Genetic relations among basic lavas and ultramafic nodules: Evidence from oxygen isotope compositions

¹⁸O values of unaltered basic lavas range from 4.9 to 8.3 but different types of basalts are usually restricted to narrow and distinct ranges of isotopic composition. The average ¹⁸O values for Hawaiian tholeiites, mid-ocean ridge tholeiites, and alkali basalts are 5.4, 5.7, and 6.2 permil, respectively. Potassic lavas and andesites tend to be more ¹⁸O rich with ¹⁸O values between 6.0 and 8.0 permil. The differences among the oxygen isotopic compositions of most of these lavas can be attributed to partial melting of isotopically distinct sources. The oxygen isotope compositions of the sources may be a function of prior melting events which produce ¹⁸O-depleted partial melts and ¹⁸O-enriched residues as a consequence of relatively large isotopic fractionations that exist at high temperatures. It is proposed that lavas with relatively low ¹⁸O values are derived from primitive, ¹⁸O-depleted sources whereas ¹⁸O-rich basalts are produced from refractory sources that have already produced partial melts. High temperature fractionations among silicate liquids and coexisting minerals can be used in conjunction with the oxygen isotope compositions of ultramafic nodules to place constraints on the genetic relations between some nodules and different types of basic lavas.     

Oxygen isotope thermometry using quartz inclusions in garnet

Oxygen isotope ratios of quartz inclusions (QI) within garnet from granulite and amphibolite facies gneisses in the Adirondack Mountains, NY were analysed and used to determine metamorphic temperatures. Primary QI for eight of 12 samples have δ¹⁸O values significantly lower than matrix quartz (MQ). The primary QI retain δ¹⁸O values representative of thermal conditions during garnet crystallization, whereas the δ¹⁸O values of MQ were raised by diffusive exchange with other matrix minerals (e.g. mica and feldspar) during cooling. The δ¹⁸O differences between QI and MQ show that garnet (a mineral with slow diffusion of oxygen) can armour QI from isotopic exchange with surrounding matrix, even during slow cooling. These differences between δ¹⁸O in MQ and QI can further be used to test cooling rates by Fast Grain Boundary diffusion modelling. Criteria for identifying QI that preserve primary compositions and are suitable for thermometry were developed based on comparative tests. Relations between δ¹⁸O and inclusion size, distance of inclusion to host–garnet rim, core–rim zonation of individual inclusions, and presence or absence of petrological features (healed cracks in QI, inclusions in contact with garnet cracks lined by secondary minerals, and secondary minerals along the inclusion grain boundary) were investigated. In this study, 61% of QI preserve primary δ¹⁸O and 39% were associated with features that were linked to reset δ¹⁸O values. If δ¹⁸O in garnet is homogeneous and inclusions are removed, laser‐fluorination δ¹⁸O values of bulk garnet are more precise, more accurate, and best for thermometry. Intragrain δ¹⁸O(Grt) profiles measured in situ by ion microprobe show no δ¹⁸O zonation. Almandine–rich garnet (Alm_60–75) from each sample was measured by laser‐fluorination mass‐spectrometry (LF‐MS) for δ¹⁸O and compared with ion microprobe measurements of δ¹⁸O in QI for thermometry. The Δ¹⁸O(Qz–Grt) values for Adirondack samples range from 2.66 to 3.24‰, corresponding to temperatures of 640–740 °C (A[Qz–Alm] = 2.71). Out of 12 samples that were used for thermometry, nine are consistent with previous estimates of peak temperature (625–800 °C) based on petrological and carbon–isotope thermometry for regional granulite and upper amphibolite facies metamorphism. The three samples that disagree with independent thermometry for peak metamorphism are from the anorthosite–mangerite–charnockite–granite suite in the central Adirondacks and yield temperatures of 640–665 °C, ~100 °C lower than previous estimates. These low temperatures could be interpreted as thermal conditions during late (post‐peak) crystallization of garnet on the retrograde path.     

Oxygen isotope thermometry in carbonatites, Fuerteventura, Canary Islands, Spain

Summary Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960°C (average 710°C). The highest temperature is obtained from pyroxene–calcite pairs. The above range is in agreement with other carbonatite thermometric studies.This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite–carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar–Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite–carbonatite magmas.     

