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‰.     

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.     

Origin of sub-lithospheric diamonds from the Juina-5 kimberlite (Brazil): constraints from carbon isotopes and inclusion compositions

Forty-one diamonds sourced from the Juina-5 kimberlite pipe in Southern Brazil, which contain optically identifiable inclusions, have been studied using an integrated approach. The diamonds contain <20 ppm nitrogen (N) that is fully aggregated as B centres. Internal structures in several diamonds revealed using cathodoluminescence (CL) are unlike those normally observed in lithospheric samples. The majority of the diamonds are composed of isotopically light carbon, and the collection has a unimodal distribution heavily skewed towards δ¹³C ~ ?25 ‰. Individual diamonds can display large carbon isotope heterogeneity of up to ~15 ‰ and predominantly have isotopically lighter cores displaying blue CL, and heavier rims with green CL. The light carbon isotopic compositions are interpreted as evidence of diamond growth from abiotic organic carbon added to the oceanic crust during hydrothermal alteration. The bulk isotopic composition of the oceanic crust, carbonates plus organics, is equal to the composition of mantle carbon (?5 ‰), and we suggest that recycling/mixing of subducted material will replenish this reservoir over geological time. Several exposed, syngenetic inclusions have bulk compositions consistent with former eclogitic magnesium silicate perovskite, calcium silicate perovskite and NAL or CF phases that have re-equilibrated during their exhumation to the surface. There are multiple occurrences of majoritic garnet with pyroxene exsolution, coesite with and without kyanite exsolution, clinopyroxene, Fe or Fe-carbide and sulphide minerals alongside single occurrences of olivine and ferropericlase. As a group, the inclusions have eclogitic affinity and provide evidence for diamond formation at pressures extending to Earth’s deep transition zone and possibly the lower mantle. It is observed that the major element composition of inclusions and isotopic compositions of host Juina-5 diamonds are not correlated. The diamond and inclusion compositions are intimately related to subducted material and record a polybaric growth history across a depth interval stretching from the lower mantle to the base of the lithosphere. It is suggested that the interaction of slab-derived melts and mantle material combined with subsequent upward transport in channelised networks or a buoyant diapir explains the formation of Juina-5 diamonds. We conclude that these samples, despite originating at great mantle depths, do not provide direct information about the ambient mantle, instead, providing a snapshot of the Earth’s deep carbon cycle.     

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions ('¹³C: peridotitic -5.4 to -2.2‰; eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side ('¹³C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (̿,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.     

Noble gas and carbon isotope ratios in Argyle diamonds,Western Australia: Evidence for a deeply subducted volatile component

The Argyle lamproite pipe of Western Australia contains diamonds formed at depths exceeding 150 km. We undertook noble gas and carbon isotope ratio (δ¹³C) analyses of three diamonds (likely of eclogitic paragenesis) from the Argyle lamproite to test for the possible presence of deeply subducted volatile components, and to further constrain the noble gas evolution of the Earth's mantle. The Argyle diamonds are characterised by mantle ³He (with ³He/⁴He ratios of 0.79 R _A to 0.25 R _A, where R _A is the atmospheric ³He/⁴He ratio of 1.4 × 10^–6), small excess Ar and Xe isotope anomalies relative to atmospheric components, and δ¹³C values of –11.6 to –10.2‰ VPDB. These observations indicate that noble gas and carbon isotopic compositions of the mantle where the Argyle diamonds formed, represent mixtures of an intrinsic mantle component with sedimentary and atmospheric components that may have been introduced through subduction processes.     

Did an extensive forest ever develop on the Chinese Loess Plateau during the past 130 ka?: a test using soil carbon isotopic signatures

Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ¹³C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ¹³C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C₃ and C₄ plants and can be distinguished from that in the patchy forest areas where exclusive C₃ trees yield a narrow δ¹³C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ¹³C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C₃ and C₄ contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.     

