Carbon isotopic composition of diamonds from the Archangelsk diamond province

The first data are reported on the carbon isotopic composition of diamond crystals from the Grib pipe kimberlite deposit of the Archangelsk diamond province (ADP). The δ¹³C value of the crystals ranges from ?2.79 to ?9.61‰. The isotopic composition of carbon was determined in three zoned crystals (δ¹³C of ?5.8 ?6.96 ‰, ?5.64/ ?5.85 ‰, and ?5.94/ ?5.69 ‰), two “diamond in diamond” samples (diamond inclusion with δ¹³C of ?4.05 and ?6.34 ‰ in host diamond crystals with δ¹³C of ?8.05 and ?7.54 ‰, respectively), and two samples of coated diamonds (cores with δ¹³C of ?6.98 and ?6.78‰ and coats with δ¹³C of ?7.51 and ?8.01 ‰, respectively). δ¹³C values were obtained for individual diamond crystals from bort-type aggregates (δ¹³C of ?4.24/ ?4.05 ‰, ?6.58/ ?7.48 ‰, and ?5.48/ ?6.08 ‰). Correlations were examined between the carbon isotopic composition of diamonds and their crystal morphology; the color; the concentration of nitrogen, hydrogen, and platelet defects; and mineral inclusions content. It was supposed that the observed δ¹³C variations in the crystals are most likely related to the fractionation of carbon isotopes rather than to the heterogeneity of carbon sources involved in diamond formation. The isotopic characteristics of diamonds from the Grib pipe were compared with those of previously investigated diamonds from the Lomonosov deposit. It was found that diamonds from these relatively closely spaced kimberlite fields are different; this also indicates the existence of spatially localized peculiarities of isotope fractionation in processes accompanying diamond formation.     

Lithium enrichment and isotopic variation in minerals from peridotite xenoliths from northwestern Ethiopian plateau

We report Lithium (Li) concentrations and isotopic compositions for co-existing olivine, orthopyroxene (opx), and clinopyroxene (cpx) mineral separates from depleted and metasomatised peridotite xenoliths hosted by basaltic lavas from northwestern Ethiopian plateau (Gundeweyn area). The peridotites contain five lherzolites and one harzburgite and are variably depleted and enriched in LREE relative to HREE. In both depleted and enriched lherzolites, Li is preferentially incorporated into olivine (2.4-3.3 ppm) compared to opx (1.4-2.1 ppm) and cpx (1.4-2.0 ppm) whereas the Li contents of olivines (5.4 ppm) from an enriched harzburgiteare higher than those of lherzolites. Olivines from the samples show higher Li abundances than normal mantle olivines (1.6-1.9 ppm) indicating the occurrence of Li enrichments through melt-preroditite interaction. The average δ⁷ Li values range from +2.2 to +6.0‰ in olivine, from -0.1 to +2.0‰ in opx and from -4.4 to -0.9‰ in cpx from the lherzolites. The Li isotopic composition (3.5‰) of olivines from harzburgite fall within the range of olivine from lherzolites but the opxs show low in δ⁷Li (-2.0‰). Overall Li isotopic compositions of olivines from the peridotites fall within the range of normal mantle olivine, δ⁷Li values of ~+4±2‰ within uncertainty, reflecting metasomatism (enrichment) of the peridotites by isotopically heavy Li-rich asthenospheric melt. Li isotope zonation is also observed in most peridotite minerals. Majority of olivine grains display isotopically heavy cores and light rims and the reverse case is observed for some olivine grains. Orthopyroxene and clinopyroxene grains show irregular distribution in δ⁷Li. These features of Li isotopic compositions within and between grains in the samples reflect the effect of diffusion-driven isotopic fractionation during meltperidotite interaction and cooling processes.     