Elemental and Sr isotope variations in basic lavas from Iceland and the surrounding ocean floor

Major and trace element data are used to establish the nature and extent of spatial and temporal chemical variations in basalts erupted in the Iceland region of the North Atlantic Ocean. The ocean floor samples are those recovered by legs 38 and 49 of the Deep Sea Drilling Project. Within each of the active zones on Iceland there are small scale variations in the light rare earth elements and ratios such as K/Y: several central complexes and their associated fissure swarms erupt basalts with values of K/Y distinct from those erupted at adjacent centres; also basalts showing a wide range of immobile trace element ratios occur together within single vertical sections and ocean floor drill holes. Although such variations can be explained in terms of the magmatic processes operating on Iceland they make extrapolations from single basalt samples to mantle sources underlying the outcrop of the sample highly tenuous. ⁸⁷Sr/86Sr ratios measured for 25 of the samples indicate a total range from 0.7028 in a tholeiite from the Reykjanes Ridge to 0.7034 in an alkali basalt from Iceland and are consistent with other published ratios from the region. A positive correlation between ⁸⁷Sr/⁸⁶Sr and Ce/Yb ratios indicates the existence of systematic isotopic and elemental variations in the mantle source region. An approximately fivefold variation in Ce/Yb ratio observed in basalts with the same ⁸⁷Sr/⁸⁶Sr ratio implies that different degrees and types of partial melting have been involved in magma genesis from a single mantle composition. ⁸⁷Sr/⁸⁶Sr ratios above 0.7028, Th/U ratios close to 4 and La/Ta ratios close to 10 distinguish most basalts erupted in this part of the North Atlantic Ocean from normal mid-ocean ridge basalt (N-type MORE) — although N-type MORB has been erupted at extinct spreading axes just to the north and northeast of Iceland as well as the presently active Iceland-Jan Mayen Ridge.Comparisons with the hygromagmatophile element and radiogenic isotope ratios of MORB and the estimated primordial mantle indicate that the mantle sources producing Iceland basalts have undergone previous depletion followed by more recent enrichment events. A veined mantle source region is proposed in preference to the mantle plume model to explain the chemical variations.     

Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of '¹⁸O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger (~1‰) variability of '¹⁸O(quartz). The youngest domes of Glass Mountain are similar to BT in '¹⁸O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The '¹⁸O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant '¹⁸O(melt)=7.8ǂ.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of '¹⁸O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of '¹⁸O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal '¹⁸O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale '¹⁸O homogeneity of BT and other large magma chambers as evidence of their longevity (>10⁵ years) and convection. However, remaining isotopic zoning in some quartz phenocrysts, trace element gradients in feldspars, and quartz and zircon crystal size distributions are more consistent with far shorter timescales (10²-10⁴ years). We propose a sidewall-crystallization model that promotes convective homogenization, roofward accumulation of more evolved and stagnant, volatile-rich liquid, and develops compositional and temperature gradients in pre-climactic magma chamber. Crystal + melt + gas bubbles mush near chamber walls of variable '¹⁸O gets periodically remobilized in response to chamber refill by new hotter magmas. One such episode of chamber refill by high-Ti, Sr, Ba, Zr, and volatile-richer magma happened 10³-10⁴ years prior to the 0.76-Ma caldera collapse that caused magma mixing at the base, mush thawing near the roof and walls, and downward settling of phenocrysts into this hybrid melt.     

Relative contributions of crust and mantle to the generation of the Tianshan Carboniferous rift-related basic lavas, northwestern China

