The trace element composition of silicate inclusions in diamonds: a review

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.     

Diamond precipitation and mantle metasomatism – evidence from the trace element chemistry of silicate inclusions in diamonds from Akwatia, Ghana

Trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxene) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS. Incompatible trace elements are hosted in garnet and clinopyroxene except for Sr which is equally distributed between orthopyroxene and garnet in harzburgitic paragenesis diamonds. The separation between lherzolitic and harzburgitic inclusion parageneses, which is commonly made using compositional fields for garnets in a CaO versus Cr₂O₃ diagram, is also apparent from the Ti and Sr contents in both olivine and garnet. Titanium is much higher in the lherzolitic and Sr in the harzburgitic inclusions. Chondrite normalised REE patterns of lherzolitic garnets are enriched (10–20 times chondrite) in HREE (La_N/Yb_N = 0.02–0.06) while harzburgitic garnets have sinusoidal REE_N patterns, with the highest concentrations for Ce and Nd (2–8 times chondritic) and a minimum at Ho (0.2–0.7 times chondritic). Clinopyroxene inclusions show negative slopes with La enrichment 10–100 times chondritic and low Lu (0.1–1 times chondritic). Both a lherzolitic and a harzburgitic garnet with very high knorringite contents (14 and 21 wt% Cr₂O₃ respectively) could be readily distinguished from other garnets of their parageneses by much higher levels of LREE enrichment. The REE patterns for calculated melt compositions from lherzolitic garnet inclusions fall into the compositional field for kimberlitic-lamproitic and carbonatitic melts. Much more strongly fractionated REE patterns calculated from harzburgitic garnets, and low concentrations in Ti, Y, Zr, and Hf, differ significantly from known alkaline and carbonatitic melts and require a different agent. Equilibration temperatures for harzburgitic inclusions are generally below the C-H-O solidus of their paragenesis, those of lherzolitic inclusions are above. Crystallisation of harzburgitic diamonds from CO₂-bearing melts or fluids may thus be excluded. Diamond inclusion chemistry and mineralogy also is inconsistent with known examples of metasomatism by H₂O-rich melts. We therefore favour diamond precipitation by oxidation of CH₄-rich fluids with highly fractionated trace element patterns which are possibly due to “chromatographic” fractionation processes. Received: 27 January 1996 / Accepted: 5 May 1997     

Diamondiferous lithospheric roots along the western margin of the Kalahari Craton—the peridotitic inclusion suite in diamonds from Orapa and Jwaneng

The Orapa and Jwaneng kimberlites are located along the western margin of the Kalahari Craton and the prevalence of eclogitic over peridotitic diamonds in both mines has recently been linked to lower P-wave velocities in the deep mantle lithosphere (relative to the bulk of the craton) to suggest a diamond formation event prompted by mid-Proterozoic growth and modification of preexisting Archean lithosphere (Shirey et al. 2002). Here we study peridotitic diamonds from both mines, with an emphasis on the style of metasomatic source enrichment, to evaluate their relationship with this major eclogitic diamond formation event. In their major element chemistry, the peridotitic inclusions compare well with a world-wide database but reveal differences to diamond sources located in the interior of the Western Terrane of the Kaapvaal block, where the classical mines in the Kimberley region are located. The most striking difference is the relative paucity of low-Ca (<2 wt% CaO in garnet) harzburgites and a low ratio of harzburgitic to lherzolitic garnets (2:1). This suggests that lithospheric mantle accreted to the rim of the Zimbabwe and Kaapvaal blocks was overall chemically less depleted. Alternatively, this more fertile signature may be assigned to stronger metasomatic re-enrichment but the trace element signature of garnet inclusions is not in favor of strong enrichment in major elements. For both mines the majority of lherzolitic and harzburgitic garnet inclusions are characterized by moderately sinusoidal REE_N patterns and low Ti, Zr and Y contents, indicative of a metasomatic agent with very high LREE/HREE and low HFSE. This is consistent with metasomatism by a CHO-fluid or, as modeled by Burgess and Harte (2003), a highly fractionated, low-volume silicate melt from the MORB-source. In both cases, changes in the major element chemistry of the affected rocks will be limited. In a few garnets from Orapa preferential MREE enrichment is observed, suggesting that the percolating fluid/melt fractionated a LREE-phyllic phase (such as crichtonite). The overall moderate degree of metasomatism reflected by the inclusion chemistry is in stark contrast to lithospheric sections for Orapa and Jwaneng based on mantle xenocrysts and xenoliths, revealing extensive mantle metasomatism (Griffin et al. 2003). This suggests that the formation of peridotitic diamonds predates the intensive modification of the subcratonic lithosphere during Proterozoic rifting and compression, implying that diamonds may survive major tectonothermal events.Editorial responsibility: J. Hoefs     