Diamonds in the Attawapiskat area of the Superior craton (Canada): evidence for a major diamond-forming event younger than 1.1 Ga

Here, we compare nitrogen aggregation characteristics and carbon isotopic compositions in diamonds from Mesoproterozoic (T1) and Jurassic (U2) kimberlites in the Attawapiskat area—the first diamond-producing area on the Superior craton. The T1 kimberlite sampled diamonds from the lithospheric mantle at 1.1 Ga, at the same time as the major Midcontinent Rift event. These diamonds have a narrow range in δ¹³C (mode of ?3.4 ‰), with compositions that overlap other diamond localities on the Superior craton. Some diamond destruction must have occurred during the Mesoproterozoic in response to the thermal impact of the Midcontinent Rift—the associated elevated geotherm caused a narrow diamond window (<30 km) close to the base of the lithosphere, compared to a wide diamond window of ~85 km following thermal relaxation (sampled by Jurassic kimberlites, such as U2). T1 diamonds have highly aggregated nitrogen, possibly due to the thermal effect of the rift. Diamond-favourable conditions were re-established in the lithospheric mantle after the thermal impact of the Midcontinent Rift dissipated. The poorly aggregated nature of nitrogen in U2 diamonds—compared to highly aggregated nitrogen in diamonds from T1—indicates that renewed diamond formation must have occurred only after the thermal impact of the Midcontinent Rift at 1.1 Ga had subsided and that these newly formed diamonds were subsequently sampled by Jurassic kimberlites. The overall δ¹³C distribution for U2 diamonds is distinct to T1 and other Superior diamonds, further suggesting that U2 diamonds are not related to the older pre-rift diamonds.     

Diamonds from Jagersfontein (South Africa): messengers from the sublithospheric mantle

The diamond population from the Jagersfontein kimberlite is characterized by a high abundance of eclogitic, besides peridotitic and a small group of websteritic diamonds. The majority of inclusions indicate that the diamonds are formed in the subcratonic lithospheric mantle. Inclusions of the eclogitic paragenesis, which generally have a wide compositional range, include two groups of eclogitic garnets (high and low Ca) which are also distinct in their rare earth element composition. Within the eclogitic and websteritic suite, diamonds with inclusions of majoritic garnets were found, which provide evidence for their formation within the asthenosphere and transition zone. Unlike the lithospheric garnets all majoritic garnet inclusions show negative Eu-anomalies. A narrow range of isotopically light carbon compositions (δ¹³C −17 to −24 ‰) of the host diamonds suggests that diamond formation in the sublithospheric mantle is principally different to that in the lithosphere. Direct conversion from graphite in a subducting slab appears to be the main mechanism responsible for diamond formation in this part of the Earth’s mantle beneath the Kaapvaal Craton. The peridotitic inclusion suite at Jagersfontein is similar to other diamond deposits on the Kaapvaal Craton and characterized by harzburgitic to low-Ca harzburgitic compositions.     

FTIR Spectroscopy Data and Carbon Isotope Characteristics of the Ophiolite‐hosted Diamonds

We report new δ¹³C ‐values data and N‐content and N‐aggregation state values for microdiamonds recovered from peridotites and chromitites of the Luobusa ophiolite (Tibet) and chromitites of the Ray‐Iz ophiolite in the Polar Urals (Russia). All analyzed microdiamonds contain significant nitrogen contents (from 108 up to 589 ± 20% atomic ppm) with a consistently low aggregation state, show identical IR spectra dominated by strong absorption between 1130 cm^?1 and 1344 cm^?1, and hence characterize Type Ib diamond. Microdiamonds from the Luobusa peridotites have δ¹³C ‐PDB‐values ranging from ‐28.7‰ to ‐16.9‰, and N‐contents from 151 to 589 atomic ppm. The δ¹³C and N‐content values for diamonds from the Luobusa chromitites are ‐29‰ to ‐15.5‰ and 152 to 428 atomic ppm, respectively. Microdiamonds from the Ray‐Iz chromitites show values varying from ‐27.6 ‰ to ‐21.6 ‰ in δ¹³C and from 108 to 499 atomic ppm in N. The carbon isotopes values bear similar features with previously analyzed metamorphic diamonds from other worldwide localities, but the samples are characterized by lower N‐contents. In every respect, they are different from diamonds occurring in kimberlites and impact craters. Our samples also differ from the few synthetic diamonds; we also analyzed showing enhanced δ¹³C ‐variability and less advanced aggregation state than synthetic diamonds. Our newly obtained N‐aggregation state and N‐content data are consistent with diamond formation over a narrow and rather cold temperature range (i.e. <950°C), and in a short residence time (i.e. within several million years) at high temperatures in the deep mantle.     

