Oxygen isotopic compositions of chondrules: Implications for evolution of oxygen isotopic reservoirs in the inner solar nebula

We review the oxygen isotopic compositions of minerals in chondrules and compound objects composed of a chondrule and a refractory inclusion, and bulk oxygen isotopic compositions of chondrules in unequilibrated ordinary, carbonaceous, enstatite, and Kakangari-like chondrites, focusing on data acquired using secondary ion mass-spectrometry and laser fluorination coupled with mass-spectrometry over the last decade. Most ferromagnesian chondrules from primitive (unmetamorphosed) chondrites are isotopically uniform (within 3–4‰ in Δ¹⁷O) and depleted in ¹⁶O (Δ¹⁷O>−7‰) relative to amoeboid olivine aggregates (AOAs) and most calcium–aluminum-rich inclusions (CAIs) (Δ¹⁷O<−20‰), suggesting that these classes of objects formed in isotopically distinct gaseous reservoirs, ¹⁶O-poor and ¹⁶O-rich, respectively. Chondrules uniformly enriched in ¹⁶O (Δ¹⁷O<−15‰) are exceptionally rare and have been reported only in CH chondrites. Oxygen isotopic heterogeneity in chondrules is mainly due to the presence of relict grains. These appear to consist of chondrules of earlier generations and rare refractory inclusions; with rare exceptions, the relict grains are ¹⁶O-enriched relative to chondrule phenocrysts and mesostasis. Within a chondrite group, the magnesium-rich (Type I) chondrules tend to be ¹⁶O-enriched relative to the ferrous (Type II) chondrules. Aluminum-rich chondrules in ordinary, enstatite, CR, and CV chondrites are generally ¹⁶O-enriched relative to ferromagnesian chondrules. No systematic differences in oxygen isotopic compositions have been found among these chondrule types in CB chondrites. Aluminum-rich chondrules in carbonaceous chondrites often contain relict refractory inclusions. Aluminum-rich chondrules with relict CAIs have heterogeneous oxygen isotopic compositions (Δ¹⁷O ranges from −20‰ to 0‰). Aluminum-rich chondrules without relict CAIs are isotopically uniform and have oxygen isotopic compositions similar to, or approaching, those of ferromagnesian chondrules. Phenocrysts and mesostases of the CAI-bearing chondrules show no clear evidence for ¹⁶O-enrichment compared to the CAI-free chondrules. Spinel, hibonite, and forsterite of the relict refractory inclusions largely retained their original oxygen isotopic compositions. In contrast, plagioclase and melilite of the relict CAIs experienced melting and ¹⁶O-depletion to various degrees, probably due to isotopic exchange with an ¹⁶O-poor nebular gas. Several igneous CAIs experienced isotopic exchange with an ¹⁶O-poor nebular gas during late-stage remelting in the chondrule-forming region. On a three-isotope diagram, bulk oxygen isotopic compositions of most chondrules in ordinary, enstatite, and carbonaceous chondrites plot above, along, and below the terrestrial fractionation line, respectively. Bulk oxygen isotopic compositions of chondrules in altered and/or metamorphosed chondrites show evidence for mass-dependent fractionation, reflecting either interaction with a gaseous/fluid reservoir on parent asteroids or open-system thermal metamorphism. Bulk oxygen isotopic compositions of chondrules and oxygen isotopic compositions of individual minerals in chondrules and refractory inclusions from primitive chondrites plot along a common line of slope of 1, suggesting that only two major reservoirs (gas and solids) are needed to explain the observed variations. However, there is no requirement that each had a permanently fixed isotopic composition. The absolute (²⁰⁷Pb–²⁰⁶Pb) and relative (²⁷Al–²⁶Mg) chronologies of CAIs and chondrules and the differences in oxygen isotopic compositions of most chondrules (¹⁶O-poor) and most refractory inclusions (¹⁶O-rich) can be interpreted in terms of isotopic self-shielding during UV photolysis of CO in the initially ¹⁶O-rich (Δ¹⁷O−25‰) parent molecular cloud or protoplanetary disk. According to these models, the UV photolysis preferentially dissociates C¹⁷O and C¹⁸O in the parent molecular cloud and in the peripheral zones of the protoplanetary disk. If this process occurs in the stability field of water ice, the released atomic ¹⁷O and ¹⁸O are incorporated into water ice, while the residual CO gas becomes enriched in ¹⁶O. During the earliest stages of evolution of the protoplanetary disk, the inner solar nebula had a solar H₂O/CO ratio and was ¹⁶O-rich. During this time, AOAs and the ¹⁶O-rich CAIs and chondrules formed. Subsequently, the inner solar nebula became H₂O- and ¹⁶O-depleted, because ice-rich dust particles, which were depleted in ¹⁶O, agglomerated outside the snowline (5 AU), drifted rapidly towards the Sun and evaporated. During this time, which may have lasted for 3 Myr, most chondrules and the ¹⁶O-depleted igneous CAIs formed. We infer that most chondrules formed from isotopically heterogeneous, but ¹⁶O-depleted precursors, and experienced isotopic exchange with an ¹⁶O-poor nebular gas during melting. Although the relative roles of the chondrule precursor materials and gas–melt isotopic exchange in establishing oxygen isotopic compositions of chondrules have not been quantified yet, mineralogical, chemical, and isotopic evidence indicate that Type I chondrules may have formed in chemical and isotopic equilibrium with nebular gas of variable isotopic composition. Whether these variations were spatial or temporal are not known yet.     

The mineral isotope composition of two Precambrian carbonatite complexes from the Kola Alkaline Province – Alteration versus primary magmatic signatures

We investigated the isotope composition (O, C, Sr, Nd, Pb) in mineral separates of the two Precambrian carbonatite complexes Tiksheozero (1.98 Ga) and Siilinjärvi (2.61 Ga) from the Karelian–Kola region in order to obtain information on Precambrian mantle heterogeneity. All isotope systems yield a large range of variations. The combination of cathodoluminescence imaging with stable and radiogenic isotopes on the same samples and mineral separates indicates various processes that caused shifts in isotope systems. Primary isotope signatures are preserved in most calcites (O, C, Sr, Pb), apatites (O, Sr, Nd), amphiboles (O), magnetites (O), and whole rocks (Sr, Nd).