Kimberlite age in the Arkhangelsk Province,Russia: Isotopic geochronologic Rb–Sr and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar and mineralogical data on phlogopite

The paper reports detailed data on phlogopite from kimberlite of three facies types in the Arkhangelsk Diamondiferous Province (ADP): (i) massive magmatic kimberlite (Ermakovskaya-7 Pipe), (ii) transitional type between massive volcaniclastic and magmatic kimberlite (Grib Pipe), and (iii) volcanic kimberlite (Karpinskii-1 and Karpinskii-2 pipes). Kimberlite from the Ermakovskaya-7 Pipe contains only groundmass phlogopite. Kimberlite from the Grib Pipe contains a number of phlogopite populations: megacrysts, macrocrysts, matrix phlogopite, and this mineral in xenoliths. Phlogopite macrocrysts and matrix phlogopite define a single compositional trend reflecting the evolution of the kimberlite melt. The composition points of phlogopite from the xenoliths lie on a single crystallization trend, i.e., the mineral also crystallized from kimberlite melt, which likely actively metasomatized the host rocks from which the xenoliths were captured. Phlogopite from volcaniclastic kimberlite from the Karpinskii-1 and Karpinskii-2 pipes does not show either any clearly distinct petrographic setting or compositional differentiation. The kimberlite was dated by the Rb–Sr technique on phlogopite and additionally by the ⁴⁰Ar/³⁹Ar method. Because it is highly probable that phlogopite from all pipes crystallized from kimberlite melt, the crystallization age of the kimberlite can be defined as 376 ± 3 Ma for the Grib Pipe, 380 ± 2 Ma for the Karpinskii-1 pipe, 375 ± 2 Ma for the Karpinskii-2 Pipe, and 377 ± 0.4 Ma for the Ermakovskaya-7 Pipe. The age of the pipes coincides within the error and suggests that the melts of the pipes were emplaced almost simultaneously. Our geochronologic data on kimberlite emplacement in ADP lie within the range of 380 ± 2 to 375 ± Ma and coincide with most age values for Devonian alkaline–ultramafic complexes in the Kola Province: 379 ± 5 Ma; Arzamastsev and Wu, 2014). These data indicate that the kimberlite was formed during the early evolution of the Kola Province, when alkaline–ultramafic complexes (including those with carbonatite) were emplaced.     

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from Shangzhi,NE China: products of recent melt/fluid-peridotite interaction

Lithium elemental and isotopic disequilibrium has frequently been observed in the continental and oceanic mantle xenoliths, but its origin remains controversial. Here, we present a combined elemental and Li isotopic study on variably metasomatised peridotite xenoliths entrained in the Cenozoic basalts from Shangzhi in Northeast (NE) China that provides insight into this issue. Li concentration (0.3–2.7 ppm) and δ⁷Li (mostly 2‰–6‰) in olivine from the Shangzhi peridotites are similar to the normal mantle values and show roughly negative correlations with the indices of melt extraction (such as modal olivine and whole rock MgO). These features are consistent with variable degrees of partial melting. In contrast, clinopyroxene from the Shangzhi xenoliths shows significant Li enrichment (0.9–6.1 ppm) and anomalously light δ⁷Li (??13.8‰ to 7.7‰) relative to normal mantle values. Such features can be explained by Li diffusion from silicate melts or Li-rich fluids occurring over a very short time (several minutes to several hours). Moreover, the light Li isotopic compositions preserved in some bulk samples also indicate that these percolated melts/fluids have not had enough time to isotopically equilibrate with the bulk peridotite. We thus emphasize that Li isotopic fractionation in the Shangzhi mantle xenoliths is mainly related to Li diffusion from silicate melts or Li-rich fluids that took place shortly before or coincident with their entrainment into the host magmas.     