Metasomatism in mantle xenoliths from the Letlhakane kimberlites: estimation of element fluxes

A suite of metasomatised xenoliths from the Letlhakane kimberlite (Botswana) forms a metasomatic sequence from garnet peridotite to garnet phlogopite peridotite to phlogopite peridotite. Before the modal metasomatism, most of the Letlhakane xenoliths were depleted harzburgites that had been subjected to an earlier cryptic metasomatic event. Modal phlogopite and clinopyroxene - Cr-spinel increase at the expense of garnet and orthopyroxene with increasing degrees of metasomatism. The most metasomatised xenolith is a wehrlite. With progressive modal metasomatism, the clinopyroxene becomes enriched in Sr, Sc and the LREE, orthopyroxene becomes depleted in Ca and Ni, but enriched in Al and Mn, and olivine becomes depleted in Al and V. Garnet chemical composition largely remains unchanged. The garnet replacement reaction seen in most xenoliths allows the measurement of the flux of trace elements through detailed modal analysis of the pseudomorphs. Mass balance calculations show that the modally metasomatised rocks became enriched in incompatible elements such as Sr, Na, K, the LREE and the HFSE (Ti, Zr and Nb). Major elements (Al, Cr and Fe) and garnet-compatible trace elements (V, Y, Sc, and the HREE) were removed during this metasomatic process. The modal metasomatism caused a strong depletion in Al, and the results challenge previous suggestions that this metasomatic process merely occurred within an Al-poor environment. The data suggest that the xenoliths represent the mantle wallrock adjacent to a major conduit for an alkaline basic silicate melt (with high contents of volatile and incompatible elements). The volatile and incompatible element-enriched component of this melt percolated into the wallrock along a strong temperature gradient and caused the observed range of metasomatism.     

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     

Amphibole-rich xenoliths and host alkali basalts: petrogenetic constraints and implications on the recent evolution of the upper mantle beneath Ahaggar (Central Sahara,Southern Algeria)

Quaternary basanitic to nephelinitic volcanoes from Tahalra (western Ahaggar, southern Algeria) contain numerous Mg-ilmenite and amphibole-rich inclusions (±olivine, ±salite) and spinel lherzolite (±pargasite) inclusions associated with kaersutite megacrysts. On the basis of petrological, geochemical and Sr isotopic study of representative xenoliths (including a composite nodule defined as a vein cross-cutting peridotite) and lavas, we attribute the series of amphibole-rich xenoliths and megacrysts to segregation under upper mantle conditions from a hydrous high Ti and LREE melt geochemically similar to the Quaternary basanite but isotopically different. Amphibole-rich rocks and megacrysts are the results of magmatic events (less than 40 Ma) probably contemporaneous with the various pre-Quaternary volcanic phases recognized in Ahaggar. The amphibole-rich veins and the Quaternary lavas have a garnet lherzolitic source enriched in REE (7 to 9 times chondritic in LREE, 2 times in HREE). This enrichment probably results from former metasomatic events unrelated to the recent magmatic history. Melts from which these veins precipitated within upper mantle peridotite also account for mantle enrichment processes; they induced a local partial melting and contact metasomatism (pargasitization). The upper mantle beneath the volcanic areas of Ahaggar is veined and hydrous, and consequently lightened: thus, the uplift of basement may be the isostatic response to magmatism and related metasomatism and therefore the result of the Cenozoïc igneous activity.     