The primary igneous C and O isotope composition is different for both complexes (Tiksheozero: δ¹³C = − 5.0‰, δ¹⁸O = 6.9‰; Siilinjärvi: δ¹³C = − 3.7‰, δ¹⁸O = 7.4‰) but very uniform and requires homogenization of both carbon and oxygen in the carbonatite melt. The lowest Sr isotope ratios of our carbonates and apatites from the Archaean Siilinjärvi (0.70137) and the Palaeoproterozoic Tiksheozero (0.70228) complexes are in the range of bulk silicate earth (BSE). Positive ε_Nd values of the two carbonatites point to very early Archaean enrichment of Sm/Nd in the Fennoscandian mantle. No HIMU components could be detected in the two complexes, whereas Tiksheozero carbonatites give the first indication of Palaeoproterozoic U depletion for Fennoscandia.

Sub-solidus exchange processes with water during emplacement and cooling of carbonatites caused an increase in the oxygen isotope composition of some carbonates and probably also an increase of their ⁸⁷Sr/⁸⁶Sr ratio. A larger increase of initial Sr isotope ratios was found in carbonatized silicic rocks compared to carbonatite bodies. The Svecofennian metamorphic overprint (1.9–1.7 Ga) caused reset of Rb/Sr (mainly mica) and Pb/Pb (mainly apatite) isochron systems.     

Distribution of diagenetic alterations in fluvial and paralic deposits within sequence stratigraphic framework: Evidence from the Petrohan Terrigenous Group and the Svidol Formation, Lower Triassic, NW Bulgaria

Elucidation of diagenetic alterations in the Petrohan Terrigenous Group (fluvial; highstand systems tract HST) sandstones and Svidol Formation (tide-dominated deltaic and tidal flat, transgressive systems tract TST and highstand systems tract HST, respectively) sandstones and calcarenite, Lower Triassic, NW Bulgaria was constrained within a sequence stratigraphic framework. Eogenetic alterations in the fluvial HST sandstones include (i) formation of grain-coating infiltrated clays as a result of percolation of mud-rich surface waters into underlying coarse-grained and permeable channel-fills and crevasse splay sandstones; (ii) formation of pseudomatrix by mechanical compaction of mud intraclasts that were incorporated into the coarse-grained channel sandstones during their lateral avulsion; and (iii) cementation by calcite (δ¹⁸O_VPDB = − 6.5‰ to − 3‰; δ¹³C_VPDB = − 5.1‰ to + 0.6‰) and dolomite (δ¹⁸O_VPDB = − 6.1‰ to − 0.3‰; δ¹³C_VPDB = − 7.2‰ to − 5.8‰) in the crevasse splay and floodplain sediments. Mesogenetic alterations that are encountered in the fluvial HST sandstones include (i) illitization of grain-coating clays, mud intraclasts, and mica, possibly because of simultaneous albitization of feldspars; (ii) cementation by calcite (δ¹⁸O_VPDB = − 14.5‰ to − 8.4‰; δ¹³C_VPDB = − 7.7‰ to + 0.6‰) and dolomite (δ¹⁸O_VPDB = − 15.8‰ to − 5‰; δ¹³C_VPDB = − 7.9‰ to + 1.5‰); and (iii) limited amounts of quartz overgrowths in the channel sandstones owing to occurrence of thick grain-coating clays.

Conversely, the tide-dominated deltaic TST sandstones and the tidal flat HST calcarenite were pervasively cemented by calcite (δ¹⁸O_VPDB = − 6.6‰ to − 3.1‰; δ¹³C_VPDB = − 5.1‰ to + 0.6‰) and siderite (δ¹⁸O_VPDB = − 7.2‰ to − 5.7‰; δ¹³C_VPDB = + 0.3‰ to + 0.9‰) particularly below marine and maximum flooding surfaces, due to the presence of abundant bioclasts and prolonged residence time of the sediments under certain geochemical conditions along these surfaces. The remaining open pores were cemented during mesodiagenesis by calcite (δ¹⁸O_VPDB = − 6.6‰ to − 3.1‰ and δ¹³C_VPDB = − 5.1‰ to + 0.6‰) and dolomite (δ¹⁸O_VPDB = − 6.6‰ to − 3.1‰ and δ¹³C_VPDB = − 5.1‰ to + 0.6‰).

This study shows that constructing a conceptual model for the distribution of diagenetic alterations is possible by integration of diagenesis with sequence stratigraphy. The model shows that tide-dominated deltaic TST sandstones and tidal flat HST calcarenite were pervasively cemented by carbonates during near-surface eodiagenesis, owing to the presence of abundant bioclasts. Conversely, fluvial LST sandstones remained poorly cemented during near-surface eodiagenesis due to the lack of bioclasts, but were cemented by mesogenetic calcite, dolomite and quartz overgrowths instead.     

The geochemical cycle of boron: Constraints from boron isotope partitioning experiments between mica and fluid

The fractionation of boron isotopes between synthetic boromuscovite and fluid was experimentally determined at 3.0 GPa/500 °C and 3.0 GPa/700 °C. For near-neutral fluids Δ¹¹B_(mica-fluid) = δ¹¹B_(mica) − δ¹¹B_(fluid) is − 10.9 ± 1.3‰ at 500 °C, and − 6.5 ± 0.4‰ at 700 °C. This supports earlier assumptions that the main fractionation effect is due to the change from trigonal coordination of boron in neutral fluids to tetrahedrally coordinated boron in micas, clays and melts. The T-dependence of this effect is approximated by the equation Δ¹¹B_{(mica,clay,melt–neutral fluid)} = − 10.69 · (1000/T [K]) + 3.88; R² = 0.992, valid from 25 °C for fluid–clay up to about 1000 °C for fluid–silicate melt. Experiments at 0.4 GPa that used strongly basic fluids produced significantly lower fractionations with Δ¹¹B_{(mica–fluid)} of − 7.4 ± 1.0‰ at 400 °C, and − 4.8 ± 1.0‰ at 500 °C, showing the reduced fractionation effect when large amounts of boron in basic fluids are tetrahedrally coordinated. Field studies have shown that boron concentrations and ¹¹B/¹⁰B-ratios in volcanic arcs systematically decrease across the arc with increasing distance from the trench, thus reflecting the thermal structure of the subducting slab. Our experiments show that the boron isotopic signature in volcanic arcs probably results from continuous dehydration of micas along a distinct P–T range. Continuous slab dehydration and boron transport via fluid into the mantle wedge is responsible for the boron isotopic signature in volcanic arcs.     