Lithium isotopic composition of Central American volcanic arc lavas: implications for modification of subarc mantle by slab-derived fluids: correction

Our previously reported lithium isotope data for the least enriched members of the Central American Volcanic Arc were in error due to problems in ion extraction from high MgO rocks. This paper presents reanalyses of the entire suite of the CAVA lavas after a systematic investigation of the elution behavior of Li as a function of the rock composition. The most significant correction pertains to the mantle end members of the Nicaragua and Costa Rica series, which now display MORB-like δ⁶Li values (−4.5‰) and not much lighter (+1‰ to +3‰) as previously reported. Also revised is the composition of a peridotite from Zabargad Island (Red Sea), considered to represent undepleted upper mantle, whose corrected δ⁶Li also resembles MORB. These new data therefore remove the speculation that Earth's primitive mantle has extremely light Li isotopic composition and that the mantle beneath CAVA contains such isotopically light domains. The δ⁶Li range for the arc segment from Costa Rica to Guatemala has now been reset to −4.5‰ to −6.4‰. Despite the narrower range, Li isotopic values remain well correlated with other subduction-related properties, including LILE and fluid-mobile elements. Model calculations show that the isotopic compositions of the lavas are consistent with small additions of slab-derived fluids to the enriched and depleted domains of the subarc mantle.     

Stable isotope characterization of pedogenic and lacustrine carbonates from the Chinese Tian Shan: Constraints on the Mesozoic–Lower Cenozoic palaeoenvironmental evolution

In the Mesozoic–Cenozoic continental deposits of the Tian Shan area, two main levels containing pedogenic carbonates have been identified on both the southern and northern foothills of the range: one in the Upper Jurassic series and one in the Upper Cretaceous–Lower Palaeocene series. In order to reconstruct the palaeoenvironmental and palaeotopographic characteristics of the Tian Shan area during these two periods, we measured the oxygen and carbon isotope composition of these pedogenic carbonates (calcrete and nodules). The stable isotope compositions are homogeneous: most δ¹⁸O values are between 21 and 25‰ and most δ¹³C values are between −4 and −6‰. No distinction can be made between the calcrete and nodule isotopic compositions. The constancy of isotopic values across the Tian Shan is evidence of a development of these calcification features in similar palaeoenvironmental conditions. The main inference is that no significant relief existed in that area at the Cretaceous−Palaeogene boundary, implying that most of the present relief developed later, during the Cenozoic. In addition to the pedogenic carbonates, few beds of limestones interstratified in the Jurassic series of the southern foothills display oxygen and carbon isotope compositions typical of lacustrine carbonates, ruling out brackish water incursion at that period in the region.     

Carbon and Nitrogen Isotopic,and Mineral Inclusion Studies on the Diamonds from the Pozanti‐Karsanti Chromitite,Turkey

He Pozanti‐Karsanti ophiolite (PKO) is one of the largest oceanic remnants in the Tauride belt, Turkey. Micro‐diamonds were recovered from the podiform chromitites, and these were investigated based on morphology, color, cathodoluminescence, nitrogen content, carbon and nitrogen isotopes, internal structure and inclusions. The diamonds recovered from the PKO are mainly mixed‐habit diamonds with sectors of different brightness under the cathodoluminescence images. The total δ¹³C range of the PKO diamonds ranges between ?18.8 ‰ and ?28.4 ‰, with a principle δ¹³C mode at ?25 ‰. Nitrogen contents of the diamonds range from 7 to 541 μg/g with a mean value of 171 μg/g, and the δ¹⁵N values range from ?19.1 ‰ to 16.6 ‰, with a δ¹⁵N mode of ?9 ‰. Stacking faults and partial dislocations are commonly observed in the Transmission Electron Microscopy foils whereas inclusions are rather rare. Combinations of (Ca_0.81Mn_0.19)SiO₃, NiMnCo‐alloy and nano‐size, quenched fluid phases were observed as inclusions in the PKO diamonds, confirming a natural origin of these diamonds. We believe that the δ¹³C‐depleted carbon signature of the PKO diamonds is a remnant of previously subducted crustal matter. These diamonds may have crystallized in metal‐rich melts in the asthenospheric mantle at depth below 250 km which were subsequently carried rapidly upward by asthenospheric melts/fliuds. We concluded that diamond‐bearing asthenospheric melts were likely involved in the formation of the Pozanti‐Karsanti podiform chromitite.     