Diamondiferous peridotitic microxenoliths from the Diavik Diamond Mine, NT

Twenty-five diamonds recovered from 21 diamondiferous peridotitic micro-xenoliths from the A154 South and North kimberlite pipes at Diavik (Slave Craton) match the general peridotitic diamond production at this mine with respect to colour, carbon isotopic composition, and nitrogen concentrations and aggregation states. Based on garnet compositions, the majority of the diamondiferous microxenoliths is lherzolitic (G9) in paragenesis, in stark contrast to a predominantly harzburgitic (G10) inclusion paragenesis for the general diamond production. For garnet inclusions in diamonds from A154 South, the lherzolitic paragenesis, compared to the harzburgitic paragenesis, is distinctly lower in Cr content. For microxenolith garnets, however, Cr contents for garnets of both the parageneses are similar and match those of the harzburgitic inclusion garnets. Assuming that the microxenolith diamonds reflect a sample of the general diamond population, the abundant Cr-rich lherzolitic garnets formed via metasomatic overprinting of original harzburgitic diamond sources subsequent to diamond formation, conversion of original harzburgitic diamond sources occurred in the course of metasomatic overprint re-fertilization. Metasomatic overprinting after diamond formation is supported by the finding of a highly magnesian olivine inclusion (Fo₉₅) in a microxenolith diamond that clearly formed in a much more depleted environment than indicated by the composition of its microxenolith host. Chondrite normalized REE patterns of microxenolith garnets are predominantly sinusoidal, similar to observations for inclusion garnets. Sinusoidal REE_N patterns are interpreted to indicate a relatively mild metasomatic overprint through a highly fractionated (very high LREE/HREE) fluid. The predominance of such patterns may explain why the proposed metasomatic conversion of harzburgite to lherzolite appears to have had no destructive effect on diamond content. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Melting and metasomatism in the continental lithosphere: laser ablation ICPMS analysis of minerals in spinel lherzolites from eastern Australia

Olivine, low-Ca pyroxene, diopside, and spinel from a suite of protogranular lherzolite xenoliths from southeastern Australia have been analysed for their major and trace element compositions using electron microprobe and laser ablation ICPMS. Bulk compositions of the lherzolites range from fertile (12–13% modal diopside) to depleted (2–3% modal diopside), with equilibration temperatures of 850–900 °C indicating entrainment of these lherzolites from relatively shallow depths (probably ≤ 35 km) within the lithosphere. Mineral compositions and abundances indicate a primary control by partial melting, with decreasing abundance of modal diopside accompanied by increasing Mg# of olivine and pyroxene, decreasing Al and Ti contents of diopside, increasing Ni contents of olivine, and increasing Cr/Al of spinel. HREE, Y, and Ga in diopside also follow melting trends, decreasing in concentration with increasing Mg#. In contrast, highly incompatible elements such as LREE, Nb, and Th reveal divergent behaviour that cannot be ascribed entirely to partial melting. Diopsides from the fertile lherzolites have mantle-normalized patterns that are depleted in Th, Nb, and the LREE relative to Y and the HREE, whereas, diopsides from the cpx-poor samples are strongly enriched in Th, Nb and the LREE, and have elevated Sm/Hf and Zr/Hf, and low Ti/Nb. All diopsides have strongly negative Nb anomalies relative to Th and the LREE. Trace element patterns of diopside in the fertile lherzolites can be reproduced by ≤ 5% batch melting of a primitive source. The negative Nb anomalies are a consequence of this melting, and do not require special conditions or tectonic environments. The low concentrations of Y and HREE in diopside from the cpx-poor lherzolites cannot be produced by realistic degrees of batch melting, but can be accomplished by up to ∼20% fractional melting, suggesting multiple episodes of melt depletion. Os isotopic compositions of these lherzolites show that the melt depletion events occurred in the middle and late Proterozoic, demonstrating the long-term stability of lithospheric mantle beneath regions of eastern Australia. The LREE-enriched diopsides are well equilibrated and record metasomatic enrichment events that pre-date the magmatism that entrained these xenoliths. Trace element patterns of these pyroxenes suggest a carbonatitic melt as the metasomatic agent. Received: 24 September 1996 / Accepted: 12 August 1997     

Peridotitic diamonds from Namibia: constraints on the composition and evolution of their mantle source

About half the diamonds studied from the Cenozoic placer deposits along the Namibian coast belong to the peridotitic suite. The peridotitic mantle source is heterogeneous ranging from lherzolitic to strongly Ca depleted (down to 0.24 wt.% CaO in garnet) and shows large variations in Cr/Al ratio, illustrated by very low to very high Cr₂O₃ contents in garnet (2.6–17.3 wt.%). The Cr-rich end of this range includes exceptionally high Cr₂O₃ contents in Mg-chromite (70.7 wt.%) and clinopyroxene (3.6 wt.%). Garnet-olivine thermometry appears to indicate two groups, one that equilibrated at temperatures between 1200 and 1220°C and a second between 960 and 1100°C. Combined estimates of pressure and temperature based on garnet-orthopyroxene pairs indicate a large variance in geothermal gradients, corresponding to 38–42 mW/m² surface heat flow.