Diagenetic mass transport in the southern San Joaquin basin, California, U.S.A.: Implications from the strontium isotopic composition of modern pore fluids

Three types of chemically and isotopically distinct pore fluids from the southern San Joaquin basin previously recognized by J.B. Fisher and J.R. Boles also have distinctive ⁸⁷Sr/⁸⁶Sr ratios and Sr concentrations. Meteoric fluids have stable isotopic compositions which lie on or near the meteoric water line and low chlorinities. Sr concentrations are between 0.01 and 2.6 mg l⁻¹, and ⁸⁷Sr/⁸⁶Sr ratios range from 0.7061 to 0.7078. Diagenetically modified connate marine fluids have δD-and δ¹⁸O-values more positive than −35‰ and 0‰, respectively, and have chlorinities generally comparable to seawater. Sr concentration are much higher than the meteoric group (16–198 mg l⁻¹), although the ⁸⁷Sr/⁸⁶Sr ratios (0.7070–0.7081) are not distinctive. Mixed meteoric-modified connate fluids have δD, δ¹⁸O and chlorinity intermediate between the meteoric and modified connate groups. Sr concentrations are also intermediate, between 16 and 22 mg l⁻¹, but ⁸⁷Sr/⁸⁶Sr ratios (0.7080–0.7087) are generally more radiogenic than either the meteoric or modified connate groups.

All of the fluids have ⁸⁷Sr/⁸⁶Sr ratios comparable to or lower than Tertiary seawater. Alteration of detrital plagioclase is the probable origin of the low isotopic ratios. Mass-balance calculations based on the Sr data suggest that essentially no transport of Sr occurred during diagenesis of sandstones containing modified connate pore fluids, while large amounts of Sr have been transported out of meteoric reservoirs by fluid flow. The chemically anomalous mixed meteoric-modified connate fluids contain the most radiogenic strontium in the basin. These fluids are spatially associated with major faults, and may represent clay mineral dehydration waters which have been transported upward from greater depth.

These results suggest that the three types of fluids identified by Fisher and Boles represent three distinct mass transport regimes: a largely stagnant deep-basin system containing modified connate pore fluids; an actively recharging meteoric system along the basin flanks; and a third system restricted to the southern basin which may be characterized by largescale cross-formational fluid flow, rather than dilution by meteoric waters.     

Isotopic composition of zinc, copper, and iron in lunar samples

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ⁶⁶Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ⁶⁵Cu  +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ⁵⁶Fe = −0.24‰, δ⁶⁵Cu = −0.42‰, and δ⁶⁶Zn  −3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰  δ⁵⁶Fe  0.51‰, 2.6‰  δ⁶⁵Cu  4.5‰, and 2.2‰  δ⁶⁶Zn  6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.     

Early Cretaceous gabbroic rocks from the Taihang Mountains: Implications for a paleosubduction-related lithospheric mantle beneath the central North China Craton

SHRIMP zircon U–Pb ages and geochemical and Sr–Nd–Pb isotopic data are presented for the gabbroic intrusive from the southern Taihang Mountains to characterize the nature of the Mesozoic lithospheric mantle beneath the central North China Craton (NCC). The gabbroic rocks emplaced at 125 Ma and are composed of plagioclase (40–50%), amphibole (20–30%), clinopyroxene (10–15%), olivine (5–10%) and biotite (5–7%). Olivines have high MgO (Fo = 78–85) and NiO content. Clinopyroxenes are high in MgO and CaO with the dominant ones having the formula of En_42–46Wo_41–50Fs_8–13. Plagioclases are dominantly andesine–labradorite (An = 46–78%) and have normal zonation from bytownite in the core to andesine in the rim. Amphiboles are mainly magnesio and actinolitic hornblende, distinct from those in the Precambrian high-pressure granulites of the NCC. These gabbroic rocks are characterized by high MgO (9.0–11.04%) and SiO₂ (52.66–55.52%), and low Al₂O₃, FeOt and TiO₂, and could be classified as high-mg basaltic andesites. They are enriched in LILEs and LREEs, depleted in HFSEs and HREEs, and exhibit (⁸⁷Sr/⁸⁶Sr)_i = 0.70492–0.70539, ε_Nd(t) = − 12.47–15.07, (²⁰⁶Pb/²⁰⁴Pb)_i = 16.63–17.10, Δ8/4 = 70.1–107.2 and Δ7/4 = − 2.1 to − 9.4, i.e., an EMI-like isotopic signatures. Such geochemical features indicate that these early Cretaceous gabbroic rocks were originated from a refractory pyroxenitic veined-plus-peridotite source previously modified by an SiO₂-rich melt that may have been derived from Paleoproterozoic subducted crustal materials. Late Mesozoic lithospheric extension might have induced the melting of the metasomatised lithospheric mantle in response to the upwelling of the asthenosphere to generate these gabbroic rocks in the southern Taihang Mountains.     