Some specific features of genesis of microdiamonds of octahedral and cubic habit from kimberlites of the Udachnaya pipe (Yakutia) inferred from carbon isotopes and main impurity defects

Microdiamonds (crystals smaller than 1 mm) of octahedral and cubic habit from Udachnaya kimberlite pipe (Yakutia) have been compared in order to distinguish genetic features inferred from carbon isotopic composition and impurity defects. Microdiamonds of cubic habit from the Udachnaya kimberlite pipe have a fibrous internal structure and a high content of nitrogen impurity (400–3000 ppm). Octahedral microdiamonds from the same deposit are distinguished by a low nitrogen content of 0 to 500 ppm and zoning structure. The isotopic composition of carbon (δ¹³C is –4.7‰ for octahedra and –4.5‰ for cuboids) suggests a common source of carbon for these morphologic groups. The studied characteristics can be due to crystallization of octahedra from carbon dissolved in the melt, and cuboids, under the conditions of the hampered diffusion of carbon.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Mg-ilmenite megacrysts from the Arkhangelsk kimberlites, Russia: Genesis and interaction with kimberlite melt and postkimberlite fluid

In the present work we studied Mg-ilmenite megacrysts from the Arkhangelsk kimberlites (the Kepino kimberlite field and mantle xenoliths from the Grib pipe). On the basis of isotopic (Rb/Sr, Sm/Nd, δ¹⁸O) and trace-element data we argue that studied Mg-ilmenite megacrysts have a genetic relation to the “protokimberlitic” magma, which was parental to the host kimberlites. Rb-Sr ages measured on phlogopite from ilmenite-clinopyroxenite xenoliths and the host Grib kimberlite overlap within the error (384 Ma and 372 ± 8 Ma, respectively; Shevchenko et al., 2004) with our estimation of the Kotuga kimberlite emplacement (378 ± 25 Ma). Sr and Nd isotopic compositions of megacrysts are close to the isotopic composition of host kimberlites (Mg-ilmenites from kimberlites have ⁸⁷Sr/⁸⁶Sr_{(t = 384)} = 0.7050–0.7063, ?Nd_{(t = 384)} = + 1.7, +1.8, ilmenite from ilmenite-garnet clinopyroxenite xenolith has ⁸⁷Sr/⁸⁶St_{(t = 384)} = 0.7049, ?Nd_{(t = 384)} = +3.5). Oxygen isotopic composition of ilmenites (δ¹⁸O = +3.8–+4.5‰) is relatively “light” in comparison with the values for mantle minerals (δ¹⁸O = +5–+6‰). Taking into account ilmenite-melt isotope fractionation, these values of δ¹⁸O indicate that ilmenites could crystallize from the “protokimberlitic” melt. Temperatures and redox conditions during the formation of ilmenite reaction rims were estimated using ilmenite-rutile and titanomagnetite-ilmenite thermo-oxybarometers. New minerals within the rims crystallized at increasing oxygen fugacity and decreasing temperature. Spinels precipitated during the interaction of ilmenite with kimberlitic melt at T = 1000–1100°C and oxygen fugacity $\Delta \log f_{O_2 }$ [QFM] ≈ 1. Rims comprised with rutile and titanomagnetite crystallized at T ≈ 1100°C, $\Delta \log f_{O_2 }$ [NNO] ≈ 4 and T = 600–613°C, $\Delta \log f_{O_2 }$ [QFM] ≈ 3.7, respectively. Rutile lamellae within ilmenite grains from clinopyroxenitic xenolith were formed T ≥ 1000–1100°C and oxygen fugacity $\Delta \log f_{O_2 }$ [NNO] = ?3.7. Since the pressure of clinopyroxene formation from this xenolith was estimated to be 45–53 kbar, redox conditions at 135–212 km depths could be close to $\Delta \log f_{O_2 }$ [NNO] = ?3.7.     