Diamond growth from oxidized carbon sources beneath the Northern Slave Craton, Canada: A δC-N study of eclogite-hosted diamonds from the Jericho kimberlite

Diamonds from high- and low-MgO groups of eclogite xenoliths from the Jericho kimberlite, Slave Craton, Canada were analyzed for carbon isotope compositions and nitrogen contents. Diamonds extracted from the two groups show remarkably different nitrogen abundances and δ¹³C values. While diamonds from high-MgO eclogites have low nitrogen contents (5-82 ppm) and extremely low δ¹³C values clustering at ∼−40‰, diamonds from the low-MgO eclogites have high nitrogen contents (>1200 ppm) and δ¹³C values from −3.5‰ to −5.3‰.Coupled cathodoluminescence (CL) imaging and SIMS analysis of the Jericho diamonds provides insight into diamond growth processes. Diamonds from the high-MgO eclogites display little CL structure and generally have constant δ¹³C values and nitrogen contents. Some of these diamonds have secondary rims with increasing δ¹³C values from −40‰ to ∼−34‰, which suggests secondary diamond growth occurred from an oxidized growth medium. The extreme negative δ¹³C values of the high-MgO eclogite diamonds cannot be produced by Rayleigh isotopic fractionation of average mantle-derived carbon (−5‰) or carbon derived from typical organic matter (∼−25‰). However, excursions in δ¹³C values to −60‰ are known in the organic sedimentary record at ca. 2.7 and 2.0 Ga, such that diamonds from the high-MgO eclogites could have formed from similar organic matter brought into the Slave lithospheric mantle by subduction.SIMS analyses of a diamond from a low-MgO eclogite show an outer core with systematic rimwards increases in δ¹³C values coupled with decreases in nitrogen contents, and a rim with pronounced alternating growth zones. The coupled δ¹³C-nitrogen data suggest that the diamond precipitated during fractional crystallization from an oxidized fluid/melt from which nitrogen was progressively depleted during growth. Model calculations of the co-variation of δ¹³C-N yielded a partition coefficient (K_N) value of 5, indicating that nitrogen is strongly compatible in diamond relative to the growth medium. δ¹³C values of diamond cores (−4‰) dictate the growth medium had higher δ¹³C values than primary mantle-derived carbon. Therefore, possible carbon sources for the low-MgO eclogite diamonds include oxidized mantle-derived (e.g. protokimberlite or carbonatite) fluids/melts that underwent some fractionation during migration or, devolatilized subducted carbonates.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

The characterisation and origin of graphite in cratonic lithospheric mantle: a petrological carbon isotope and Raman spectroscopic study

Graphite-bearing peridotites, pyroxenites and eclogite xenoliths from the Kaapvaal craton of southern Africa and the Siberian craton, Russia, have been studied with the aim of: 1) better characterising the abundance and distribution of elemental carbon in the shallow continental lithospheric mantle; (2) determining the isotopic composition of the graphite; (3) testing for significant metastability of graphite in mantle rocks using mineral thermobarometry. Graphite crystals in peridotie, pyroxenite and eclogite xenoliths have X-ray diffraction patterns and Raman spectra characteristic of highly crystalline graphite of high-temperature origin and are interpreted to have crystallised within the mantle. Thermobarometry on the graphite-peridotite assemblages using a variety of element partitions and formulations yield estimated equilibration conditions that plot at lower temperatures and pressures than diamondiferous assemblages. Moreover, estimated pressures and temperatures for the graphite-peridotites fall almost exclusively within the experimentally determined graphite stability field and thus we find no evidence for substantial graphite metastability. The carbon isotopic composition of graphite in peridotites from this and other studies varies from δ¹³ C_PDB = ? 12.3 to ? ?3.8%o with a mean of-6.7‰, σ=2.1 (n=22) and a mode between-7 and-6‰. This mean is within one standard deviation of the-4‰ mean displayed by diamonds from peridotite xenoliths, and is identical to that of diamonds containing peridotite-suite inclusions. The carbon isotope range of graphite and diamonds in peridotites is more restricted than that observed for either phase in eclogites or pyroxenites. The isotopic range displayed by peridotite-suite graphite and diamond encompasses the carbon isotope range observed in mid-ocean-ridge-basalt (MORB) glasses and ocean-island basalts (OIB). Similarity between the isotopic compositions of carbon associated with cratonic peridotites and the carbon (as CO₂) in oceanic magmas (MORB/OIB) indicates that the source of the fluids that deposited carbon, as graphite or diamond, in catonic peridotites lies within the convecting mantle, below the lithosphere. Textural observations provide evidence that some of graphite in cratonic peridotites is of sub-solidus metasomatic origin, probably deposited from a cooling C-H-O fluid phase permeating the lithosphere along fractures. Macrocrystalline graphite of primary appearance has not been found in mantle xenoliths from kimberlitic or basaltic rocks erupted away from cratonic areas. Hence, graphite in mantle-derived xenoliths appears to be restricted to Archaean cratons and occurs exclusively in low-temperature, coarse peridotites thought to be characteristic of the lithospheric mantle. The tectonic association of graphite within the mantle is very similar to that of diamond. It is unlikely that this restricted occurrence is due solely to unique conditions of oxygen fugacity in the cratonic lithospheric mantle because some peridotite xenoliths from off-craton localities are as reduced as those from within cratons. Radiogenic isotope systematics of peridotite-suite diamond inclusions suggest that diamond crystallisation was not directly related to the melting events that formed lithospheric peridotites. However, some diamond (and graphite?) crystallisation in southern Africa occurred within the time span associated with the stabilisation of the lithospheric mantle (Pearson et al. 1993). The nature of the process causing localisation of carbon in cratonic mantle roots is not yet clearly understood.     