The trace-element composition of peridotitic garnet inclusions (determined by SIMS) also indicates large diversity. Two principal groups, corresponding to different styles of metasomatic source enrichment, are recognized. The first group ranges from extremely LREE_N-depleted patterns, through trough-shaped REE_N to sinusoidal patterns with the position of the first peak gradually moving from the LREE_N to the MREE_N. This series of REE patterns is interpreted to reflect a range of metasomatic agents with decreasing LREE/HREE. Only in the case of the two garnets with REE_N peaking at Sm–Eu is this process connected with enrichment in Zr, without significant introduction of Y and Ti. The metasomatism responsible is interpreted as reflecting percolation of CHO-fluids through harzburgite under sub-solidus conditions. A second group of garnets shows an increase from LREE_N–MREE_N and almost flat (lherzolitic garnet) to moderately declining MREE_N–HREE_N at super-chondritic levels. This second style of metasomatism is caused by an agent carrying HFSE and showing only moderate enrichment in LREE over HREE, which points towards silicate melts.     

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

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

Multiple-mineral inclusions in diamonds from the Snap Lake/King Lake kimberlite dike, Slave craton, Canada: a trace-element perspective

Multiple inclusions of minerals in diamonds from the Snap Lake/King Lake kimberlites of the southeastern Slave craton in Canada have been analyzed for trace elements to elucidate the petrogenetic history of these inclusions, and of their host diamonds. As observed worldwide, the harzburgitic-garnet diamond inclusions (DIs) possess sinusoidal REE patterns that indicate an early depletion event, followed by metasomatism by LREE-enriched, HREE-depleted fluids. Furthermore, these fluids appear to contain appreciable concentrations of LILE and HFSE, based on the increasing abundances of these elements in the olivine inclusion that occurs at the outer portion of a diamond compared to that near the core. The compositions of these fluids are probably a mixture of hydrous-silicic melt, carbonatitic melt, and brine, similar to the compositions of micro-inclusions in diamonds reported by Navon et al. (2003). Comparison between the compositions of majoritic and normal harzburgitic garnets shows that the former are more depleted in terms of major/minor elements (higher Cr#) but significantly more enriched in the REE (up to 10×). This characteristic may indicate the higher susceptibility for metasomatic enrichment of previously more depleted garnets. Garnets of eclogitic paragenesis show strong LREE-depleted patterns, whereas the coexisting omphacite inclusion has relatively flat light- and middle-REE but depleted HREE. Whole-rock reconstruction from coexisting garnet and omphacite inclusions indicates that the protolith of these inclusions was probably the extrusive section of an oceanic crust, subducted beneath the Slave craton.     

Composition and processes of the mantle lithosphere in northeastern Brazil and Fernando de Noronha: evidence from mantle xenoliths