Type C Ca, Al-rich inclusions from Allende: Evidence for multistage formation

The coarse-grained, igneous, anorthite-rich (Type C) CAIs from Allende studied (100, 160, 6-1-72, 3529-40, CG5, ABC, TS26, and 93) have diverse textures and mineralogies, suggesting complex nebular and asteroidal formation histories. CAIs 100, 160, 6-1-72, and 3529-40 consist of Al,Ti-diopside (fassaite; 13-23 wt% Al₂O₃, 2-14 wt% TiO₂), Na-bearing åkermanitic melilite (0.1-0.4 wt% Na₂O; Åk_30-75), spinel, and fine-grained (∼5-10 μm) anorthite groundmass. Most of the fassaite and melilite grains have “lacy” textures characterized by the presence of abundant rounded and prismatic inclusions of anorthite ∼5-10 μm in size. Lacy melilite is pseudomorphed to varying degrees by grossular, monticellite, and pure forsterite or wollastonite. CAI 6-1-72 contains a relict Type B CAI-like portion composed of polycrystalline gehlenitic melilite (Åk_10-40), fassaite, spinel, perovskite, and platinum-group element nuggets; the Type B-like material is overgrown by lacy melilite and fassaite. Some melilite and fassaite grains in CAIs 100 and 160 are texturally similar to those in the Type B portion of 6-1-72. CAIs ABC and TS26 contain relict chondrule fragments composed of forsteritic olivine and low-Ca pyroxene; CAI 93 is overgrown by a coarse-grained igneous rim of pigeonite, augite, and anorthitic plagioclase. These three CAIs contain very sodium-rich åkermanitic melilite (0.4-0.6 wt% Na₂O; Åk_63-74) and Cr-bearing Al,Ti-diopside (up to 1.6 wt% Cr₂O₃, 1-23 wt% Al₂O, 0.5-7 wt% TiO₂). Melilite and anorthite in the Allende Type C CAI peripheries are replaced by nepheline and sodalite, which are crosscut by andradite-bearing veins; spinel is enriched in FeO. The CAI fragment CG5 is texturally and mineralogically distinct from other Allende Type Cs. It is anorthite-poor and very rich in spinel poikilitically enclosed by Na-free gehlenitic melilite (Åk_20-30), fassaite, and anorthite; neither melilite nor pyroxene have lacy textures; secondary minerals are absent. The Al-rich chondrules 3655b-2 and 3510-7 contain aluminum-rich and ferromagnesian portions. The Al-rich portions consist of anorthitic plagioclase, Al-rich low-Ca pyroxene, and Cr-bearing spinel; the ferromagnesium portions consist of fosteritic olivine, low-Ca pyroxene, and opaque nodules.We conclude that Type C CAIs 100, 160, 6-1-72, and 3529-40 formed by melting of coarse-grained Type B-like CAIs which experienced either extensive replacement of melilite and spinel mainly by anorthite and diopside (traces of secondary Na-bearing minerals, e.g., nepheline or sodalite, might have formed as well), or addition of silica and sodium during the melting event. CG5 could have formed by melting of fine-grained spinel-melilite CAI with melilite and spinel partially replaced anorthite and diopside. CAIs ABC, 93, and TS-26 experienced melting in the chondrule-forming regions with addition of chondrule-like material, such as forsteritic olivine, low-Ca pyroxene, and high-Ca pyroxene. Anorthite-rich chondrules formed by melting of the Al-rich (Type C CAI-like) precursors mixed with ferromagnesian, Type I chondrule-like precursors. The Allende Type C CAIs and Al-rich chondrules experienced fluid-assisted thermal metamorphism, which resulted in pseudomorphic replacement of melilite and anorthite by grossular, monticellite, and forsterite (100, 160, 6-1-72, 3592-40) or by grossular, monticellite, and wollastonite (ABC, 93, TS-26). The pseudomorphic replacement was followed or accompanied by iron-alkali metasomatic alteration resulting in replacement of melilite and anorthite by nepheline and sodalite, enrichment of spinel in FeO, and precipitation of salite-hedenbergite pyroxenes, wollastonite, and andradite in fractures and pores in and around CAIs.     

Oxygen isotopic SIMS analysis in Allende CAI: details of the very early thermal history of the solar system

The oxygen isotopic micro-distributions within and among minerals in a coarse-grained Ca, Al-rich inclusion (CAI), 7R-19-1 from the Allende meteorite, were measured by in situ using secondary ion mass spectrometry (SIMS). All values of O isotopic ratios in 7R-19-1 minerals fall along the carbonaceous chondrite anhydrous mineral mixing (CCAM) line on a δ¹⁷O_SMOW vs. δ¹⁸O_SMOW plot. Major refractory minerals (spinel, fassaite and melilite) in 7R-19-1 showed large negative anomalies of Δ¹⁷O in the order, spinel (−21‰) > ¹⁶O-rich melilite (∼−18‰) > fassaite (−15 to +1‰) > ¹⁶O-poor melilite (−8 to +2‰). However, the lower limit values of Δ¹⁷O are similar at about −21‰, a value commonly observed in CAIs. The similarity in the extreme values of the isotope anomaly anomalies suggests that crystallization of all CAIs started from an ¹⁶O enrichment of 21‰ (Δ¹⁷O) relative to terrestrial values. The order of the O isotopic anomalies observed for 7R-19-1, except for ¹⁶O-poor melilite, is parallel to the crystallization sequence determined by experiment from CAI liquid (Stolper, 1982), indicating that the O isotopic exchange in 7R-19-1 occurred between CAI melt and surrounding gas while 7R-19-1 was crystallizing from the ¹⁶O enriched CAI liquid (∼−21‰ in Δ¹⁷O) in the ¹⁶O-poor solar nebula. However, the a single crystallization sequence during the cooling stage cannot explain the existence of ¹⁶O-poor melilite. The presence of ¹⁶O-poor melilite suggests that multiple heating events occurred during CAI formation. The sharp contact between ¹⁶O-rich and ¹⁶O-poor melilite crystals and within ¹⁶O-rich melilite indicates that these multiple heatings occurred quickly. Based on the O isotopic and chemical compositions, fassaite crystals were aggregates of relic crystals formed from CAI melt whichthat have had various O isotopic compositions from the remelting processes. The results of intra-mineral distributions of O isotopes also support multiple heating events during CAI formation.     