The Tianshan Carboniferous–Permian rift-related volcanism in northwestern China represents a newly recognized large igneous province extending over at least 1.5 × 10⁶ km². The volcanic successions comprise thick piles of basaltic lavas and subordinate intermediate and silicic lavas and pyroclastics, and are interpreted to result from a mantle plume head with component of ε_Nd(t) ≈ +5, ⁸⁷Sr/⁸⁶Sr(t) ≈ 0.704 and La/Nb ≈ 0.9. On the basis of petrogeochemical data, the Carboniferous basic lavas can be generally incorporated into low-Ti/Y (LT, Ti/Y < 500) magma type that can be further divided into three subtypes: LT1, LT2 and LT3. The chemical evolution of the LT1, LT2 (in central Tianshan) and LT3 (in western Tianshan and Jungar) lavas is controlled by an olivine (ol) + clinopyroxene (cpx) fractionation, but gabbroic fractionation accounts for the chemical variation of the LT3 lavas from eastern Tianshan. Elemental and isotopic data suggest that the chemical variation of Tianshan Carboniferous basic lavas cannot be explained by crystallization from a common parental magma.The Sr–Nd isotopic variation of the crustally contaminated LT3 lavas is related to the nature of lithosphere through which the plume-derived melts have erupted. The involvement of an older (Precambrian) lithosphere led the LT3 lavas in western Tianshan to have lower to negative ε_Nd(t) (−1.2 to +6.1) and variable ⁸⁷Sr/⁸⁶Sr(t) (0.7036–0.7061), whereas the LT3 lavas from eastern Tianshan and Jungar are characterized by high ε_Nd(t) (+4.2 to +9.7) and low ⁸⁷Sr/⁸⁶Sr(t) (0.7035–0.7044), that are related to the contamination of upper crust containing early Paleozoic and Devonian arc-basin volcanic rocks and/or to a pre-Carboniferous subduction enrichment of the lithospheric mantle source region. The observed geochemical variations in the Tianshan data are consistent with an AFC process.The Tianshan Carboniferous rift-related volcanic rocks display a spatial petrogeochemical variation in which predominantly uncontaminated LT1 and less-contaminated LT2 tholeiitic lavas erupted in central Tianshan rift and predominantly the strongly contaminated LT3 tholeiites erupted in the circumjacent regions of the central Tianshan rift. The LT1 and LT2 lavas were generated by a higher degree (10–30%) of partial melting in the garnet stability field of the mantle plume compared to the LT3 lavas. The lower degree (<10%) of partial melting in the spinel–garnet transition zone of the mantle plume, as is characteristic of the LT3 lavas, may be the result of a relatively lower geotherm.     

Paleoclimate reconstruction using carbonate clumped isotope thermometry

Carbonate clumped isotope thermometry is a relatively new paleotemperature proxy based on measurements of the degree of ordering of ¹³C and ¹⁸O into bonds with each other (making the ¹³C¹⁸O¹⁶O₂^?2 ion group) in lattices of carbonate minerals. This technique has several unusual properties that complement existing methods of paleoclimate reconstruction. Most importantly, it is based on a homogeneous isotope exchange equilibrium and thus constrains temperature independent of the isotopic composition of waters from which carbonates grew. This method also appears to be generally insensitive to ‘vital effects’ that compromise many other paleothermometers based on the chemical properties of biominerals or organic matter, at least for those organisms that have been subjected to systematic study to-date (corals and foraminifera); however, discrepancies among some calibrations, particularly at low temperatures, may point toward the existence of vital effects in mollusks and other organisms. This review discusses the principles and calibrations of the technique, its uses in combination with conventional stable isotope measurements to constrain the δ¹⁸O of past waters, preservation of paleotemperatures in ancient materials, as well as current problems in our understanding of calibrations and interlaboratory data comparisons.     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: insights from olivine phenocrysts