Diamond resource potential of kimberlites from the Zimny Bereg field,Arkhangel’sk oblast

Kimberlites with different diamond grades from the Zolotitsa, Verkhotina, and Kepina occurrences of the Zimny Bereg field (Arkangel’sk oblast) have been compared in order to ascertain geochemical criteria of their diamond resource potential. A new collection of 21 core samples taken within a depth interval of 207–940 m from nine boreholes drilled in the central and western portions of the high-grade diamond-bearing Grib kimberlite pipe was subjected to comprehensive petrographic and geochemical examination, including Sr, Nd, and Pb isotopes and trace elements determined with ICP-MS. The compositional variations in kimberlites are controlled by the structural types of rocks. Porphyritic kimberlite (PK) distinctly differs from autolithic kimberlite breccia (AKB). Autoliths (Av) and PK are enriched in Th, U, Nb, Ta, La, Ce, Pr, P, Nd, Sm, Eu, Ti, LREE, and MREE, whereas HREE contents are rather uniform in all types of kimberlites. No lateral zoning was observed in pipes pertaining to the same structural type. The composition of kimberlites in the Zimny Bereg field and their diamond resource potential are variable. In the series of the Zolotitsa, Verkhotina, and Kepina occurrences, the Ti content increases, the La/Yb ratio grows from 18–44 to 70–130, and the diamond grade diminishes in the Kepina occurrence. The variations in kimberlite compositions are considered in terms of the degree of partial melting in the mantle, the role of volatiles, etc. As follows from the variation in the Ce/Y ratio, kimberlites from the Zolotitsa occurrence were formed at a lower degree of partial melting in comparison with the Kepina occurrence. Products of different degrees of partial melting are recognized within the Grib pipe; Av were likely formed at a somewhat higher degree of melting than AKB. An appreciable isotopic heterogeneity of the mantle is recorded in variable Nd and Sr isotopic compositions of kimberlites. The Kepina kimberlites were derived from a source slightly depleted relative to CHUR (?_Nd(t) reaches +4) and are close to kimberlites of group I in South Africa. Kimberlites from the Grib pipe with transitional Nd isotopic composition plotted near the Bulk Silicate Earth (BSE) value in the ?_Nd(t)-?_Sr(t) diagram adjoin the first group. The source of kimberlites of the Zolotitsa occurrence falls in the field of enriched mantle and is considered to be a product of interaction of an asthenospheric plume with the ancient enriched lithospheric mantle. Kimberlites depleted in Ti, Zr, and Th are related to a source formed as a result of a multistage process that included mantle metasomatism with participation of fluids. Devonian kimberlites derived from sources that involve crustal material (a shift of ²⁰⁶Pb/²⁰⁴Pb, minimums of Th, U, Nb, and Ta contents) are diamond-bearing both in the East European Platform (the Zolotitsa and Verkhotina occurrences) and in the Siberian Craton (the Nakyn field).     

The P3 kimberlite and P4 lamproite,Wajrakarur kimberlite field,India: mineralogy,and major and minor element compositions of olivines as records of their phenocrystic vs xenocrystic origin

Distinctly different groundmass mineralogy characterise the hypabyssal facies, Mesoproterozoic diamondiferous P3 and P4 intrusions from the Wajrakarur Kimberlite Field, southern India. P3 is an archetypal kimberlite with macrocrysts of olivine and phlogopite set in a groundmass dominated by phlogopite and monticellite with subordinate amounts of serpentine, spinel, perovskite, apatite, calcite and rare baddeleyite. P4 contains mega- and macrocrysts of olivine set in a groundmass dominated by clinopyroxene and phlogopite with subordinate amounts of serpentine, spinel, perovskite, apatite, and occasional gittinsite, and is mineralogically interpreted as an olivine lamproite. Three distinct populations of olivine, phlogopite and clinopyroxene are recognized based on their microtextural and compositional characteristics. The first population includes glimmerite and phlogopite–clinopyroxene nodules, and Mg-rich olivine macrocrysts (Fo 90–93) which are interpreted to be derived from disaggregated mantle xenoliths. The second population comprises macrocrysts of phlogopite and Fe-rich olivine (Fo 81–89) from P3, megacrysts and macrocrysts of Fe-rich olivine (Fo 85–87) from P4 and a rare olivine–clinopyroxene nodule from P4 which are suggested to have a genetic link with the precursor melt of the respective intrusions. The third population represents clearly magmatic minerals such as euhedral phenocrysts of Fe-rich olivine (Fo 85–90) crystallised at mantle depths, and olivine overgrowth rims formed contemporaneously with groundmass minerals at crustal levels. Close spatial association and contemporaneous emplacement of P3 kimberlite and P4 lamproite is explained by a unifying petrogenetic model which involves the interaction of a silica-poor carbonatite melt with differently metasomatised wall rocks in the lithospheric mantle. It is proposed that the metasomatised wall rock for lamproite contained abundant MARID-type and phlogopite-rich metasomatic veins, while that for kimberlite was relatively refractory in nature.