Gypsum as a monitor of the paleo-limnological–hydrological conditions in Lake Lisan and the Dead Sea

The isotopic composition and mass balances of sources and sinks of sulfur are used to constrain the limnological–hydrological evolution of the last glacial Lake Lisan (70–14 ka BP) and the Holocene Dead Sea. Lake Lisan deposited large amounts of primary gypsum during discrete episodes of lake level decline. This gypsum, which appears in massive or laminated forms, displays δ³⁴S values in the range of 14–28‰. In addition, Lake Lisan’s deposits (the Lisan Formation) contain thinly laminated and disseminated gypsum as well as native sulfur which display significantly lower δ³⁴S values (−26 to 1‰ and −20 to −10‰, respectively). The calculated bulk isotopic compositions of sulfur in the sources and sinks of Lake Lisan lacustrine system are similar (δ³⁴S ≈ 10‰), indicating that freshwater sulfate was the main source of sulfur to the lake. The large range in δ³⁴S found within the Lisan Formation (−26 to +28‰) is the result of bacterial sulfate reduction (BSR) within the anoxic lower water body (the monimolimnion) and bottom sediments of the lake.

Precipitation of primary gypsum from the Ca-chloride solution of Lake Lisan is limited by sulfate concentration, which could not exceed 3000 mg/l. The Upper Gypsum Unit, deposited before ca. 17–15 ka, is the thickest gypsum unit in the section and displays the highest δ³⁴S values (25–28‰). Yet, our calculations indicate that no more than a third of this Unit could have precipitated directly from the water column. This implies that during the lake level decline that instigated the precipitation of the Upper Gypsum Unit, significant amounts of dissolved sulfate had to reach the lake from external sources. We propose a mechanism that operated during cycles of high-low stands of the lakes that occupied the Dead Sea basin during the late Pleistocene. During high-stand intervals (i.e., Marine Isotopic Stages 2 and 4), lake brine underwent BSR and infiltrated the lake’s margins and adjacent strata. As lake level dropped, these brines, carrying ³⁴S-enriched sulfate, were flushed back to the shrinking lake and replenished the water column with sulfate, thereby promoting massive gypsum precipitation.

The Holocene Dead Sea precipitated relatively small amounts of primary gypsum, mainly in the form of thin laminae. δ³⁴S values of these laminae and disseminated gypsum are relatively constant (15 ± 0.7‰) and are close to present-day lake composition. This reflects the lower supply of freshwater to the lake and the limited BSR activity during the arid Holocene time and possibly during former arid interglacials in the Levant.     

Geochemical and Sr–Nd–Pb isotopic compositions of the Eocene Dölek and Sariçiçek Plutons, Eastern Turkey: Implications for magma interaction in the genesis of high-K calc-alkaline granitoids in a post-collision extensional setting

The major and trace elements and Sr–Nd–Pb isotopes of the host rocks and the mafic microgranular enclaves (MME) gathered from the Dölek and Sariçiçek plutons, Eastern Turkey, were studied to understand the underlying petrogenesis and geodynamic setting. The plutons were emplaced at  43 Ma at shallow depths ( 5 to 9 km) as estimated from Al-in hornblende geobarometry. The host rocks consist of a variety of rock types ranging from diorite to granite (SiO₂ = 56.98–72.67 wt.%; Mg# = 36.8–50.0) populated by MMEs of gabbroic diorite to monzodiorite in composition (SiO₂ = 53.21–60.94 wt.%; Mg# = 44.4–53.5). All the rocks show a high-K calc-alkaline differentiation trend. Chondrite-normalized REE patterns are moderately fractionated and relatively flat [(La/Yb)_N = 5.11 to 8.51]. They display small negative Eu anomalies (Eu/Eu = 0.62 to 0.88), with enrichment of LILE and depletion of HFSE. Initial Nd–Sr isotopic compositions for the host rocks are ε_Nd(43 Ma) = − 0.6 to 0.8 and mostly I_Sr = 0.70482–0.70548. The Nd model ages (T_DM) vary from 0.84 to 0.99 Ga. The Pb isotopic ratios are (²⁰⁶Pb/²⁰⁴Pb) = 18.60–18.65, (²⁰⁷Pb/²⁰⁴Pb) = 15.61–15.66 and (²⁰⁸Pb/²⁰⁴Pb) = 38.69–38.85. Compared with the host rocks, the MMEs are relatively homogeneous in isotopic composition, with I_Sr ranging from 0.70485 to 0.70517, ε_Nd(43 Ma) − 0.1 to 0.8 and with Pb isotopic ratios of (²⁰⁶Pb/²⁰⁴Pb) = 18.58–18.64, (²⁰⁷Pb/²⁰⁴Pb) = 15.60–15.66 and (²⁰⁸Pb/²⁰⁴Pb) = 38.64–38.77. The MMEs have T_DM ranging from 0.86 to 1.36 Ga. The geochemical and isotopic similarities between the MMEs and their host rocks indicate that the enclaves are of mixed origin and are most probably formed by the interaction between the lower crust- and mantle-derived magmas. All the geochemical data, in conjunction with the geodynamic evidence, suggest that a basic magma derived from an enriched subcontinental lithospheric mantle, probably triggered by the upwelling of the asthenophere, and interacted with a crustal melt that originated from the dehydration melting of the mafic lower crust at deep crustal levels. Modeling based on the Sr–Nd isotope data indicates that  77–83% of the subcontinental lithospheric mantle involved in the genesis. Consequently, the interaction process played an important role in the genesis of the hybrid granitoid bodies, which subsequently underwent a fractional crystallization process along with minor amounts of crustal assimilation, en route to the upper crustal levels generating a wide variety of rock types ranging from diorite to granite in an extensional regime.     