A relatively narrow range of oxygen isotopic ratios (?? ¹⁸O?=?5.0?C5.4??) is preserved in olivine of mantle xenoliths, mid-ocean ridge (MORB), and most ocean island basalts (OIB). The values in excess of this range are generally attributed either to the presence of a recycled component in the Earth??s mantle or to shallow level contamination processes. A viable way forward to trace source heterogeneity is to find a link between chemical (elemental and isotopic) composition of the earlier crystallized mineral phases (olivine) and the composition of their parental magmas, then using them to reconstruct the composition of source region. The Canary hotspot is one of a few that contains ~1- to 2-Ga-old recycled ocean crust that can be traced to the core-mantle boundary using seismic tomography and whose origin is attributed to the mixing of at least three main isotopically distinct mantle components i.e. HIMU, DMM, and EM. This work reports ion microprobe and single crystal laser fluorination oxygen isotope data of 148 olivine grains also analyzed for major and minor elements in the same spot. The olivines are from 20 samples resembling the most primitive shield stage picrite through alkali basalt to basanite series erupted on Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro, Canary Islands, for which shallow level contamination processes were not recognized. A broad range of ?? ¹⁸O_olivine values from 4.6 to 6.1?? was obtained and explained by stable, long-term oxygen isotope heterogeneity of crystal cumulates present under different volcanoes. These cumulates are thought to have crystallized from mantle-derived magmas uncontaminated at crustal depth, representing oxygen isotope heterogeneity of source region. A relationship between Ni?×?FeO/MgO and ?? ¹⁸O_olivine values found in one basanitic lava erupted on El Hierro, the westernmost island of the Canary Archipelago, was used to estimate oxygen isotope compositions of partial melts presumably originated from peridotite (HIMU-type component inherited its radiogenic isotope composition from ancient, ~1 to 2?Ga, recycled ocean crust) and pyroxenite (young, <1?Ga, recycled oceanic crust preserved as eclogite with depleted MORB-type isotopic signature) components of the Canary plume. The model calculations yield 5.2 and 5.9?±?0.3?? for peridotite- and pyroxenite-derived melts, respectively, which appeared to correspond closely to the worldwide HIMU-type OIB and upper limit N-MORB ?? ¹⁸O values. This difference together with the broad range of ?? ¹⁸O variations found in the Canarian olivines cannot be explained by thermodynamic effects of oxygen isotopic fractionation and are believed to represent true variations in the mantle, due to oceanic crust and continental lithosphere recycling.     

Himalayan inverted metamorphism constrained by oxygen isotope thermometry

Inverted metamorphic field gradients are preserved in two amphibolite facies metapelitic sequences forming the crystalline core zone of the Himalayan orogen in the Sutlej valley (NW India). In the High Himalayan Crystalline Sequence (HHCS), metamorphic conditions increase upwards from the staurolite zone at the base, through the kyanite-in and sillimanite-in isograds, finally to reach partial melting conditions at the top. The structurally lower Lesser Himalayan Crystalline Sequence (LHCS) shows a gradual superposition of garnet-in, staurolite-in and kyanite + sillimanite-in isograds. Although phase equilibria constraints imply inverted temperature field gradients in both units, garnet-biotite (GARB) rim thermometry indicates final equilibration at a nearly uniform temperature around T ≈ 600 °C across these sequences. The P-T path and garnet zoning data show that this apparent lack of thermal field gradient is mainly the consequence of a resetting of the GARB equilibria during cooling. In order to constrain peak temperature conditions, 20 samples along the studied section have been analysed for oxygen isotope thermometry. The isotopic fractionations recorded by quartz-garnet and quartz-aluminosilicate mineral pairs indicate temperatures consistent with phase equilibria and P-T path constraints for metamorphic peak conditions. Together with barometry results, based on net transfer continuous reactions, the oxygen isotope thermometry indicates peak conditions characterized by: (1) a temperature increase from T ≈ 570 to 750 °C at a nearly constant pressure around P ≈ 800 MPa, from the base to the top of the HHCS unit; (2) a temperature increase from T ≈ 610 to 700 °C and a pressure decrease from P ≈ 900 to 700 MPa, from the base to the top of the LHCS metapelites. Oxygen isotope thermometry thus provides the first quantitative data demonstrating that the Himalayan inverted metamorphism can be associated with a complete inversion of the thermal field gradient across the crystalline core zone of this orogen. Received: 1 April 1999 / Accepted: 12 July 1999     

Oxygen isotope composition of phenocrysts from Tristan da Cunha and Gough Island lavas: variation with fractional crystallization and evidence for assimilation