     

Isotope compositions of C and O of magmatic calcites from the Udachnaya–East pipe kimberlite,Yakutia

It has been demonstrated for the first time that the isotopic compositions of carbon (δ¹³C) in magmatic calcites from the Udachnaya–East pipe kimberlite groundmass varies from–2.5 to–1.0‰ (V-PDB), while those of oxygen (δ¹⁸O) range from 15.0 to 18.2‰ (V-SMOW). The obtained results imply that during the terminal late magmatic and postmagmatic stages of the kimberlite pipe formation, the carbonates in the kimberlite groundmass became successively heavier isotopically, which indicates the hybrid nature of the carbonate component of the kimberlite: it was formed with contributions from mantle and sedimentary marine sources.

     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Sub-arc mantle heterogeneity in oxygen isotopes: evidence from Permian mafic–ultramafic intrusions in the Central Asian Orogenic Belt

Integrated zircon–olivine O–Hf isotope data have been successfully used to unravel the nature of the source mantle for the early Permian post-collisional mafic–ultramafic intrusive rocks in the southern margin of the Central Asian Orogenic Belt in NW China. Olivine crystals with forsterite (Fo) contents varying from 91 to 87 mol% from the Permian Pobei mafic–ultramafic complex in the region yield highly elevated δ¹⁸O from 6.0 to 7.2‰. These values are much higher than typical mantle values (~?5.3‰) and are apparently at odds with the mantle-like ε_Nd(t) values of whole rocks (4.9–5.4). Magmatic zircon crystals from troctolite and gabbroic rocks show divergent oxygen and hafnium isotopic compositions: mantle-like ε_Hf(t) values from 5.1 to 11.9 and crust-like δ¹⁸O values from 7.6 to 10.1‰. The observed increase of δ¹⁸O values from olivine (an early crystallizing phase) to zircon (a late crystallizing phase) in the mafic–ultramafic rocks is generally consistent with an AFC process. However, this process cannot fully explain the highly elevated δ¹⁸O values (6–7‰) for the most primitive olivine containing Fo as high as mantle olivine (>?90 mol%) and the mantle-like Hf isotope composition of zircon. Mixing calculation indicates that such highly unusual isotope compositions can be explained by the previous source mantle contamination with subducted sediment-derived melts and slab-derived fluids. Our results show that the combination of zircon O–Hf isotopes and olivine oxygen isotopes is more effective than the data of zircon or olivine alone to distinguish the effect of AFC process from source contamination. The results from this study provide a new line of evidence that the sub-arc mantle is not homogeneous in oxygen isotopes.     

Mineralogy and equilibrium P-T estimates for peridotite assemblages from the V. Grib kimberlite pipe (Arkhangelsk Kimberlite Province)

This study presents mineralogical and thermobarometric data for equilibrium peridotite assemblages from the V. Grib kimberlite pipe of the Arkhangelsk diamond province. We provided the first constraints on the composition, structure, thermal state, and lower boundary of the lithospheric mantle beneath the V. Grib kimberlite pipe. It was found that phlogopite-free and phlogopite-bearing peridotite xenoliths can be distinguished by their mineral chemistry. The occurrence of phlogopite in peridotites may represent evidence for modal metasomatism responsible for variation in the mineral composition of phlogopite-pyrope and pyrope peridotites. On the basis of P-T estimates, we conclude that modal metasomatism may have affected the entire thickness of the lithospheric mantle beneath the V. Grib kimberlite pipe. Comparison of our results with the available data from the literature shows strong vertical and lateral mantle heterogeneity beneath kimberlite pipes of the Lomonosov deposit and the V. Grib pipe.     