Sr–Nd–Pb isotopic compositions of the Kovdor phoscorite–carbonatite complex, Kola Peninsula, NW Russia

The Sr, Nd and Pb isotopic compositions for the Kovdor phoscorite–carbonatite complex (PCC), Kola Peninsula, NW Russia, have been determined to characterize the mantle sources involved and to evaluate the relative contributions of a plume and subcontinental lithospheric mantle in the formation of the complex. The Kovdor PCC is a part of the Kovdor ultramafic–alkaline–carbonatite massif, and consists of six intrusions. The initial isotopic ratios of the analyzed samples, calculated at 380 Ma, display limited variations: ε_Nd, + 2.0 to + 4.7; ⁸⁷Sr/⁸⁶Sr, 0.70319 to 0.70361 (ε_Sr, − 12.2 to − 6.2); ²⁰⁶Pb/²⁰⁴Pb, 18.38 to 18.74; ²⁰⁷Pb/²⁰⁴Pb, 15.45 to 15.50; ²⁰⁸Pb/²⁰⁴Pb, 37.98 to 39.28. The Nd and Sr isotope data of the Kovdor PCC generally fit the patterns of the other phoscorites and carbonatites from the Kola Alkaline Province (KAP), but some data are slightly shifted from the mixing line defined as the Kola Carbonatite Line, having more radiogenic ⁸⁷Sr/⁸⁶Sr ratios. However, the less radiogenic Nd isotopic compositions and negative Δ7/4 values of Pb isotopes of the analyzed samples exclude crustal contamination, but imply the involvement of a metasomatized lithospheric mantle source. Isotopic variations indicate mixing of at least three distinct mantle components: FOZO-like primitive plume component, EMI-like enriched component and DMM-like depleted component. The isotopic nature of the EMI- and DMM-like mantle component observed in the Kovdor samples is considered to be inherited from metasomatized subcontinental lithospheric mantle. This supports the previous models invoking plume–lithosphere interaction to explain the origin of the Devonian alkaline carbonatite magmatism in the KAP.     

Lithium isotopic composition of Central American Volcanic Arc lavas: implications for modification of subarc mantle by slab-derived fluids

Li contents and isotopic compositions were determined for a suite of well-characterized basaltic lavas from the Central American Volcanic Arc (CAVA). Variable Li/Y (0.2–0.5), Li/Sc (0.1–0.4), and δ⁶Li values (+2.6 to −7.7‰) attest to significant compositional heterogeneity in the subarc mantle. Within specific arc segments, these parameters correlate strongly with each other and with a number of other constituents (e.g., K, Rb, Ba, B/La, ¹⁰Be/⁹Be, ⁸⁷Sr/⁸⁶Sr, U/Ce, and ²³⁰Th/²³²Th, among others); these correlations are particularly strong for Nicaragua samples. Coupling of this particular set of constituents is best explained in terms of addition of ‘subduction components' to the subarc mantle. Moreover, their selective enrichment with respect to relatively fluid-immobile incompatible elements signifies the dominance of fluid vs. silicate melt transport of slab components to the subarc mantle. Several interesting nuances are revealed by the Li data. First, although Li and B are strongly correlated in both Costa Rica and Nicaragua, there are systematic along-strike variations in Li/B that are consistent with these elements having different ‘fluid release patterns' from subducted slab segments. For example, Li/B is highest in Costa Rica where auxiliary evidence indicates higher subduction zone temperatures; apparently B is preferentially depleted and Li retained in the slab under warmer conditions. The same relations are reflected in Li/¹⁰Be and other subduction tracer systematics, all of which point to larger subduction contributions below Nicaragua. Yet, even Nicaragua lavas vary widely in levels of subduction enrichment. High-Ti basalts from Nejapa are the least enriched and have the highest δ⁶Li (1.4 to 2.6‰); these values are greater than in fresh MORB (ca. −4‰) and are not easily explained by additions of subducted Li because most oceanic crustal rocks and marine sediments have lower δ⁶Li than MORB (with typical values between −8 and −20‰). Thus, it appears the Nejapa data may be representative of isotopically light mantle domains. Relatively light δ⁶Li values in an undepleted spinel lherzolite (+11.3‰) from Zabargad Is. (Red Sea) and in primitive backarc basalts (−1.6 to −0.5‰) from Lau Basin support this conclusion. Considering representative fluid and mantle endmember compositions, the CAVA data are consistent with limited (up to a few percent) additions of slab-derived fluids to a heterogeneous mantle containing variably depleted and enriched domains to form the respective magma sources. In our view, the subarc mantle is heterogeneous on a small scale, but some arc sectors clearly received greater slab inputs than others.     

Provenance of the Neoproterozoic Maricá Formation (Sul-rio-grandense Shield, Southern Brazil): Petrographic and Sm–Nd isotopic constraints

This paper reports the integrated application of petrographic and Sm–Nd isotopic analyses for studying the provenance of the Neoproterozoic Maricá Formation, southern Brazil. This unit encompasses sedimentary rocks of fluvial and marine affiliations. In the lower fluvial succession, sandstones plot in the “craton interior” and “transitional continental” fields of the QFL diagram. Chemical weathering probably caused the decrease of the ¹⁴⁷Sm/¹⁴⁴Nd ratios to 0.0826 and 0.0960, consequently lowering originally > 2.0 Ga T_DM ages to 1.76 and 1.81 Ga. ¹⁴³Nd/¹⁴⁴Nd ratios are also low (0.511521 to 0.511633), corresponding to negative ε_Nd present-day values (− 21.8 and − 19.6). In the intermediate marine succession, sandstones plot in the “dissected arc” field, reflecting the input of andesitic clasts. Siltstones and shales reveal low ¹⁴³Nd/¹⁴⁴Nd ratios (0.511429 to 0.511710), ε_Nd values of − 18.1 and − 23.6, and T_DM ages of 2.16 and 2.37 Ga. Sandstones of the upper fluvial succession have “dissected arc” and “recycled orogen” provenance. ¹⁴³Nd/¹⁴⁴Nd isotopic ratios are also relatively low, from 0.511487 to 0.511560, corresponding to ε_Nd values of − 22.4 and − 21.0 and T_DM of 2.07 Ga. A uniform granite–gneissic basement block of Paleoproterozoic age, with subordinate volcanic rocks, is suggested as the main sediment source of the Maricá Formation.     