We have measured the δ¹⁸O values of the major phenocrysts (olivine, clinopyroxene and plagioclase) present in lavas from Tristan da Cunha and Gough Island. These islands, which result from the same mantle plume, have enriched radiogenic isotope ratios and are, therefore, prime candidates for an oxygen isotope signature that is distinct from that of MORB. Consistent differences between the δ¹⁸O values of olivine, pyroxene and feldspar in the Gough lavas show that the phenocrysts in the mafic Gough Island lavas are in oxygen isotope equilibrium. The olivines in lavas with SiO₂ <50 wt% have a mean δ¹⁸O value of 5.19‰, consistent with crystallization from a magma having the same oxygen isotope composition as MORB. Phenocrysts in all the Gough lavas show a systematic increase in δ¹⁸O value as silica content increases, which is consistent with closed-system fractional crystallization. The lack of enrichment in δ¹⁸O of the Gough magmas suggests that the mantle source contained <2% recycled sediment. In contrast, the Tristan lavas with SiO₂ >48 wt% contain phenocrysts which have δ¹⁸O values that are systematically ∼0.3‰ lower than their counterparts from Gough. We suggest that the parental mafic Tristan magmas were contaminated by material from the volcanic edifice that acquired low δ¹⁸O values by interaction with water at high temperatures. The highly porphyritic SiO₂-poor lavas show a negative correlation between olivine δ¹⁸O value and whole-rock silica content rather than the expected positive correlation. The minimum δ¹⁸O value occurs at an SiO₂ content of about 45 wt%. Below 45 wt% SiO₂, magmas evolved via a combination of assimilation, fractionational crystallization and crystal accumulation; above 45 wt% SiO₂, magmas appeared to have evolved via closed-system fractional crystallization. Received: 23 November 1998 / Accepted: 27 September 1999     

Oxygen isotope cosmothermometer revisited

A previously published estimate of the oxygen isotopic composition of the gas of the early solar nebula must be revised in light of the discovery of non-chemical isotope effects in carbonaceous chondrites. The solids which accreted to form the Earth, Moon and ordinary chondrites probably did not equilibrate isotopically with the gas below 1000 K.     

Oxygen isotope evidence for subduction and rift-related mantle metasomatism beneath the Colorado Plateau–Rio Grande rift transition

Spinel lherzolite and pyroxenite xenoliths from the Rio Puerco Volcanic Field, New Mexico, were analyzed for oxygen isotope ratios by laser fluorination. In lherzolites, olivine δ¹⁸O values are high (+5.5‰), whereas δ¹⁸O values for pyroxenes are low (cpx=+5.1‰; opx=+5.4‰) compared to average mantle values. Pyroxenite δ¹⁸O values (cpx=+5.0‰; opx=+5.3‰) are similar to those of the lherzolites and are also lower than typical mantle oxygen isotope compositions. Texturally and chemically primary calcite in pyroxenite xenoliths is far from isotopic equilibrium with other phases, with δ¹⁸O values of +21‰. The isotopic characteristics of the pyroxenite xenoliths are consistent with a petrogenetic origin from mixing of lherzolitic mantle with slab-derived silicate and carbonatite melts. The anomalously low δ¹⁸O in the pyroxenes reflects metasomatism by a silicate melt from subducted altered oceanic crust, and high δ¹⁸O calcite is interpreted to have crystallized from a high δ¹⁸O carbonatitic melt derived from subducted ophicarbonate. Similar isotopic signatures of metasomatism are seen throughout the Rio Puerco xenolith suite and at Kilbourne Hole in the southern Rio Grande rift. The discrete metasomatic components likely originated from the subducted Farallon slab but were not mobilized until heating associated with Rio Grande rifting occurred. Oxygen diffusion modeling requires that metasomatism leading to the isotopic disequilibrium between calcite and pyroxene in the pyroxenites occurred immediately prior to entrainment. Melt infiltration into spinel-facies mantle (xenoliths) prior to eruption was thus likely connected to garnet-facies melting that resulted in eruption of the host alkali basalt.     

Ultra-high temperatures from oxygen isotope thermometry of a coesite-sanidine grospydite