Primitive Magma From the Jericho Pipe, N.W.T., Canada: Constraints on Primary Kimberlite Melt Chemistry

We report the first estimates of primary kimberlite melt compositionfrom the Slave craton, based on samples of aphanitic kimberlitefrom the Jericho kimberlite pipe, N.W.T., Canada. Three samplesderive from the margins of dykes where kimberlite chilled againstwall rock (JD51, JD69 and JD82) and are shown to be texturallyconsistent with crystallization from a melt. Samples JD69 andJD82 have geochemical characteristics of primitive melts: theyhave high MgO (20–25 wt %), high mg-numbers (86–88),and high Cr (1300–1900 ppm) and Ni (800–1400 ppm)contents. They also have high contents of CO₂ (10–17 wt%). Relative to bulk macrocrystal kimberlite, they have lowermg-numbers and lower MgO but are enriched in incompatible elements(e.g. Zr, Nb and Y), because the bulk kimberlite compositionsare strongly controlled by accumulation of mantle olivine andother macrocrysts. The compositions of aphanitic kimberlitefrom Jericho are similar to melts produced experimentally bypartial melting of a carbonate-bearing garnet lherzolite. Onthe basis of these experimental data, we show that the primarymagmas from the Jericho kimberlite could represent 0·7–0·9%melting of a carbonated lherzolitic mantle source at pressuresand temperatures found in the uppermost asthenosphere to theSlave craton. The measured CO₂ contents for samples JD69 andJD82 are only slightly lower than the CO₂ contents of the correspondingexperimental melts; this suggests that the earliest hypabyssalphase of the Jericho kimberlite retained most of its originalvolatile content. As such these samples provide a minimum CO₂content for the primary kimberlite magmas from the Slave craton. KEY WORDS: kimberlite; melt; primitive; primary magma; Slave craton     

Lithium elemental and isotopic variations in rock-melt interaction

Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ⁷Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ⁷Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ⁷Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ⁷Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ⁷Li, the carbonatite and silicate melts produced remarkably contrasting δ⁷Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ⁷Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.     

Re-Os geochronology,O isotopes and mineral geochemistry of the Neoproterozoic Songshugou ultramafic massif in the Qinling Orogenic Belt,China