Spinel–peridotite facies mantle xenoliths in Cenozoic alkali basalts of the Pico Cabuji volcano (Rio Grande do Norte State, Northeast Brazil) and the adjacent South Atlantic oceanic island of Fernando de Noronha are studied for: (1) the information they provide on the composition of the lithospheric component in the erupted basalt geochemistry, and (2) to check the effects of the Fernando de Noronha plume track on the mantle lithosphere. Xenoliths from Pico Cabuji are protogranular lherzolites and porphyroclastic harzburgites recording average equilibrium temperatures of 825 ± 116 and 1248 ± 19 °C, respectively. Pressure in the porphyroclastic xenoliths ranges from 1.9 to 2.7 GPa (Ca-in-olivine geobarometer). Both groups show major element chemical variation trends in whole-rock and Ti and HREE (Er, Yb) variations in clinopyroxene consistent with fractional melting and basalt extraction. REE (rare earth element) profiles of clinopyroxenes vary from LREE (La, Ce) enriched (spoon shaped) to LREE depleted in the protogranular group, whereas they are slightly convex upward in most porphyroclastic clinopyroxenes. HFSE (Ti and Zr) negative anomalies are in general modest in the clinopyroxenes of both groups. Xenoliths from Fernando de Noronha have textural variations similar to those of Pico Cabuji. Protogranular and porphyroclastic samples have similar temperature (1035 ± 80 °C) and the pressure is 1–1.9 and 2.3 GPa, respectively. Whole-rock chemical variation trends overlap and extend further than those of Pico Cabuji. The trace element profiles of the clinopyroxenes of the porphyroclastic xenoliths are enriched in La up to 30 × PM and are smoothly fractionated from LREE to HREE, with deep, negative, Zr and Ti anomalies. The geochemical heterogeneities of the xenoliths from both localities are interpreted in terms of reactive porous percolation. The porphyroclastic xenoliths from Pico Cabuji represent the lower part of a mantle column (the head of a mantle diapir, at the transition conductive–adiabatic mantle), where OIB infiltration triggers melting, and the protogranular xenoliths the top of the mantle column, chromatographically enriched by percolation at a low melt/rock ratio. This interpretation may also apply for Fernando de Noronha, but the different geochemical signature recorded by the clinopyroxenes requires a different composition of the infiltrated melt. Nd and Sr isotopes of the Pico Cabuji porphyroclastic clinopyroxenes (¹⁴³Nd/¹⁴⁴Nd= 0.51339–0.51255, ⁸⁷Sr/⁸⁶Sr=0.70275–0.70319) and of Fernando de Noronha (¹⁴³Nd/¹⁴⁴Nd=0.51323–0.51285, ⁸⁷Sr/⁸⁶Sr=0.70323–0.70465) plot on distinct arrays originating from a similar, isotopically depleted composition and trending to low Nd–low Sr (EMI) and low Nd–high Sr (EMII), respectively. Correlation of the isotope variation with geochemical parameters indicates that the isotopic variation was induced by the metasomatic component, of EMI type at Pico Cabuji and of EMII type at Fernando de Noronha. These different components enriched a lithosphere isotopically similar to DMM (depleted MORB mantle) at both localities. At Fernando de Noronha, the isotopic signature of the metasomatic component is similar to that of the ∼ 8 Ma old lavas of the Remedios Formation, suggesting that this is the age of metasomatism. At Pico Cabuji, the mantle xenoliths do not record the high ⁸⁷Sr/⁸⁶Sr component present in the basalts. We speculate that the EMII component derives from a lithospheric reservoir, which was not thermally affected during mantle metasomatism at Pico Cabuji, but was mobilized by the hotspot thermal influence at Fernando de Noronha. This interpretation provides a plausible explanation for the presence of distinct metasomatic components at the two localities, which would be difficult to reconcile with their genetic relationship with the same plume. Received: 12 June 1999 / Accepted: 13 December 1999     

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.     

Conditions of crystallization of olivine shonkinites in the Inagli massif (Central Aldan)

The olivine shonkinites localized among dunites and alkali gabbroids in the northern part of the alkaline ultrabasic Inagli massif (northwestern part of Central Aldan) have been studied. The obtained data on the chemical and trace-element compositions of the rocks and minerals and the results of melt inclusion study showed that the olivine shonkinites crystallized from alkaline basanite melt enriched in Cl, S, CO2, and trace elements. Clinopyroxene crystallized at 1180-1200 °C from a homogeneous silicate-salt melt, which was probably separated into immiscible silicate and carbonate-salt fractions with temperature decreasing. The composition of the silicate fraction evolved from alkaline basanite to alkaline trachyte. The carbonate-salt fraction had an alkaline carbonate composition and was enriched in S and Cl. The same trend of evolution of clinopyroxene-hosted melts and the igneous rocks of the Inagli massif suggests that the alkali gabbroids, melanocratic alkali syenites, and pulaskites formed from the same magma, which had a near-alkaline basanite composition during its crystallization differentiation. The geochemical studies showed that the olivine shonkinites and glasses of homogenized melt inclusions in clinopyroxene grains have similar contents of trace elements, one or two orders of magnitude higher than those in the primitive mantle. The high contents of LILE (K, Rb, and Sr) and LREE in the olivine shoshonites and homogenized inclusions suggest the enriched mantle source, and the negative anomalies of HFSE and Ti are a specific feature of igneous rocks formed with the participation of crustal material. The slight depletion in HREE relative to LREE and the high (La/Yb)_n ratios in the rocks and inclusion glasses (10.0-11.4 and 4.7-6.2, respectively) suggest the presence of garnet in the mantle source.     