Oxygen isotope compositions of chondrules in CR chondrites

We report in situ ion microprobe analyses of oxygen isotopic compositions of olivine, low-Ca pyroxene, high-Ca pyroxene, anorthitic plagioclase, glassy mesostasis, and spinel in five aluminum-rich chondrules and nine ferromagnesian chondrules from the CR carbonaceous chondrites EET92042, GRA95229, and MAC87320. Ferromagnesian chondrules are isotopically homogeneous within ±2‰ in Δ¹⁷O; the interchondrule variations in Δ¹⁷O range from 0 to −5‰. Small oxygen isotopic heterogeneities found in two ferromagnesian chondrules are due to the presence of relict olivine grains. In contrast, two out of five aluminum-rich chondrules are isotopically heterogeneous with Δ¹⁷O values ranging from −6 to −15‰ and from −2 to −11‰, respectively. This isotopic heterogeneity is due to the presence of ¹⁶O-enriched spinel and anorthite (Δ¹⁷O = −10 to −15‰), which are relict phases of Ca,Al-rich inclusions (CAIs) incorporated into chondrule precursors and incompletely melted during chondrule formation. These observations and the high abundance of relict CAIs in the aluminum-rich chondrules suggest a close genetic relationship between these objects: aluminum-rich chondrules formed by melting of spinel-anorthite-pyroxene CAIs mixed with ferromagnesian precursors compositionally similar to magnesium-rich (Type I) chondrules. The aluminum-rich chondrules without relict CAIs have oxygen isotopic compositions (Δ¹⁷O = −2 to −8‰) similar to those of ferromagnesian chondrules. In contrast to the aluminum-rich chondrules from ordinary chondrites, those from CRs plot on a three-oxygen isotope diagram along the carbonaceous chondrite anhydrous mineral line and form a continuum with amoeboid olivine aggregates and CAIs from CRs. We conclude that oxygen isotope compositions of chondrules resulted from two processes: homogenization of isotopically heterogeneous materials during chondrule melting and oxygen isotopic exchange between chondrule melt and ¹⁶O-poor nebular gas.     

Hydrothermal gases offshore Milos Island, Greece

Hydrothermal fluids emerge from the seafloor of Paleohori Bay on Milos. The gases in these fluids contain mostly CO₂ but CH₄ concentrations up to 2% are present. The stable carbon isotopic composition of the CO₂ (near 0%) indicates an inorganic carbon source (dissociation of underlying marine carbonates). The carbon and hydrogen isotopes of most CH₄ samples are enriched in the heavy species (δ¹³C = −9.4 to −17.8‰; δD = −102 to −189‰) which is believed to be characteristic for an abiogenic production of CH₄ by CO₂-reduction (Fischer-Tropsch reactions). Depletions in the deuterium content of three CH₄ samples (to −377%) are probably caused by unknown subsurface rock alteration processes. Secondary hydrogen isotope exchange processes between methane, hydrogen and water are most likely responsible for calculated unrealistic methane formation temperatures.

We show that excess helium, slightly enriched in ³He, is present in the hydrothermal fluids emerging the seafloor of Paleohori Bay. When the isotopic ratio of the excess component is calculated a ³He/⁴He_excess of 3.6 · 10⁻⁶ is obtained: This indicates that the excess component consists of about one third of mantle helium and two thirds of radiogenic helium. We infer that the mantle-derived component has been strongly diluted by radiogenic helium during the ascent of the fluids to the surface.     

New insights into the occurrence of C-depleted carbon in the mantle from two closely associated kimberlites: Letlhakane and Orapa, Botswana

Carbon isotope measurements on diamonds from the Letlhakane kimberlite, and the analyses of their inclusions, permit the examination of km-scale mantle-composition variations by comparing the results with those for the nearby Orapa kimberlite. Diamonds from Letlhakane have a wide range in carbon isotopic composition (−3‰ to −21‰); however, the relative abundance of diamonds depleted in ¹³C is significantly lower than in the Orapa kimberlite. Most of the ¹³C-depleted diamonds belong to the eclogictic or websteritic paragenesis. The relative abundance of inclusions in diamonds and their composition indicate that there are significant differences in petrology in the mantle below the two locations. At Letlhakane, peridotitic compositions are more prevalent than at Orapa and the protolith of P-Type inclusions in diamonds may have experienced a higher degree of partial melting at Letlhakane compared to Orapa. P/T estimates for both W- and E-Type diamonds indicate that a region of ¹³C-depletion may exist beneath the two kimberlites. The relationships between carbon isotopic composition of the host diamond and the Al₂O₃/Cr₂O₃ ratios of their websteritic and eclogitic garnet inclusions indicate that the low δ¹³C regions may represent a primary mantle feature, unrelated to a crustal component.     

Neo-Proterozoic rift-related syenites (Northern Damara Belt, Namibia): Geochemical and Nd–Sr–Pb–O isotope constraints for mantle sources and petrogenesis