The Qinling Orogenic Belt was formed by subduction and collision between the North and South China Blocks along the Shangdan suture. The Songshugou ultramafic massif located on the northern side of the Shangdan suture provides essential insights into the mantle origin and evolutionary processes during spreading and subduction of the Shangdan oceanic lithosphere. The ultramafic massif comprises harzburgite, coarse- and fine-grained dunites. The spinels from harzburgite exhibit low Cr# and high Mg# numbers, suggesting a mid-ocean ridge peridotite origin, whereas spinels from both coarse- and fine-grained dunites are indicated as resulted from melt-rock reaction due to their systematic higher Cr# and low Mg# numbers. This melt-rock reaction in the dunites is also indicated by the low TiO₂ (mostly <0.4 wt%) in the spinel and high Fo (90–92) in olivines. Due to its relatively homogeneous nature in the mantle, oxygen isotopic composition is a sensitive indicator for the petrogenesis and tectonic setting of the Songshugou ultramafic rocks. Based on in-situ oxygen isotope analyses of olivines from twenty-six rock samples, most harzburgites from the Songshugou ultramafic massif show low δ¹⁸O values of 4.54–5.30‰, suggesting the olivines are equilibrium with N-MORB magmas and originally formed in a mid-ocean ridge setting. The coarse- and fine-grained dunites exhibit slightly higher olivine δ¹⁸O values of 4.69–6.00‰ and 5.00–6.11‰, respectively, suggesting they may have been modified by subduction-related boninitic melt-rock reaction. The δ¹⁸O values of olivines systematically increasing from the harzburgites, to coarse-grained dunites and fine-grained dunites may suggest enhancing of melt-rock reaction. The decreasing of Os concentration, ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios from harzburgite to dunite suggest an ¹⁸⁷Os-enriched, subduction zone melt was responsible for creating the melt channel for melt-rock reactions. Together with the high-temperature ductile deformation microstructures, these isotopic and mineral geochemical features suggest that the harzburgites represent mantle residues after partial melting at mid-ocean ridge or supra-subduction zone, while the dunites were probably resulted from reactions between boninitic melt and harzburgites in a supra-subduction zone. Re-Os geochronology yields a maximum Re depletion model age (T_RD) of 805 Ma, constraining the minimum formation age of the harzburgites derived from oceanic mantle. Eight samples of whole rock and chromite yield a Re-Os isochron age of 500 ± 120 Ma, constraining the timing of melt-rock reactions. Combined with the regional geology and our previous investigations, the Songshugou ultramafic rocks favors a mantle origin at mid-ocean ridge before 805 Ma, and were modified by boninitic melt percolations in a SSZ setting at ca. 500 Ma. This long-term tectonic process from spreading to subduction might imply a huge Pan-Tethyan ocean between the Laurasia (e.g., North China Block) and Gondwana (e.g., South China Block) and/or a one-side subduction.     

Searching for parental kimberlite melt

Constraining the composition of primitive kimberlite magma is not trivial. This study reconstructs a kimberlite melt composition using vesicular, quenched kimberlite found at the contact of a thin hypabyssal dyke. We examined the 4 mm selvage of the dyke where the most elongate shapes of the smallest calcite laths suggest the strongest undercooling. The analyzed bulk compositions of several 0.09-1.1 mm² areas of the kimberlite free from macrocrysts were considered to be representative of the melt. The bulk analyses conducted with a new “chemical point-counting” technique were supplemented by modal estimates, studies of mineral compositions, and FTIR analysis of olivine phenocrysts. The melt was estimated to contain 26-29.5 wt% SiO₂, ∼7 wt% of FeO_T, 25.7-28.7 wt% MgO, 11.3-15 wt% CaO, 8.3-11.3 wt% CO₂, and 7.6-9.4 wt% H₂O. Like many other estimates of primitive kimberlite magma, the melt is too magnesian (Mg# = 0.87) to be in equilibrium with the mantle and thus cannot be primary. The observed dyke contact and the chemistry of the melt implies it is highly fluid (η = 10¹-10³ Pa s at 1100-1000 °C) and depolymerized (NBO/T = 2.3-3.2), but entrains with 40-50% of olivine crystals increasing its viscosity. The olivine phenocrysts contain 190-350 ppm of water suggesting crystallization from a low SiO₂ magma (a_SiO2 below the olivine-orthopyroxene equilibrium) at 30-50 kb. Crystallization continued until the final emplacement at depths of few hundred meters which led to progressively more Ca- and CO₂-rich residual liquids. The melt crystallised phlogopite (6-10%), monticellite (replaced by serpentine, ∼10%), calcite rich in Sr, Mg and Fe (19-27%), serpentine (29-31%) and minor amounts of apatite, ulvöspinel-magnetite, picroilmenite and perovskite. The observed content of H₂O can be fully dissolved in the primitive melt at pressures greater than 0.8-1.2 kbar, whereas the amount of primary CO₂ in the kimberlite exceeds CO₂ soluble in the primitive kimberlite melt. A mechanism for retaining CO₂ in the melt may require a separate fluid phase accompanying kimberlite ascent and later dissolution in residual carbonatitic melt. Deep fragmentation of the melt as a result of volatile supersaturation is not inevitable if kimberlite magma has an opportunity to evolve.     

