletedto LREE-enriched. Trace-element modelling for depleted samplesindicates that the Leizhou lherzolites are the residues of amantle peridotite source after extraction of 1–11% meltgenerated by incremental melting in the spinel lherzolite fieldwith the degree of melting increasing upwards from about 60km to 30 km. This process is consistent with gradational meltingat different depths in an upwelling asthenospheric column thatsubsequently cooled to form the current lithospheric mantlein this region. The calculated melt production rate of thiscolumn could generate mafic crust 5–6 km thick, whichwould account for most of the present-day lower crust. The formationof the lithospheric column is inferred to be related to Mesozoiclithosphere thinning. Al-augite pyroxenites occur in compositexenoliths; these are geochemically similar to HIMU-type oceanisland basalt. These pyroxenites postdate the lithospheric columnformation and belong to two episodes of magmatism. Early magmatism(forming metapyroxenites) is inferred to have occurred duringthe opening of the South China Sea Basin (32–15 Ma), whereasthe most recent magmatic episode (producing pyroxenites withigneous microstructures) occurred shortly before the eruptionof the host magmas (6–0·3 Ma). Trace-element traversesfrom the contacts of the Al-augite pyroxenite with the spinelperidotite wall-rock in composite xenoliths record gradientsin the strength and nature of metasomatic effects away fromthe contact, showing that equilibrium was not attained. Significantenrichment in highly incompatible elements close to the contacts,with only slight enrichment in Sr, LREE and Nb away from thecontact, is inferred to reflect the different diffusion ratesof specific trace elements. The observed geochemical gradientsin metasomatic zones show that Sr, La, Ce and Nb have the highestdiffusion rates, other REE are intermediate, and Zr, Hf andTi have the lowest diffusion rates. Lower diffusion rates observedfor Nb, Zr, Hf and Ti compared with REE may cause high fieldstrength element (HFSE) negative anomalies in metasomatizedperidotites. Therefore, metasomatized lherzolites with HFSEnegative anomalies do not necessarily require a carbonatiticmetasomatizing agent. KEY WORDS: China; lithosphere; mantle xenoliths; clinopyroxene trace elements; mantle partial melting; mantle metasomatism; trace-element diffusion rates