Genesis of kalsilite melilitite at Cupaello,Central Italy: Evidence from melt inclusions

The paper presents data on primary carbonate–silicate melt inclusions hosted in diopside phenocrysts from kalsilite melilitite of Cupaello volcano in Central Italy. The melt inclusions are partly crystalline and contain kalsilite, phlogopite, pectolite, combeite, calcite, Ba–Sr carbonate, baryte, halite, apatite, residual glass, and a gas phase. Daughter pectolite and combeite identified in the inclusions are the first finds of these minerals in kamafugite rocks from central Italy. Our detailed data on the melt inclusions in minerals indicate that the diopside phenocrysts crystallized at 1170–1190°C from a homogeneous melilitite magma enriched in volatile components (CO₂, 0.5–0.6 wt % H₂O, and 0.1–0.2 wt % F). In the process of crystallization at the small variation in P-T parameters two-phase silicate-carbonate liquid immiscibility occurred at lower temperatures (below 1080–1150°C), when spatially separated melilitite silicate and Sr-Ba-rich alkalicarbonate melts already existed. The silicate–carbonate immiscibility was definitely responsible for the formation of the carbonatite tuff at the volcano. The melilitite melt was rich in incompatible elements, first of all, LILE and LREE. This specific enrichment of the melt in these elements and the previously established high isotopic ratios are common to all Italian kamafugites and seem to be related to the specific ITEM mantle source, which underwent metasomatism and enrichment in incompatible elements.     

Trace element compositions of submicroscopic inclusions in coated diamond: A tool for understanding diamond petrogenesis

Trace element compositions of submicroscopic inclusions in both the core and the coat of five coated diamonds from the Democratic Republic of Congo (DRC, formerly Zaire) have been analyzed by Laser Ablation Inductively Coupled Mass Plasma Spectrometry (LA-ICP-MS). Both the diamond core and coat inclusions show a general 2-4-fold enrichment in incompatible elements relative to major elements. This level of enrichment is unlikely to be explained by the entrapment of silicate mantle minerals (olivine, garnet, clinopyroxene, phlogopite) alone and thus submicroscopic fluid or glass inclusions are inferred in both the diamond coat and in the gem quality diamond core. The diamond core fluids have elevated High Field Strength Element (Ti, Ta, Zr, Nb) concentrations and are enriched in U relative to inclusions in the diamond coats and relative to chondrite. The core fluids are also moderately enriched in LILE (Ba, Sr, K). Therefore, we suggest that the diamond cores contain inclusions of silicate melt. However, the Ni content and Ni/Fe ratio of the trapped fluid are very high for a silicate melt in equilibrium with mantle minerals; high Ni and Co concentrations in the diamond cores are attributed to the presence of a sulfide phase coexisting with silicate melt in the diamond core inclusions. Inclusions in the diamond coat are enriched in LILE (U, Ba, Sr, K) and La over the diamond core fluids and to chondrite. The coats have incompatible element ratios similar to natural carbonatite (coat fluid: Na/Ba ≈0.66, La/Ta≈130). The coat fluid is also moderately enriched in HFSE (Ta, Nb, Zr) when normalized to chondritic Al. LILE and La enrichment is related to the presence of a carbonatitic fluid in the diamond coat inclusions, which is mixed with a HFSE-rich hydrous silicate fluid similar to that in the core. The composition of the coat fluid is consistent with a genetic link to group 1 kimberlite.     