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

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

Multiple metasomatism in Sulu ultrahigh-P garnet peridotite constrained by petrological and geochemical investigations

The pre‐pilot hole (PP1) of the Chinese Continental Scientific Drilling Project (CCSD) recovered drill core samples from a 118 m‐thick section of peridotites located at Zhimafang in the southern Sulu UHP terrane, China. The peridotites consist of phlogopite‐bearing garnet lherzolite, harzburgite, wehrlite and dunite. Some peridotite layers contain magnesite and Ti‐clinohumite, and are characterized by LREE and LILE enrichment and HFSE depletion. Phlogopite (Phl) occurs in the peridotite matrix and is LILE‐enriched with low Zr/Hf ratios (0.19–0.60). Phlogopite shows a mantle signature in H and O isotopes (δ¹⁸O: +5.4‰ to +5.9‰, and δD: ?76‰ to ?91‰). Ti‐clinohumite (Ti‐Chu) is Nb and Ta‐enriched and has higher Ti and HREE concentrations than phlogopite. Magnesite (Mgs) occurs as megacrysts, as a matrix phase, and as veins (±Phl ± Ti‐Chu), and contains low REE^total contents (<0.3 ppm) with a flat REE pattern. The δ¹⁸O values (+5.5‰ to +8.0‰) of magnesite are in the range of primary carbonatite, but the δ¹³C values (?2.4‰ to ?3.4‰) are slightly more positive than those of the mantle and of primary carbonatite. Petrochemical data indicate that the Zhimafang peridotite was subjected to three episodes of metasomatism, listed in succession from oldest to youngest: (1) crystallization of phlogopite in the mantle caused by infiltration of K‐rich hydrous fluid/melt; (2) formation of Mgs and Mgs ± Phl ± Ti‐Chu veins possibly caused by infiltration of mantle‐derived carbonatitic melt with a hydrous silicate component; and (3) replacement of magnesite, garnet and diopside by dolomite and secondary hydrous phases caused by a crust‐related, CO₂‐bearing, aqueous fluid. Stable isotopic compositions of phlogopite and magnesite indicate metasomatic agents for events (1) and (2) are from an enriched mantle. Multiple metasomatism imposed on mantle peridotite of variable composition led to significant compositional heterogeneity at all scales within the Zhimafang peridotite.     

Stable carbon isotopes in selected granitic,mafic, and ultramafic igneous rocks

Noncarbonate (combustion) and carbonate (acid decomposition) carbon were separately analyzed in 18 granitic rocks from a group of related Tertiary intrusions near Crested Butte, Colorado, and 14 mafic and ultramafic rocks from various localities in the western United States. Among the granites, carbonate carbon ranges from nil to 0.76 per cent with δC¹³-values from ?5.6 to ? 9.0‰ (vs PDB); noncarbonate carbon varies from 32–360 ppm with δC¹³-values from ?19.7 to ?26.6‰, The mafic and ultramafic rocks have carbonate carbon contents ranging from 53 ppm to about 2 per cent with δC¹³-values from + 2.9 to ?10.3‰; noncarbonate carbon varies from 26 to 150 ppm with δC¹³-values of ?22.2 to ? 27.l‰ For these samples, carbonate carbon ranges from 12.0 to 29.4‰ heavier than coexisting noncarbonate carbon. This consistent difference between δC¹³ of carbonate and noncarbonate carbon may be an isotopic fractionation effect. Because the specific indigenous form of noncarbonate (combustion) carbon is in doubt, conclusive interpretations regarding isotopic equilibration and fractionation cannot be made.These results have bearing on the assessment of the isotopic composition of mantle carbon and consequently are germane to the question of the origin (source) and history of crustal carbon. If mantle carbon is isotopically similar to noncarbonate (combustion) carbon, i.e. δC¹³-values from ?19.7 to ? 27.1‰, then a simple mantle degassing source for crustal carbon is improbable. Such a result would indicate an additional source of crustal carbon such as from a primitive atmosphere or extra-terrestrial accretion.