Geology and Isotope Geochemistry of the Dongzhongla Pb–Zn Deposit in Tibet: Implications for the Origin of the Ore‐Forming Fluids and Storage Condition of Certain Metals

As a newly discovered medium‐sized deposit (proven Pb + Zn resources of 0.23 Mt, 9.43% Pb and 8.73% Zn), the Dongzhongla skarn Pb–Zn deposit is located in the northern margin of the eastern Gangdese, central Lhasa block. Based on the geological conditions in this deposit of ore‐forming fluids, H, O, C, S, Pb, Sr, and noble gas isotopic compositions were analyzed. Results show that δ¹⁸O_SMOW of quartz and calcite ranged from −9.85 to 4.17‰, and δD_SMOW ranged from −124.7 to −99.6‰ (where SMOW is the standard mean ocean water), indicating magma fluids mixed with meteoric water in ore‐forming fluids. The δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from −1.4 to −1.1‰ and from 5.3 to 15.90‰, respectively, show compositions consistent with the carbonate limestone in the surrounding rocks, implying that the carbon was primarily sourced from the dissolution of carbonate strata in the Luobadui Formation. The ore δ³⁴S composition varied in a narrow range of 2.8 to 5.7‰, mostly between 4‰ and 5‰. The total sulfur isotopic value δ³⁴S was 4.7‰ with characteristics of magmatic sulfur. The ³He/⁴He values of pyrite and galena ranged from 0.101 to 5.7 Ra, lower than those of mantle‐derived fluids (6 ± 1 Ra), but higher than those of the crust (0.01–0.05 Ra), and therefore classified as a crust–mantle mixed source. The Pb isotopic composition for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of the ores were in the ranges of 18.628–18.746, 15.698–15.802, and 39.077–39.430, respectively, consistent with the Pb isotopic composition of magmatic rocks in the deposit, classified as upper‐crust lead. The ore lead was likely sourced partially from the crustal basement of the Lhasa Terrane. The initial (⁸⁷Sr/⁸⁶Sr)_i value from five sulfide samples ranged from 0.71732 to 0.72767, and associated ore‐forming fluids were mainly sourced from the partial melting of the upper‐crust materials. Pb isotopic compositions of ore sulfides from the Dongzhongla deposit are similar to that of the Yuiguila and Mengya'a deposit, indicating that they have similar sources of metal‐rich ore‐forming solution. According to basic skarn mineralogy, the economic metals, and the origin of the ore‐forming fluids, the Dongzhongla deposit was classified as a skarn‐type Pb–Zn deposit.     

Regional patterns in the paragenesis and age of inclusions in diamond, diamond composition, and the lithospheric seismic structure of Southern Africa

The Archean lithospheric mantle beneath the Kaapvaal–Zimbabwe craton of Southern Africa shows ±1% variations in seismic P-wave velocity at depths within the diamond stability field (150–250 km) that correlate regionally with differences in the composition of diamonds and their syngenetic inclusions. Seismically slower mantle trends from the mantle below Swaziland to that below southeastern Botswana, roughly following the surface outcrop pattern of the Bushveld-Molopo Farms Complex. Seismically slower mantle also is evident under the southwestern side of the Zimbabwe craton below crust metamorphosed around 2 Ga. Individual eclogitic sulfide inclusions in diamonds from the Kimberley area kimberlites, Koffiefontein, Orapa, and Jwaneng have Re–Os isotopic ages that range from circa 2.9 Ga to the Proterozoic and show little correspondence with these lithospheric variations. However, silicate inclusions in diamonds and their host diamond compositions for the above kimberlites, Finsch, Jagersfontein, Roberts Victor, Premier, Venetia, and Letlhakane do show some regional relationship to the seismic velocity of the lithosphere. Mantle lithosphere with slower P-wave velocity correlates with a greater proportion of eclogitic versus peridotitic silicate inclusions in diamond, a greater incidence of younger Sm–Nd ages of silicate inclusions, a greater proportion of diamonds with lighter C isotopic composition, and a lower percentage of low-N diamonds whereas the converse is true for diamonds from higher velocity mantle. The oldest formation ages of diamonds indicate that the mantle keels which became continental nuclei were created by middle Archean (3.2–3.3 Ga) mantle depletion events with high degrees of melting and early harzburgite formation. The predominance of sulfide inclusions that are eclogitic in the 2.9 Ga age population links late Archean (2.9 Ga) subduction-accretion events involving an oceanic lithosphere component to craton stabilization. These events resulted in a widely distributed younger Archean generation of eclogitic diamonds in the lithospheric mantle. Subsequent Proterozoic tectonic and magmatic events altered the composition of the continental lithosphere and added new lherzolitic and eclogitic diamonds to the already extensive Archean diamond suite.     