Subduction zone geochemistry

Crustal recycling at convergent plate boundaries is essential to mantle heterogeneity.However,crustal signatures in the mantle source of basaltic rocks above subduction zones were primarily incorporated in the form of liquid rather than solid phases.The physicochemical property of liquid phases is determined by the dehydration behavior of crustal rocks at the slab-mantle interface in subduction channels.Because of the significant fractionation in incompatible trace elements but the full inheritance in radiogenic isotopes relative to their crustal sources,the production of liquid phases is crucial to the geochemical transfer from the subducting crust into the mantle.In this process,the stability of specific minerals in subducting crustal rocks exerts a primary control on the enrichment of given trace elements in the liquid phases.For this reason,geochemically enriched oceanic basalts can be categorized into two types in terms of their trace element distribution patterns in the primitive mantle-normalized diagram.One is island arc basalts(IAB),showing enrichment in LILE,Pb and LREE but depletion in HFSE such as Nb and Ta relative to HREE,The other is ocean island basalts(OIB),exhibiting enrichment in LILE and LREE,enrichment or non-depletion in HFSE but depletion in Pb relative to HREE.In either types,these basalts show the enhanced enrichment of LILE and LREE with increasing their incompatibility relative to normal mid-ocean ridge basalts(MORB).The thermal regime of subduction zones can be categorized into two stages in both time and space,The first stage is characterized by compressional tectonism at low thermal gradients.As a consequence,metamorphic dehydration of the subducting crust prevails at forearc to subarc depths due to the breakdown of hydrous minerals such as mica and amphibole in the stability field of garnet and rutile,resulting in the liberation of aqueous solutions with the trace element composition that is considerably enriched in LILE,Pb and LREE but depleted in HFSE and HREE relative to normal MORB.This provides the crustal signature for the mantle sources of IAB.The second stage is indicated by extensional tectonism at high thermal gradients,leading to the partial melting of metamorphically dehydrated crustal rocks at subarc to postarc depths.This involves not only the breakdown of hydrous minerals such as amphibole,phengite and allanite in the stability field of garnet but also the dissolution of rutile into hydrous melts.As such,the hydrous melts can acquire the trace element composition that is significantly enriched in LILE,HFSE and LREE but depleted in Pb and HREE relative to normal MORB,providing the crustal signature for the mantle sources of OIB.In either case,these liquid phases would metasomatize the overlying mantle wedge peridotite at different depths,generating ultramafic metasomatites such as serpentinized and chloritized peridotites,and olivine-poor pyroxenites and hornblendites.As a consequence,the crustal signatures are transferred by the liquid phases from the subducting slab into the mantle.     

海南岛陆缘扩张带形成及新生代岩石圈动力学机制:来自幔源包体的地球化学证据

海南岛陆缘扩张带蓬莱地区新生代玄武岩中捕获大量尖晶石二辉橄榄岩和方辉橄榄岩幔源包体。激光剥蚀等离子体质谱(LA-ICP-MS)分析结果表明,蓬莱地幔橄榄岩含有三种不同地球化学特征的单斜辉石(Cpx):(1)a类单斜辉石Mg~#=92.3~93.4,来自富集Cpx的二辉橄榄岩,具有极低的LREE和不相容元素含量,HREE平坦,Th、U、La、Sr正异常,经历了7%~10%的尖晶石相部分熔融,仅受到极低程度强不相容元素(Th、U、La、Sr)初期富集交代作用;(2)b类单斜辉石Mg~#=89.9~90.3,来自较富集Cpx的二辉橄榄岩,具有中等的LREE和LILE含量,HREE平坦,微量元素蛛网图上显示Th、U正异常,Rb、Ba、Nb、Ta、Sr、Ti负异常,经历4%~5%的尖晶石相部分熔融,可能受到了含LREE和Th、U等不相容元素的硅酸盐熔体交代;(3)c类单斜辉石Mg~#=91.4~92.8,来自贫Cpx的二辉橄榄岩和方辉橄榄岩,具有富集的LREE和LILE含量,HREE弱分异,微量元素蛛网图上显示Th、U正异常及强烈的Nb、Ta、Ti负异常,经历了8%~20%的尖晶石相部分熔融,其交代熔体可能是来自源区有石榴子石残留的碳酸盐熔体。全岩主、微量元素及模拟计算结果表明,这些幔源包体的主量元素主要受部分熔融程度影响,并且方辉橄榄岩经历的部分熔融程度大于二辉橄榄岩。地幔橄榄岩的Sr-Nd同位素组成表明该区具有MORB-OIB型亏损地幔特征。此外,蓬莱部分地幔橄榄岩包体显示正斜率的HREE分异特征((Gd/Yb)_N=0.4~0.7),暗示该区地幔经历了源自石榴子石稳定区的变压熔融,总体熔融程度为18%以上,指示了较高的地幔潜能温度。综合前人对海南岛新生代玄武岩最新研究成果,我们认为海南地幔柱可能为该区软流圈地幔置换古老岩石圈地幔提供了热源,导致了区域岩石圈地幔的破坏,从而引起包括地幔柱本身、软流圈和富集岩石圈的熔融。岩石圈地幔性质的改变和不均一性可能是海南岛陆缘扩张带新生代岩石圈减薄的主要动力学机制。     