Major element, trace element and Nd–Sr–Pb–O isotope data for a suite of Neo-Proterozic, pre-orogenic, rift-related syenites from the Northern Damara orogen (Namibia) constrain their sources and petrogenesis. New U–Pb ages obtained on euhdreal titanite of inferred magmatic origin constrain the age of intrusion of the Lofdal and Oas syenites to ca. 750 Ma compatible with previous high-precision zircon analyses from the Oas complex. Major rock types from Lofdal and Oas are mildly sodic nepheline-normative and quartz-normative syenites and were primarily generated by fractional crystallization from a mantle-derived alkaline magma. Primitive samples from Lofdal and Oas show depletion of Rb, K and Th relative to Ba and Nb together with variable negative anomalies of P and Ti on a primitive mantle-normalized diagram. Evolved samples from Oas develop significant negative Ba, Sr, P and Ti anomalies and positive U and Th anomalies mainly as a function of crystal fractionation processes. The lack of a pronounced negative Nb anomaly in samples from Lofdal suggests that involvement of a crustal component is negligible. For the nepheline-normative samples from Lofdal, the unradiogenic Sr and radiogenic Nd isotope composition and low δ¹⁸O values suggest derivation of these samples from a moderately depleted lithospheric upper mantle with crustal-like U/Pb ratios (⁸⁷Sr/⁸⁶Sr: 0.7031–0.7035, ε Nd: ca. + 1, δ¹⁸O: 7‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.58–15.60). Primitive samples of the Oas quartz-normative syenites have identical isotope characteristics (⁸⁷Sr/⁸⁶Sr: 0.7034, ε Nd: ca. + 1, δ¹⁸O: 6.5‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.59) whereas more differentiated samples have higher ⁸⁷Sr/⁸⁶Sr ratios (0.709–0.714), slightly higher δ¹⁸O values (7.0–7.1‰), less radiogenic ε Nd values (− 1.1 to − 1.4) and more radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios up to 18.27. These features together with model calculations using Sr–Nd–Pb isotopes suggest modification of a primary syenite magma by combined AFC processes involving ancient continental crust. In this case, high Nb abundances of the parental syenite liquid prevent the development of significant negative Nb anomalies that may be expected due to interaction with continental crust.     

The isotopic composition of zircon and garnet: A record of the metamorphic history of Naxos, Greece

Growth of zircon with respect to that of garnet has been studied using a combination of petrography, U–Pb dating and oxygen isotope analysis. The aim is to document the mechanism and pressure–temperature conditions of zircon growth during metamorphism in order to better constrain the Tertiary metamorphic history of Naxos, Greece. Two metamorphisms are recognised: (1) an Eocene Franciscan metamorphism (M1) and (2) a widespread Miocene Barrovian metamorphism (M2) that increases from greenschist facies up to partial melting. An amphibolite sample contains zircon crystals characterised by a magmatic core and two metamorphic rims, denoted as A and B, dated at 200–270, 42–69, and 14–19 Ma, respectively. The first metamorphic rim A (δ¹⁸O = 7 ± 1‰) preserves the δ¹⁸O value of the magmatic core (6.2 ± 0.8‰), whereas rim B is characterised by higher δ¹⁸O values (7.8 ± 1.8‰). These observations indicate the formation of A rims by solid-state recrystallisation in a closed system with regard to oxygen and those of B in an open system. Compositional zoning in garnet is interpreted as the result of decompressional heating. Zircon B rims and garnet rims display similar δ¹⁸O values which indicates a contemporaneous growth of garnet and zircon rims during the Miocene Barrovian event (M2). Calcic gneiss and metapelite samples contain zircon crystals with single metamorphic overgrowths aged 41–57 Ma. δ¹⁸O values measured in zircon overgrowths (11.8 ± 1.4‰) from the calcic gneiss are similar to those measured in garnet rims (11.4 ± 1.1‰) from the same rock. This suggests that garnet rims and zircon overgrowths grew during the high pressure–low temperature event in equilibrium with prograde fluids. In the metapelite sample, δ¹⁸O values are similar in garnet cores (14.8 ± 0.2‰) and in zircon metamorphic overgrowths (14.2 ± 0.5‰). As zircon overgrowths have been dated at ca. 50 Ma by U–Pb, garnet cores and zircon overgrowths are interpreted to have grown during the high pressure event.

As demonstrated here for the island of Naxos, correlating the crystallisation of zircon with that of metamorphic index minerals such as garnet using stable isotope composition and U–Pb determination is a powerful tool for deciphering the mechanism of zircon growth and pin-pointing zircon crystallisation within the metamorphic history of a terrain. This approach is potentially hampered by an inability to verify the degree of textural equilibrium of zircon with other mineral phases, and the possible preservation (in metamorphic rims) of isotopic signatures from pre-existing zircon when they form by recrystallisation. Nevertheless, this study illustrates the application of this approach in providing key constraints on the timing and mechanism of growth of minerals important to understanding metamorphic petrogenesis.     

Oxygen and carbon isotope composition of cold-water Berriedale Limestone (Lower Permian), Tasmania, Australia

The Berriedale Limestone formed at about 80°S paleolatitude and contains many glacial dropstones. It formed during a period of major Gondwana deglaciation.

The Berriedale Limestone contains mostly bryozoans, brachiopods and bivalves, with some intraclasts and rare pellets. The faunal diversity is low and the fauna are similar to the modern cold-water foramol faunal assemblage. Micrite, microspar and spar occur as equant to well developed rhombs of calcite. The coarse spar cements are bored and are ruptured by dropstones, indicating submarine origin of low-Mg calcite at water-temperatures of around 3°C. The mixing zone cementation was preceded by erosion of early formed crystals. The eroded crystals occur as inclusions in mixing zone cements.

The fauna are characterized by heavy δ¹³C and light δ¹⁸O. The whole-rock field of δ¹⁸O-δ¹³C falls at the edge of “Normal Marine Limestone” and deviates to lighter δ¹⁸O values (down to −16.7‰ PDB). Lightest δ¹⁸O values ( −22‰ PDB) of fresh-water sparry calcite cement are similar to those in the Early Permian continental tillites, suggesting that the Permian sea was diluted by isotopically light melt waters. Micrite δ¹⁸O values (−9.2 to −12.6‰ PDB) are within the range of whole-rock values. The δ¹⁸O values of calcite in shales are lighter than limestone values.

The δ¹⁸O values of the fauna give an unrealistic range of sea-water temperatures because the fauna have equilibrated with variable amounts of melt waters. However, calculated original δ¹⁸O values of the fauna indicate temperatures < 4°C. The heaviest δ¹⁸O of fauna gives cold temperatures of 9°C (with δ_w −2.8‰) and −3°C (with δ_w −6‰). The lightest values of sparry calcite cements (−22‰ PDB) indicate that the limestone reacted with cold melt waters.

The δ¹⁸O of Permian sea is estimated to be about +1.2‰ and was diluted by melt waters as light as −27‰ SMOW.