Evidence for large scale fractionation of carbon isotopes and of nitrogen impurity during crystallization of gem quality cubic diamonds from placers of North Yakutia

The spatial distribution of carbon and nitrogen isotopes and of nitrogen concentrations is studied in detail in three gem quality cubic diamonds of variety II according to Orlov’s classification. Combined with the data on composition of fluid inclusions our results point to the crystallization of the diamonds from a presumably oxidized carbonate fluid. It is shown that in the growth direction δ¹³C of the diamond becomes systematically lighter by 2–3‰ (from –13.7 to –15.6‰ for one profile and from –11.7 to –14.1‰ for a second profile). Simultaneously, we observe substantial decrease in the nitrogen concentration (from 400–1000 to 10–30 at ppm) and a previously unrecognized enrichment of nitrogen in light isotope, exceeding 30‰. The systematic and substantial changes of the chemical and isotopic composition can be explained using the Burton-Prim-Slichter model, which relates partition coefficients of an impurity with the crystal growth rate. It is shown that changes in effective partition coefficients due to a gradual decrease in crystal growth rate describes fairly well the observed scale of the chemical and isotopic variations if the diamond-fluid partition coefficient for nitrogen is significantly smaller than unity. This model shows that nitrogen isotopic composition in diamond may result from isotopic fractionation during growth and not reflect isotopic composition of the mantle fluid. Furthermore, it is shown that the infra-red absorption at 1332 сm^-1 is an integral part of the Y-defect spectrum. In the studied natural diamonds the 1290 сm^-1 IR absorption band does not correlate with boron concentration.     

Diamonds from the Buffalo Head Hills,Alberta: Formation in a non-conventional setting

Kimberlite pipes K11, K91 and K252 in the Buffalo Head Hills, northern Alberta show an unusually large abundance (20%) of Type II (no detectable nitrogen) diamonds. Type I diamonds range in nitrogen content from 6 ppm to 3300 ppm and in aggregation states from low (IaA) to complete (IaB). The Type IaB diamonds extend to the lowest nitrogen concentrations yet observed at such high aggregation states, implying that mantle residence occurred at temperatures well above normal lithospheric conditions. Syngenetic mineral inclusions indicate lherzolitic, harzburgitic, wehrlitic and eclogitic sources. Pyropic garnet and forsteritic olivine characterize the peridotitic paragenesis from these pipes. One lherzolitic garnet inclusion has a moderately majoritic composition indicating a formation depth of ∼ 400 km. A wehrlitic paragenesis is documented by a Ca-rich, high-chromium garnet and very CaO-rich (0.11–0.14 wt.%) olivine. Omphacitic pyroxene and almandine-rich garnet are characteristic of the eclogitic paragenesis. A bimodal δ¹³C distribution with peaks at − 5‰ and − 17‰ is observed for diamonds from all three kimberlite pipes. A large proportion (∼ 40%) of isotopically light diamonds (δ¹³C < −10‰) indicates a predominantly eclogitic paragenesis.The Buffalo Head Terrane is of Lower Proterozoic metamorphic age (2.3–2.0 Ga) and hence an unconventional setting for diamond exploration. Buffalo Hills diamonds formed during multiple events in an atypical mantle setting. The presence of majorite and abundance of Type II and Type IaB diamonds suggests formation under sublithospheric conditions, possibly in a subducting slab and resulting megalith. Type IaA to IaAB diamonds indicate formation and storage under lower temperature in normal lithospheric conditions.