Geochemistry of mid-ocean ridge mafic intrusives from the Manipur Ophiolitic Complex,Indo-Myanmar Orogenic Belt,NE India

Mafic intrusives emplaced within the mélange zone of the Manipur Ophiolitic Complex are subalkalinetholeiitic affinity with Fe-enrichment. Based on the field occurrences, textures-mineralogy and whole-rock compositions, these mafic intrusives can be identified as type-I (gabbro intrusives) and type-II (basalt-dolerite dykes). The type-I resembling enriched-type mid-ocean ridge basalt (E-MORB) shows moderate LREE enrichment (La_N/Sm_N = 2.5–2.6), slightly enriched MORB normalized HFSE patterns possibly represent melts derived from enriched MORB sub-oceanic mantle sources by small degree of partial melting. The other type-II has normal-type mid-ocean ridge basalt (N-MORB) geochemical features, as it exhibits nearly flat to depleted LREE (La_N/Sm_N = 1.0–0.6), flat MORB normalized HFSE patterns with slight LREE/HREE depletion (Ce_N/Yb_N = 1.37–0.46). It might have been derived from depleted MORB type sub-oceanic mantle source. The MORB signature displayed by these mafic intrusives indicates that they are dismembered fragments of oceanic crust generated at mid-ocean spreading ridge system and support the hypothesis that the Manipur ophiolites was initially formed in the divergent plate margin.     

Evidence from Muriah, Indonesia, for the Interplay of Supra-Subduction Zone and Intraplate Processes in the Genesis of Potassic Alkaline Magmas

The high-K alkaline volcano Muriah is situated in central Javaand has erupted two lava series, a younger highly potassic series(HK) and an older potassic series (K). The HK series has higherK2O contents for a given MgO content; greater silica undersaturation;and higher concentrations of LILE (Rb, Sr, Ba, and K), LREE(La and Ce), and HFSE (Nb, Zr, Ti, and P), than the K series.The HK series lavas have incompatible trace element patternssimilar in many respects to ocean island basalts. The K serieshas slightly higher ⁸⁷Sr/⁸⁶Sr (O70453 [GenBank] -O70498) and ¹⁸O (+6?2to + 8?4%o) and lower ¹⁴³Nd/¹⁴⁴Nd (0?512530–0?5126588)than the HK series (for which 87Sr/86Sr = 0?70426–0?70451,<518O = +6?52 to +7–0%o, and 1*3Nd/1*4Nd= 0?512623–0?512679),and higher LILE/HFSE and LREE/ HFSE ratios. A7/4 and A8/4 arehigh and do not show any systematic change from the K to theHK series. The proposed model for the Muriah lavas involvesthree source components: (1) the astheno-sphere of the mantlewedge of the Sunda arc, which has Indian Ocean MORB characteristics;(2) a metasomatic layer situated at the base of the lithosphere,which has characteristics similar to enriched mantle (i.e.,EMU); (3) subducted pelagic sediments from the Indian Ocean. Trace element and isotope data indicate that the characteristicsof the K series are produced by mixing of two endmember magmas:an undersaturated magma derived wholly from within-plate sourcesand a calc-alkaline magma derived from the subduction-modifiedasthenospheric mantle. The calc-alkaline magma is believed tobe contaminated by the arc crust before mixing. Low-pressurefractionation took place in the K series after mixing. Initiallithospheric extension in the Bawean trough (in which Muriahis located), may be responsible for decompressive melting ofthe metasomatic layer and thus the production of the HK serieslavas. The magmas erupted from Muriah show a transition fromintraplate to subduction zone processes in their genesis.