The oxygen isotope compositions of coesite, sanidine, kyanite, clinopyroxene and garnet were measured in an ultra-high pressure-temperature grospydite from the Roberts Victor kimberlite, South Africa. The ¹⁸O values (per mil v. SMOW) of each phase and (1 ) are as follows: coesite, 8.62 (0.31); sanidine, 8.31 (0.02); kyanite, 7.98 (0.08); pyroxene, 7.63 (0.11); garnet, 7.53 (0.03). In situ analyses of the coesite with the laser extraction system are ¹⁸O=9.35 (0.08), n=4, demonstrating that the coesite is homogeneous. The coesite has partially inverted to polycrystalline quartz and the pyroxene is extensively altered during uplift. The larger scatter for the mineral separate coesite and pyroxene data may be due to partial reequilibration between the decompression-related breakdown products of these two phases. The anomalously high ¹⁸O value of the grospydite (¹⁸O_wholerock=7.7) is consistent with altered oceanic crust as a source rock. Temperature estimates from a linear regression of all the data to three different published calibrations correspond to an equilibrium temperature of 1310±80°C. The calculated isotopic pressure effect is to lower these estimates by about 40°C at 40 kb. The estimated temperature based on Al–Si disorder in sanidine is 1200±100°C and that from Fe–Mg exchange thermometry between garnet and clinopyroxene is 1100±50°C. Given the large errors associated with thermometry at such high temperatures, it is concluded that the xenolith equilibrated that 1200±100°C. Pressure estimates are 45±5 kb, based on dilution of the univariant equilibria albite = jadeite + coesite and 2 kyanite + 3 diopside = grossular + pyrope + 2coesite. Zoning in the outer 20 m of the feldspar from Ab_0.8 to Ab₁₆ indicates rapid decompression to 25 kb or less. The isotopic temperature estimates are the highest ever obtained and combined with the high degree of Al–Si disorder in sanidine require rapid cooling from ultra-high temperatures. It is inferred that the xenolith was sampled at the time of equilibration, providing a point on the upper Cretaceous geotherm in the mantle below South Africa.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

Oxygen isotope heterogeneity of the mantle deduced from global 18O systematics of basalts from different geotectonic settings

Based upon a compilation and analysis of O-isotope data for Neogene volcanic rocks worldwide, the ¹⁸O variation for 743 basalts (historic lavas, submarine glasses, and lavas with <0.75 wt% H₂O) is +2.9 to +11.4. Mid-ocean-ridge basalt (MORB) has a uniform O-isotope composition with ¹⁸0=+5.7±0.2. Basalts erupted in different tectonic settings have mean ¹⁸O/¹⁶O ratios that are both lower and higher than MORB, with continental basalts enriched in ¹⁸O by ca. 1 over oceanic basalts. The ¹⁸O range for the subset of 88 basalts with Mg# [100·Mg(Mg+Fe²⁺)] 75–68, considered to be unmodified primary mantle partial melts, is +3.6 to +8.7. These features are a clear indication that: (1) the Earth's upper mantle is heterogeneous with respect to its O-isotope composition; (2) that both low-¹⁸O and high-¹⁸O reservoirs have contributed to basalt petrogenesis. Large-ion lithophile element-enriched basalts associated with subduction at convergent plate margins are slightly enriched in ¹⁸O, a characteristic that is considered to be an intrinsic feature of the subduction process. Intraplate oceanic and continental basalts have highly variable ¹⁸O/¹⁶O ratios, with individual localities displaying ¹⁸O ranges in excess of 1.5 to 2. Systematic co-variations between O-, Sr-, Nd-, and Pb-isotope ratios reflect the same principal intramantle end-member isotopic components (DMM, HIMU, EM-I, EM-II) deduced from radiogenic isotope considerations and, therefore, imply that a common process is responsible for the origin of upper mantle stable and radiogenic isotope heterogeneity, namely the recycling of lithospheric material into the mantle.     

安徽女山橄榄岩包体的氧同位素比值和微量元素组成：地幔交代作用

1本文的研究对象是9个来自安徽女山新生代玄武岩的橄榄岩包体,利用激光氟化技术系统分析了橄榄石、单斜辉石和斜方辉石的氧同位素比值;利用LA-ICPMS技术分析了单斜辉石的微量元素组成,结果显示,女山橄榄岩存在辉石与橄榄石之间的氧同位素不平衡分馏现象,其中△Cpx-O1^18O（=δ^18OCpx-δ^18OO1））出现低至-0．5‰的负值;合角闪石包体中的单斜辉石明显富集大离子亲石元素（LILE,如Sr、Th、LREE）和亏损高场强元素（HFSE,如Nb、Zr、Ti）,氧同位素的数据表明,女山上地幔曾经经历过俯冲洋壳流体参与的交代作用,根据单斜辉石和橄榄石之间氧同位素分馏值△Cpx-O1^18O与包体形成深度之间的负相关性,提出了一个“上升＋缓冲”的流体交代模型,虽然微量元素特征也表明女山上地慢受到过地壳流体的影响,但是氧同位素的不平衡分馏和LILE的富集／HFSE的亏损并不是同步的,对这种现象的可能解释是：引起氧同位素不平衡分馏的交代作用和造成女山单斜辉石微量元素特征的交代作用不是同一期的,即女山上地幔曾经发生过至少2次交代事件.     

Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration

We measure the clumped isotopic signature of carbonatites to assess the integrity of the clumped isotope paleothermometer over long timescales (10⁷-10⁹ years) and the susceptibility of the proxy to closed system re-equilibration of isotopes during burial diagenesis. We find pristine carbonatites that have primary oxygen isotope signatures, along with a Carrara marble standard, do not record clumped isotope signatures lighter than 0.31‰ suggesting atoms of carbon and oxygen freely exchange within the carbonate lattice at temperatures above 250-300 °C. There is no systematic trend in the clumped isotope signature of pristine carbonatites with age, although partial re-equilibration to lower temperatures can occur if a carbonatite has been exposed to burial temperatures for long periods of time. We conclude that the solid-state re-ordering of carbon and oxygen atoms is sufficiently slow to enable the use of clumped isotope paleothermometry on timescales of 10⁸ years, but that diagenetic resetting can still occur, even without bulk recrystallization. In addition to the carbonatite data, an inorganic calibration of the clumped isotope paleothermometer for low temperature carbonates (7.5-77 °C) is presented and highlights the need for further inter-lab standardization.     

The Ethiopian subcontinental mantle domains: geochemical evidence from Cenozoic mafic lavas

Summary Since the Cenozoic, Ethiopia was affected by a widespread volcanic activity related to the geodynamic evolution of the Afar triple junction. The plateau building phase was followed by the formation of the Main Ethiopian Rift (MER) accompanied by a bimodal volcanic activity in both the inner parts of the rift and its shoulders. Outside the rift, a concurrent volcanic activity occurred mainly along transversal tectonic lineaments, the most important of which is the Yerer-Tullu Wellel Volcano-Tectonic Lineament (YTVL) developing for ∼500 km westward of Addis Abeba. Scattered Pliocene – Quaternary volcanoes are reported also inside the plateau such as those out cropping nearby Lake Tana. Here we present the result of a study on carefully screened mafic lavas outcropping in two sectors located off-axis the MER, namely, the YTVL and the southern part of Lake Tana; and in one sector located in the southern tip of the MER close to Megado, in the Sidamo region. The screened samples are petrographically fresh and have SiO₂<52 wt.% and MgO>4 wt.%, to minimise crystal fractionation effects. Most of the samples belong to the Late Miocene – Quaternary volcanic activity of the East African Rift System (EARS), although a number of samples along the YTVL are representative of the Late Eocene – Early Miocene Ethiopian Volcanic Plateau flood basalts. The selected mafic lavas offer the opportunity to assess the geochemical diversity, if any, of the subcontinental mantle domains along the MER (Megado and the easternmost part of the YTVL) and in sectors far away from the MER (YTVL and Lake Tana). The samples have a wide compositional range: from basanite to alkali basalt, hy-normative basalt, qz-normative basalt, basaltic andesite, hawaiite, trachybasalt, and trachyandesite. The major and trace element characteristics of the mafic lavas demonstrate an origin from a relatively fertile and trace element enriched lithospheric mantle at pressure variable from ∼2.0 to 3.5 GPa. Moreover, systematic variations in K/Nb, Ba/Nb, and Ba/Rb demand for the contribution of trace amounts of phlogopite to melt production. The geochemical signature coupled with the geographical distribution of the Late Miocene – Quaternary samples along the YTVL (∼500 km) and the Lake Tana and Megado sectors set constraints on a relatively homogenous lateral continuity of the deeper lithospheric mantle domains (∼2–3.5 GPa). On the other hand, the trace element characteristics of the Ethiopian Volcanic Plateau samples along the YTVL, demand for a chromatographic process en route to the surface and indicate a shallower lithospheric mantle domain (<2 GPa) with a different geochemical signature. Overall, the selected mafic lavas provide evidence for vertically zoned lithospheric mantle domains: the shallower domain (<2 GPa) consists of an enriched mantle component with a geochemical signature similar to continental crust material (EM II), whilst the deeper domain (∼2–3.5 GPa) consists of an enriched component similar to the average composition of the subcontinental lithospheric mantle (SCLM). Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material